U.S. patent application number 09/776657 was filed with the patent office on 2001-10-18 for organometallic monoacylarylphosphines.
Invention is credited to Aebli, Beat Michael, Hug, Gebhard, Wolf, Jean-Pierre.
Application Number | 20010031898 09/776657 |
Document ID | / |
Family ID | 4471003 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031898 |
Kind Code |
A1 |
Wolf, Jean-Pierre ; et
al. |
October 18, 2001 |
Organometallic monoacylarylphosphines
Abstract
1 R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen; R.sub.3,
R.sub.4 and R.sub.5 independently of one another are hydrogen,
C-C.sub.20alkyl, OR.sub.11 or halogen; R.sub.6, R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 independently of one another are hydrogen,
C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.20alkyl which is interrupted
once or more than once by nonconsecutive O atoms and which is
unsubstituted or substituted by OH and/or SH; or R.sub.6, R.sub.7,
R.sub.8, R.sub.9 and R.sub.10 are OR.sub.11, SR.sub.11,
N(R.sub.12)(R.sub.13), phenyl or halogen; R.sub.11 is
C.sub.1-C.sub.20alkyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl or
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH and/or
SH; R.sub.12 and R.sub.13 independently of one another are
hydrogen, C.sub.1-C.sub.20alkyl, C.sub.3-C.sub.8cycloalkyl, phenyl,
benzyl or C.sub.2-C.sub.20alkyl which is interrupted once or more
than once by nonconsecutive O atoms and which is unsubstituted or
substituted by OH and/or SH; or R.sub.12 and R.sub.13 together are
C.sub.3-C.sub.5alkylene which can be interrupted by O, S or
NR.sub.14; R.sub.14 is hydrogen, phenyl, C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH and/or
SH; and M is hydrogen, Li, Na or K; are valuable intermediates for
the preparation of unsymmetrical bisacylphosphine oxides and
monoacylphosphine oxides.
Inventors: |
Wolf, Jean-Pierre;
(Maisprach, CH) ; Aebli, Beat Michael; (Basel,
CH) ; Hug, Gebhard; (Rheinfelden, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
4471003 |
Appl. No.: |
09/776657 |
Filed: |
February 5, 2001 |
Current U.S.
Class: |
568/13 ; 546/22;
548/413 |
Current CPC
Class: |
C07F 9/5036 20130101;
C09D 11/101 20130101; C07F 9/6521 20130101; C07F 9/5337 20130101;
B33Y 70/00 20141201; Y10S 430/124 20130101; A61K 6/62 20200101;
G03F 7/029 20130101; G03F 7/0384 20130101; C07F 9/28 20130101; G03F
7/0045 20130101; C08F 2/50 20130101; G03F 7/0388 20130101; G03F
7/0755 20130101; C09D 4/00 20130101; A61K 6/884 20200101; A61K
6/887 20200101; C08L 33/08 20130101; A61K 6/887 20200101; C08L
33/10 20130101; A61K 6/887 20200101; C08L 33/20 20130101; A61K
6/887 20200101; C08L 33/26 20130101; A61K 6/887 20200101; C08L
27/00 20130101; A61K 6/887 20200101; C08L 31/04 20130101; A61K
6/887 20200101; C08L 25/06 20130101; A61K 6/887 20200101; C08L
27/04 20130101; A61K 6/887 20200101; C08L 39/06 20130101; A61K
6/893 20200101; C08L 75/04 20130101; A61K 6/891 20200101; C08L
67/00 20130101; A61K 6/891 20200101; C08L 71/02 20130101; A61K
6/898 20200101; C08L 1/08 20130101; A61K 6/898 20200101; C08L 1/08
20130101; A61K 6/893 20200101; C08L 75/04 20130101; A61K 6/891
20200101; C08L 67/00 20130101; A61K 6/891 20200101; C08L 71/02
20130101; A61K 6/887 20200101; C08L 33/08 20130101; A61K 6/887
20200101; C08L 33/10 20130101; A61K 6/887 20200101; C08L 33/20
20130101; A61K 6/887 20200101; C08L 33/26 20130101; A61K 6/887
20200101; C08L 27/00 20130101; A61K 6/887 20200101; C08L 31/04
20130101; A61K 6/887 20200101; C08L 25/06 20130101; A61K 6/887
20200101; C08L 27/04 20130101; A61K 6/887 20200101; C08L 39/06
20130101 |
Class at
Publication: |
568/13 ; 548/413;
546/22 |
International
Class: |
C07F 009/576; C07F
009/28; C07F 009/572 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 8, 2000 |
CH |
255/00 |
Claims
What is claimed is:
1. A compound of the formula I 173in which Ar is a group 174or Ar
is cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthracyl or an
O-, S- or N-containing 5- or 6-membered heterocyclic ring, where
the radicals cyclopentyl, cyclohexyl, naphthyl, biphenylyl,
anthracyl or O-, S- or N-containing 5- or 6-membered heterocyclic
ring are unsubstituted or substituted by halogen, Cl-C.sub.4alkyl
and/or C.sub.1-C.sub.4alkoxy; R.sub.1 and R.sub.2 independently of
one another are C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or
halogen; R.sub.3, R.sub.4 and R.sub.5 independently of one another
are hydrogen, C.sub.1-C.sub.20alkyl, OR.sub.11 or halogen; or in
each case two of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4
and/or R.sub.5 together form C.sub.1-C.sub.20alkylene, which can be
interrupted by O, S or NR.sub.14; R.sub.6, R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 independently of one another are hydrogen,
C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.20alkyl which is interrupted
once or more than once by nonconsecutive O atoms and which can be
substituted by OH and/or SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9
and R.sub.10 are OR.sub.11, phenyl or halogen; R.sub.11 is
hydrogen, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.3-C.sub.8cycloalkyl- , phenyl, benzyl or
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or is substituted by OH and/or
SH; R.sub.14 is hydrogen, phenyl, C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by O or S and which can be substituted by OH and/or SH; and M is
hydrogen, Li, Na or K.
2. A compound of the formula II 175in which A is O or S; x is 0 or
1; Ar is a group 176or Ar is cyclopentyl, cyclohexyl, naphthyl,
biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, where the radicals cyclopentyl, cyclohexyl,
naphthyl, biphenylyl, anthracyl or O-, S- or N-containing 5- or
6-membered heterocyclic ring are unsubstituted or substituted by
halogen, Cl-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; R.sub.1 and
R.sub.2 independently of one another are C.sub.1-C.sub.20alkyl,
OR.sub.11, CF.sub.3 or halogen; R.sub.3, R.sub.4 and R.sub.5
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl,
OR.sub.11 or halogen; or in each case two of the radicals R.sub.1,
R.sub.2, R.sub.3, R.sub.4 and/or R.sub.5 together form
C.sub.1-C.sub.20alkylene which can be interrupted by O, S or
NR.sub.14; R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl;
C.sub.2-C.sub.20alkyl, which is interrupted once or more than once
by nonconsecutive O atoms and which can be substituted by OH and/or
SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
OR.sub.11, phenyl or halogen; R.sub.11 is hydrogen,
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.3-C.sub.8cycloalkyl- , phenyl, benzyl or
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which is unsubstituted or substituted
by OH and/or SH; Y.sub.1 is C.sub.1-C.sub.18alkyl which is
unsubstituted or substituted by one or more phenyl;
C.sub.1-C.sub.18-halogenoalkyl; C.sub.2-C.sub.18alkyl which is
interrupted once or more than once by O or S and which is
unsubstituted or substituted by OH and/or SH; unsubstituted
C.sub.3-C.sub.18cycloalkyl or C.sub.3-C.sub.18cycloalkyl
substituted by C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or
halogen; C.sub.2-C.sub.18alkenyl; naphthyl, biphenylyl, anthracyl
or an O-, S or N-containing 5- or 6-membered heterocyclic ring,
where the radicals naphthyl, biphenylyl, anthracyl or O-, S- or
N-containing 5- or 6-membered heterocyclic ring are unsubstituted
or are substituted by halogen, C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or Y.sub.1 is OR.sub.11, N(R16)(R.sub.17),
177Y.sub.2 is a direct bond, C.sub.1-C.sub.18alkylene optionally
substituted by phenyl; unsubstituted C.sub.4-C.sub.18-cycloalkylene
or C.sub.4-C.sub.18cycloalkylene substituted by
C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or phenyl;
unsubstituted C.sub.5-C.sub.18cycloalke- nylene or
C.sub.5-C.sub.18cycloalkenylene substituted by
C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or phenyl;
unsubstituted phenylene or phenylene substituted one to four times
by C.sub.1-C.sub.12alkyl, OR.sub.11, halogen, -(CO)OR.sub.14,
--(CO)N(R.sub.12)(R.sub.13) and/or phenyl; or Y.sub.2 is a radical
178where these radicals are unsubstituted or are substituted one to
four times on one or both aromatic ring(s) by
C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or phenyl; Y.sub.3 is
O, S, SO, SO.sub.2, CH.sub.2, C(CH.sub.3).sub.2, CHCH.sub.3,
C(CF.sub.3).sub.2, (CO), or a direct bond; R.sub.12 and R.sub.13
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl or C.sub.2-C.sub.20alkyl
which is interrupted once or more than once by O or S and which is
unsubstituted or substituted by OH and/or SH; or R.sub.12 and
R.sub.13 together are C.sub.3-C.sub.5alkylene which can be
interrupted by O, S or NR.sub.14; R.sub.14 is hydrogen, phenyl,
C.sub.1-C.sub.12alkyl or C.sub.2-C.sub.12alkyl which is interrupted
once or more than once by O or S and which is unsubstituted or
substituted by OH and/or SH; R.sub.1' and R.sub.2' independently of
one another have the same meanings as given for R.sub.1 and
R.sub.2; and R.sub.3', R.sub.4' and R.sub.5' independently of one
another have the same meanings as given for R.sub.3, R.sub.4 and
R.sub.5; with the proviso that if Y.sub.1 is a radical 179naphthyl,
biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, this is not identical to the other benzoyl group
on the phosphorus atom.
3. A compound of the formula III 180in which A is O or S; x is 0 or
1; Ar is a group 181or Ar is cyclopentyl, cyclohexyl, naphthyl,
biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, where the radicals cyclopentyl, cyclohexyl,
naphthyl, biphenylyl, anthracyl or O-, S- or N-containing 5- or
6-membered heterocyclic ring are unsubstituted or are substituted
by halogen, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen; R.sub.3,
R.sub.4 and R.sub.5 independently of one another are hydrogen,
C.sub.1-C.sub.20alkyl, OR.sub.11 or halogen or in each case two of
the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4 and/or R.sub.5
together form a C.sub.1-C.sub.20alkylene which can be interrupted
by O, S or NR.sub.14; R.sub.6, R.sub.7, R.sub.8, R.sub.9 and
R.sub.10 independently of one another are hydrogen,
C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.20alkyl which is interrupted
once or more than once by nonconsecutive O atoms and which is
unsubstituted or substituted by OH and/or SH; or R.sub.6, R.sub.7,
R.sub.8, R.sub.9 and R.sub.10 are OR.sub.11; halogen or
unsubstituted phenyl or phenyl substituted once or more than once
by C.sub.1-C.sub.4alkyl; R.sub.11 is hydrogen,
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl or C.sub.2-C.sub.20alkyl
which is interrupted once or more than once by nonconsecutive O
atoms and which is unsubstituted or substituted by OH and/or SH;
Z.sub.1 is C.sub.1-C.sub.24alkyl which is unsubstituted or
substituted once or more than once by OR.sub.15, SR.sub.15,
N(R.sub.16)(R.sub.17), phenyl, halogen, CN, NCO, 182and/or 183or
Z.sub.1 is C.sub.2-C.sub.24alkyl which is interrupted once or more
than once by O, S or NR.sub.14 and which is unsubstituted or
substituted by OR.sub.15, SR.sub.15, N(R.sub.16)(R.sub.17), phenyl,
halogen, 184and/or 185or Z.sub.1 is C.sub.1-C.sub.24alkoxy, which
is substituted once or more than once by phenyl, CN, NCO, 186and/or
187or Z.sub.1 is 188or Z.sub.1 is unsubstituted
C.sub.3-C.sub.24-cycloalkyl or C.sub.3-C.sub.24cycloalkyl
substituted by C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or
halogen; unsubstituted C.sub.2-C.sub.24alkenyl or
C.sub.2-C.sub.24-alkenyl substituted by C.sub.6-C.sub.12aryl, CN,
(CO)OR.sub.15 or (CO)N(R.sub.18).sub.2; or Z.sub.1 is
C.sub.3-C.sub.24cycloalkenyl or is one of the radicals 189or
Z.sub.1 is C.sub.1-C.sub.24alkylthio, in which the alkyl radical is
uninterrupted or is interrupted once or more than once by
nonconsecutive O or S, and is unsubstituted or substituted by
OR.sub.15, SR.sub.15 and/or halogen; A.sub.1 is O, S or NR.sub.18a;
Z.sub.2 is C.sub.1-C.sub.24alkylene; C.sub.2-C.sub.24alkylene
interrupted once or more than once by O, S, or NR.sub.14;
C.sub.2-C.sub.24alkenylene; C.sub.2-C.sub.24alkenylene interrupted
once or more than once by O, S, or NR.sub.14;
C.sub.3-C.sub.24cycloalkylene; C.sub.3-C.sub.24cycloalkylene
interrupted once or more than once by O, S, or NR.sub.14;
C.sub.3-C.sub.24cycloalkyle- ne; C.sub.3-C.sub.24cycloalkenylene
interrupted once or more than once by O, S, or NR.sub.14; where the
radicals C.sub.1 -C.sub.24alkylene, C.sub.2-C.sub.24alkylene,
C.sub.2-C.sub.24alkenylene, C.sub.3-C.sub.24cycloalkylene and
C.sub.3-C.sub.24cycloalkenylene are unsubstituted or are
substituted by OR.sub.11, SR.sub.11, N(R.sub.12)(R.sub.13) and/or
halogen; or Z.sub.2 is one of the radicals 190where these radicals
are unsubstituted or are substituted on the aromatic by
C.sub.1-C.sub.20alkyl which is interrupted once or more than once
by non-consecutive O atoms and which is unsubstituted or
substituted by OH and/or SH; OR.sub.11, SR.sub.11,
N(R.sub.12)(R.sub.13), phenyl, halogen, NO.sub.2, CN,
(CO)--OR.sub.18, (CO)--R.sub.19, (CO)--N(R.sub.18).sub.2,
SO.sub.2R.sub.24, OSO.sub.2R.sub.24, CF.sub.3 and/or CCl.sub.3; or
Z.sub.2 is a group 191Z.sub.3 is CH.sub.2, CHCH.sub.3 or
C(CH.sub.3).sub.2; Z.sub.4 is S, O, CH.sub.2, C.dbd.O, NR.sub.14 or
a direct bond; Z.sub.5 is S, O, CH.sub.2, CHCH.sub.3,
C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, CO, SO, SO.sub.2; Z.sub.6 and
Z.sub.7 independently of one another are CH.sub.2, CHCH.sub.3 or
C(CH.sub.3).sub.2; r is 0, 1 or 2; s is a number from 1 to 12; q is
a number from 0 to 50; t and p are each a number from 0 to 20; E,
G, G.sub.3 and G.sub.4 independently of one another are
unsubstituted C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkyl
substituted by halogen, or are unsubstituted phenyl or phenyl
substituted by one or more C.sub.1-C.sub.4alkyl; R.sub.11a is
C.sub.1-C.sub.20alkyl substituted once or more than once by
OR.sub.1,.sub.5, halogen or 192or is C.sub.2-C.sub.20alkyl
interrupted once or more than once by nonconsecutive O atoms and
which optionally is substituted once or more than once by
OR.sub.15, halogen or 193or is C.sub.2-C.sub.20alkenyl or
C.sub.3-C.sub.12alkynyl; or is C.sub.3-C.sub.12cycloalkyl
substituted once or more than once by C.sub.1-C.sub.6alkyl or
halogen; or is C.sub.6-C.sub.12aryl optionally substituted once or
more than once by halogen, NO.sub.2, C.sub.1-C.sub.6alkyl,
OR.sub.11 or C(O)OR.sub.18; or is C.sub.7-C.sub.16arylalkyl or
C.sub.8-C.sub.16arylcycloalkyl; R.sub.14 is hydrogen, phenyl,
C.sub.1-C.sub.12alkoxy, C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH and/or
SH; R.sub.15 has one of the meanings given for R.sub.11 or is a
radical 194R.sub.16 and R.sub.17 independently of one another have
one of the meanings given for R.sub.12 or are a radical 195R.sub.18
is hydrogen, C.sub.1-C.sub.24alkyl, C.sub.2-C.sub.12alkenyl,
C.sub.3-C.sub.8cycloalkyl- , phenyl, benzyl; C.sub.2-C.sub.20alkyl
which is interrupted once or more than once by O or S and which is
unsubstituted or substituted by OH; R.sub.18a and R.sub.18b
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl
which is substituted once or more than once by OR.sub.15, halogen,
styryl, methylstyryl, --N.dbd.C.dbd.A or 196or are
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which optionally is substituted once
or more than once by OR.sub.15, halogen, styryl, methylstyryl or
197or are C.sub.2-C.sub.12alkenyl; or are
C.sub.5-C.sub.12cycloalkyl substituted by --N.dbd.C.dbd.A or
--CH.sub.2--N.dbd.C.dbd.A and optionally additionally once or more
than once substituted by C.sub.1-C.sub.4alkyl; or are
C.sub.6-C.sub.12aryl optionally once or more than once substituted
by halogen, NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.4alkenyl,
OR.sub.11--N.dbd.C.dbd.A, --CH.sub.2--N.dbd.C.dbd.A or
C(O)OR.sub.18; or are C.sub.7-C.sub.16arylalkyl; or both groups
R.sub.18a and R.sub.18b together are
C.sub.8-C.sub.16arylcycloalkyl; or R.sub.18a and R.sub.18b
independently of one another are 198Y.sub.3 is O, S, SO, SO.sub.2,
CH.sub.2, C(CH.sub.3).sub.2, CHCH.sub.3, C(CF.sub.3).sub.2, (CO),
or a direct bond; R.sub.19, R.sub.20, R.sub.21, R.sub.22 and
R.sub.23 have one of the meanings given for R.sub.6 or are
NO.sub.2, CN, SO.sub.2R.sub.24, OSO.sub.2R.sub.24, CF.sub.3,
CCl.sub.3 or halogen; R.sub.24 is C.sub.1-C.sub.12alkyl,
halogen-substituted C.sub.1-C.sub.12alkyl, phenyl, or phenyl
substituted by OR.sub.15 and/or SR.sub.15; with the proviso that if
Z.sub.1 is a radical 199this is not identical to the other aromatic
radical 200on the phosphorus atom.
4. A compound of the formula I, II or III, 201in which Ar is a
group 202R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or halogen; R.sub.3,
R.sub.4 and R.sub.5 independently of one another are hydrogen or
C.sub.1-C.sub.4alkyl; R.sub.6, R.sub.7, R.sub.8, R.sub.9 and
R.sub.10 are hydrogen, C.sub.1-C.sub.4alkyl, OR.sub.11 or phenyl;
R.sub.11 is C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.8alkenyl or benzyl;
M is hydrogen or Li; A is O or S; x is 1; Y.sub.1 is
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by one
or more phenyl; or Y.sub.1 is naphthyl, anthracyl, OR.sub.11,
N(R.sub.16)(R.sub.17), OR.sub.11a, N(R.sub.18a)(R.sub.18b),
203Y.sub.2 is unsubstituted phenylene or phenylene substituted one
to four times by C.sub.1-C.sub.4alkyl; R.sub.1' and R.sub.2'
independently of one another have the same meanings as given for
R.sub.1 and R.sub.2; and R.sub.3', R.sub.4' and R.sub.5'
independently of one another have the same meanings as given for
R.sub.3, R.sub.4 and R.sub.5; with the proviso that if Y.sub.1 is a
radical 204naphthyl or anthracyl, this is not identical to the
other benzoyl group on the phosphorus atom; Z.sub.1 is
C.sub.1-C.sub.12alkyl; C.sub.1-C.sub.4alkyl which is substituted by
phenyl, halogen or 205or Z.sub.1 is unsubstituted
C.sub.2-C.sub.8alkenyl or C.sub.2-C.sub.8alkenyl substituted by
C.sub.6-C.sub.12aryl, CN, (CO)OR.sub.15 or (CO)N(R.sub.18).sub.2 or
is 206with the proviso that if Z.sub.1 is a radical 207this is not
identical to the other aromatic radical 208on the phosphorus atom;
Z.sub.3 is CH.sub.2; Z.sub.4 is S; r is 0; s is a number from 1 to
4; q is a number from 0 to 4; E, G, G.sub.3 and G.sub.4
independently of one another are unsubstituted C.sub.1-C.sub.4alkyl
or are C.sub.1-C.sub.4alkyl substituted by chlorine; R.sub.11a is
C.sub.1-C.sub.8alkyl, substituted by OR.sub.15, halogen or 209or is
C.sub.2-C.sub.6alkenyl, C.sub.3-C.sub.6cycloalkyl or
C.sub.7-C.sub.12arylalkyl; or is C.sub.6-C.sub.10aryl optionally
once or more than once substituted by C.sub.1-C.sub.4alkyl;
R.sub.15 is C.sub.1-C.sub.8alkyl or (CO)R.sub.18; R.sub.16 and
R.sub.17 independently of one another are hydrogen,
C.sub.1-C.sub.8alkyl; C.sub.2-C.sub.6alkenyl,
C.sub.3-C.sub.6cycloalkyl, phenyl or benzyl; or R.sub.16 and
R.sub.17 together are C.sub.3-C.sub.5alkylene optionally
interrupted by O, S or NR.sub.18; R.sub.18 is C.sub.1-C.sub.8alkyl
or C.sub.1-C.sub.8alkenyl; R.sub.18a and R.sub.18b independently of
one another are C.sub.1-C.sub.8alkyl, substituted by OR.sub.15,
halogen, --N.dbd.C.dbd.A or 210or are C.sub.2-C.sub.8alkenyl; or
are C.sub.5-C.sub.12cycloalkyl substituted by --N.dbd.C.dbd.A or
--CH.sub.2--N.dbd.C.dbd.A and optionally additionally once or more
than once substituted by methyl; or are C.sub.6-C.sub.10aryl
optionally substituted by C.sub.1-C.sub.4alkyl and/or
--N.dbd.C.dbd.A; or are C.sub.7-C.sub.12arylalkyl; R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are hydrogen, CF.sub.3,
CCl.sub.3 or halogen.
5. A process for the selective preparation of compounds of the
formula I according to claim 1, by (1) reaction of an acyl halide
of the formula IV 211in which Ar is as defined in claim 1, and X is
Cl or Br; with a dimetalated arylphosphine of the formula V 212in
which R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10, are as
defined in claim 1; and M.sub.1 is Na, Li or K; in the molar ratio
1:1; and (2) where appropriate, subsequent hydrolysis if compounds
of the formula I in which M is hydrogen are to be obtained.
6. A process for the preparation of compounds of the formula II
according to claim 2 by (1) reaction of an acyl halide of the
formula IV 213in which, Ar is as defined in claim 2, and X is Cl or
Br; with a dimetalated arylphosphine of the formula V 214in which
R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as defined in
claim 2; and M.sub.1 is Na, Li or K; in the molar ratio of
approximately 1:1; (2) subsequent reaction of the product with an
acyl halide of the formula IVa 215in which Y.sub.1 is as defined in
claim 2; and X is as defined above; with the proviso that the acyl
halide of the formula IV is not identical to the acyl halide of the
formula IVa; in the molar ratio of approximately 1:1; and (3) if
compounds of the formula II in which A is oxygen or sulfur are to
be obtained, subsequent oxidation or thionation of the resulting
phosphine compounds.
7. A process for the preparation of compounds of the formula II in
which A is oxygen and X is 1, by (1) reaction of a compound of the
formula (1) according to claim 1 216in which Ar, M, R.sub.6,
R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as defined in claim 1,
with phosgene to give the corresponding phosphine chloride (Ii)
217(2) subsequent reaction with an alcohol to give the compound of
the formula (Iii) 218in which R is the radical of an alcohol; and
(3) reaction of the resulting compound of the formula (Iii) with an
acyl halide 219in which Y.sub.1 is as defined in claim 2, but is
not identical to Ar from the formula (I) and X is Cl or Br, to give
the compound of the formula II.
8. A process for the preparation of compounds of the formula III
(1) by reaction of an acyl halide of the formula IV 220in which Ar
is as defined in claim 3, and X is Cl or Br; with a dimetalated
arylphosphine of the formula V 221in which R.sub.6, R.sub.7,
R.sub.8, R.sub.9 and R.sub.10 are as defined in claim 1; and
M.sub.1 is Na, Li or K; in the molar ratio of approximately 1:1;
(2) subsequent reaction of the product with a compound of the
formula VI Z.sub.1--X (VI), in which Z.sub.1 is as defined in claim
3, with the exception of the groups (v), (w) and
C.sub.1-C.sub.24alkylthio; and X is as defined above; with the
proviso that, if Z.sub.1 is a radical 222this radical is not
identical to the radical 223of the formula V; in the molar ratio of
approximately 1:1; and, (3) if compounds of the formula III in
which A is oxygen or sulfur are to be obtained, subsequent
oxidation or thionation of the resulting phosphine compounds.
9. A process for the preparation of compounds of the formula III,
according to claim 3, in which Z.sub.1 is C.sub.1-C.sub.24alkyl,
(1) by reaction of an acyl halide of the formula IV 224in which Ar
is as defined in claim 3, and X is Cl or Br; with an unsymmetrical
phosphine of the formula VII 225in which R.sub.6, R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 are as defined in claim 1, and Z.sub.1' is
C.sub.1-C.sub.24alkyl; in the molar ratio of approximately 1:1, in
the presence of a base, to give the corresponding acylphosphine;
and (2) subsequent oxidation or thionation of the thus obtained
acylphosphine.
10. A process for the preparation of compounds of the formula III
in which A is oxygen and x is 1, by (1) reaction of the compound of
the formula (I) according to claim 1 226in which Ar, M, R.sub.6,
R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as defined in claim 3,
with phosgene to give the corresponding phosphine chloride (Ii)
227(2) subsequent reaction with an alcohol to give the compound of
the formula (Iii) 228in which R is the radical of an alcohol; and
(3) reaction of the resulting compound of the formula (Iii) with an
organohalide Z.sub.1--X, in which Z.sub.1 is as defined in claim 3,
but is not identical to Ar from the formula (I), and X is Cl or Br,
to give the compound of the formula III.
11. A photocurable composition comprising (a) at least one
ethylenically unsaturated photopolymerizable compound and (b) at
least one compound of the formula II or III as photoinitiator.
12. A photocurable composition according to claim 11, comprising,
in addition to components (a) and (b), further photoinitiators (c)
and/or further additives (d).
13. A photocurable composition as claimed in claim 12, comprising,
as further photoinitiator (c), at least one compound of the formula
VIII, IX, X, XI 229in which R.sub.25 is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
--OCH.sub.2CH.sub.2--OR.sub.29, morpholino, SCH.sub.3, a group
230or a group 231n has a value from 2 to 10; G.sub.1 and G.sub.2
independently of one another are end-groups of the polymeric unit,
in particular hydrogen or CH.sub.3; R.sub.26 is hydroxyl,
C.sub.1-Cl6alkoxy, morpholino, dimethylamino or
--O(CH.sub.2CH.sub.2O).su- b.m--C.sub.1-C.sub.16alkyl; R.sub.27 and
R.sub.28 independently of one another are hydrogen,
C.sub.1-C.sub.6alkyl, phenyl, benzyl, C.sub.1-C.sub.16alkoxy or
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16a- lkyl, or R.sub.27
and R.sub.28 together with the carbon atom to which they are bonded
form a cyclohexyl ring; m is a number from 1-20; where R.sub.26,
R.sub.27 and R.sub.28 are not all C.sub.1-C.sub.16alkoxy or
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16alkyl at the same
time, and R.sub.29 is hydrogen, 232R.sub.30 and R.sub.32
independently of one another are hydrogen or methyl; R.sub.31 is
hydrogen, methyl or phenylthio, where the phenyl ring of the
phenylthio radical is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl in the 4-, 2-, 2,4- or 2,4,6-position;
R.sub.33 and R.sub.34 independently of one another are
C.sub.1-C.sub.20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or
biphenyl, where these radicals are unsubstituted or are substituted
by halogen, C.sub.1-C.sub.12alkyl and/or C.sub.1-C.sub.12alkoxy, or
R.sub.33 is an S- or N-containing 5- or 6-membered heterocyclic
ring, or are 233R.sub.35 is cyclohexyl, cyclopentyl, phenyl,
naphthyl or biphenyl, these radicals being unsubstituted or
substituted by halogen, C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy, or R.sub.35 is an S- or N-containing 5- or
6-membered heterocyclic ring; R.sub.36 and R.sub.37 independently
of one another are unsubstituted cyclopentadienyl or
cyclopentadienyl substituted once, twice or three times by
Cl-C.sub.18alkyl, Cl-C,.sub.8alkoxy, cyclopentyl, cyclohexyl or
halogen; and R.sub.38 and R.sub.39 independently of one another are
phenyl which is substituted in at least one of the two ortho
positions relative to the titanium-carbon bond by fluorine atoms or
CF.sub.3, and which on the aromatic ring may contain, as further
substituents, unsubstituted pyrrolinyl or pyrrolinyl substituted by
one or two C.sub.1-C.sub.12alkyl,
di(C.sub.1-C.sub.12alkyl)aminomethyl, morpholinomethyl,
C.sub.2-C.sub.4alkenyl, methoxymethyl, ethoxymethyl,
trimethylsilyl, formyl, methoxy or phenyl; or polyoxaalkyl, or
R.sub.38 and R.sub.39 are 234R.sub.40, R.sub.41 and R.sub.42
independently of one another are hydrogen, halogen,
C.sub.2-C.sub.12alkenyl, C.sub.1-C.sub.12alkoxy,
C.sub.2-C.sub.12alkoxy interrupted by one to four O atoms,
cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, unsubstituted
phenyl or phenyl substituted by C.sub.1-C.sub.4alkoxy, halogen,
phenylthio or C.sub.1-C.sub.4-alkylthio; or biphenyl, where
R.sub.40 and R.sub.42 are not both hydrogen at the same time and in
the radical 235at least one radical R.sub.40 or R.sub.42 is
C.sub.1-C.sub.12alkoxy, C.sub.2-C.sub.12alkoxy interrupted by one
to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or
benzyloxy; E.sub.1 is O, S or NR.sub.43; and R.sub.43 is
C.sub.1-C.sub.8alkyl, phenyl or cyclohexyl.
14. A process for the photopolymerization of nonvolatile monomeric,
oligomeric or polymeric compounds having at least one ethylenically
unsaturated double bond, which comprises irradiating a composition
according to claim 11 with light in the range from 200 to 600
nm.
15. A process according to claim 14 for the preparation of
pigmented and nonpigmented surface coatings, printing inks, screen
printing inks, offset printing inks, flexographic printing inks,
powder coatings, printing plates, adhesives, dental materials,
optical waveguides, optical switches, colour testing systems,
composite materials, glass-fibre cable coatings, screen printing
stencils, resist materials, colour filters, for the encapsulation
of electrical and electronic components, for the preparation of
magnetic recording materials, of three-dimensional objects by means
of stereolithography, of photographic reproductions, image
recording material, in particular for holographic recordings, for
the preparation of decolouring materials, in particular decolouring
materials for image recording materials, for the preparation of
image recording materials using microcapsules.
16. A coated substrate which has been coated on at least one
surface with a composition according to claim 11.
17. A process for the photographic production of relief images in
which a coated substrate according to claim 16 is subjected to
imagewise exposure and then the unexposed portions are removed with
a solvent.
Description
[0001] The present application relates to organometallic
monoacylarylphosphines, to the preparation thereof, and to the use
thereof as starting materials for the preparation of
acylphosphines, acylphosphine oxides or acylphosphine sulfides.
[0002] Various metalated phosphines have become known as
intermediates in the preparation of acylphosphine oxides. Thus, for
example, in EP 40721, acylphosphines are obtained by reaction of
acyl halides with metalated diorganophosphines or silylated
phosphines or diorganophosphines.
[0003] By oxidation of the acyldiorganophosphines, the
corresponding acylphosphine oxide photoinitiators can be prepared
therefrom. Swiss Patent Application No 2376/98 discloses a one-pot
process for the preparation of bisacylphosphine oxides in which
dichloroorganophosphines are metalated, then reacted with acyl
halides to give the corresponding acylphosphines and then, by
oxidation or sulfurization, the bisacylphosphine oxides or
bisacylphosphine sulfides are obtained.
[0004] Arylacylphosphines and the corresponding metalated compounds
are not known in the prior art.
[0005] U.S. Pat. No. 5,399,770 discloses a bisacylphosphine oxide
having two different acyl groups, and U.S. Pat. No. 5,218,009
specifically discloses a monoacylphosphine oxide having two
different non-acyl substituents on the phosphorus atom.
[0006] For the technology, readily accessible starting materials
for the preparation of acylphosphine oxides and acylphosphine
sulfides are of great importance. Of particular interest are
starting materials which permit the preparation of "unsymmetrical"
bisacylphosphine oxides and bisacylphosphine sulfides, i.e. those
with two different acyl groups, in a simple manner.
[0007] A process for the preparation of metalated
arylacylphosphines which are suitable as starting materials for the
preparation of acylphosphine oxide or acylphosphine sulfide
photoinitiators has been found. The phosphines, phosphine oxides
and phosphine sulfides obtained are novel.
[0008] The invention provides compounds of the formula I 2
[0009] Ar is a group 3
[0010] or Ar is cyclopentyl, cyclohexyl, naphthyl, biphenylyl,
anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, where the radicals cyclopentyl, cyclohexyl,
naphthyl, biphenylyl, anthracyl or O-, S- or N-containing 5- or
6-membered heterocyclic ring are unsubstituted or substituted by
halogen, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
[0011] R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen; R.sub.3,
R.sub.4 and R.sub.5 independently of one another are hydrogen,
C.sub.1-C.sub.20alkyl, OR.sub.11 or halogen; or in each case two of
the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4 and/or R.sub.5
together form C.sub.1-C.sub.20alkylene, which can be interrupted by
O, S or NR.sub.14;
[0012] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl;
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which is unsubstituted or substituted
by OH and/or SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
OR.sub.11, phenyl or halogen;
[0013] R.sub.11 is hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl
or C.sub.2-C.sub.20alkyl, which is interrupted once or more than
once by O or S and which is unsubstituted or is substituted by OH
and/or SH;
[0014] R.sub.14 is hydrogen, phenyl, C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH and/or
SH; and M is hydrogen, Li, Na or K.
[0015] C.sub.1-C.sub.24alkyl is linear or branched and is, for
example, C.sub.2-C.sub.24alkyl, C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.4alkyl. Examples are methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl,
nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, nonadecyl, icosyl or tetraicosyl.
[0016] For example, R.sub.1, R.sub.2, R.sub.3, R.sub.1', R.sub.2'
and R.sub.3' are C.sub.1-C.sub.8alkyl, in particular
C.sub.1-C.sub.6alkyl, preferably C.sub.1-C.sub.4alkyl, particularly
preferably methyl.
[0017] C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.6alkyl and
C.sub.1-C.sub.4alkyl are likewise linear or branched and have, for
example, the meanings given above apart from the corresponding
number of carbon atoms.
[0018] R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10,
R.sub.11, R.sub.12, R.sub.13, R.sub.19, R.sub.20, R.sub.21,
R.sub.22 and R.sub.23 are, for example, C.sub.1-C.sub.8alkyl, in
particular C.sub.1-C.sub.6alkyl, preferably C.sub.1-C.sub.4alkyl,
for example methyl or butyl.
[0019] C.sub.2-C.sub.24alkyl which is interrupted once or more than
once by O, S or NR.sub.14 is, for example, interrupted 1-9 times,
e.g. 1-7 times or once or twice, by O, S or NR.sub.14. If the
radicals are interrupted by two or more O, S or NR.sub.14, then the
O atoms, S atoms or NR.sub.14 groups are in each case separated
from one another by at least one methylene group. The O atoms, S
atoms or NR.sub.14 groups are thus not directly consecutive. The
alkyl radical can be linear or branched. For example, structural
units such as --CH.sub.2--O--CH.sub.3,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.3,
--[CH.sub.2CH.sub.2O].sub.z--CH.- sub.3, where z=1 to 9,
--(CH.sub.2CH.sub.2O).sub.7CH.sub.2CH.sub.3,
--CH.sub.2--CH(CH.sub.3)--O--CH.sub.2--CH.sub.2CH.sub.3,
--CH.sub.2--CH(CH.sub.3)--O--CH.sub.2--CH.sub.3,
--CH.sub.2SCH.sub.3 or --CH.sub.2--N(CH.sub.3).sub.2 arise.
[0020] C.sub.2-C.sub.20alkyl, C.sub.2-C.sub.18alkyl,
C.sub.2-C.sub.12alkyl which are interrupted by O and optionally by
S are likewise linear or branched and can, for example, have the
meanings given above apart from the given number of carbon atoms.
Here too, the O atoms are not consecutive.
[0021] C.sub.1-C.sub.18haloalkyl is C.sub.1-C.sub.18alkyl as
described above which is mono- or polysubstituted by halogen. This
is, for example, perfluorinated C.sub.1-C.sub.18alkyl. Examples are
chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, in
particular trifluoromethyl or trichloromethyl.
[0022] C.sub.3-C.sub.24cycloalkyl, e.g. C.sub.5-C.sub.12cycloalkyl,
C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.8cycloalkyl, stands both
for individual alkyl ring systems and also bridged alkyl ring
systems. Furthermore, the radicals can also contain linear or
branched alkyl groups (as described above apart from the
corresponding number of carbon atoms). Examples are cyclopropyl,
cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloicosyl,
adamantyl, in particular cyclopentyl and cyclohexyl, preferably
cyclohexyl. Further examples are 4
[0023] C.sub.3-C.sub.8cycloalkyl, e.g. C.sub.3-C.sub.6cycloalkyl,
can have the meanings given above apart from the corresponding
number of carbon atoms.
[0024] C.sub.3-C.sub.18cycloalkyl substituted by
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen is preferably
tri- or disubstituted in the 2,4,6- or 2,6-positions respectively,
of the cycloalkyl ring. Preference is given to
2,4,6-trimethylcyclohexyl and 2,6-dimethoxycyclohexyl.
[0025] C.sub.2-C.sub.24alkenyl radicals are mono- or
polyunsaturated, and are linear or branched and are, for example,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.8alkenyl,
C.sub.2-C.sub.6alkenyl or C.sub.2-C.sub.4alkenyl. Examples are
vinyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 2-butenyl,
1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, in
particular allyl. C.sub.2-C.sub.18alkenyl has the same meanings as
given above apart from the corresponding number of carbon
atoms.
[0026] If C.sub.2-C.sub.24alkenyl radicals are interrupted, for
example, by 0, then the following structures are, for example,
included: --(CH.sub.2).sub.y--O--(CH.sub.2).sub.x--CH.dbd.CH.sub.2,
--(CH.sub.2).sub.y--O--(CH.sub.2).sub.x--C(CH.sub.3).dbd.CH.sub.2
or --(CH.sub.2).sub.y--O--CH.dbd.CH.sub.2, where x and y
independently of one another are a number from 1 to 21.
[0027] C.sub.3-C.sub.24cycloalkenyl, e.g.
C.sub.5-C.sub.12cycloalkenyl, C.sub.3-C.sub.12cycloalkenyl,
C.sub.3-C.sub.8cycloalkenyl, stands both for individual alkyl ring
systems and also bridged alkyl ring systems and can be mono- or
polyunsaturated, e.g. mono- or diunsaturated. Furthermore, the
radicals can also contain linear or branched alkyl groups (as
described above apart from the corresponding number of carbon
atoms). Examples are cyclopropenyl, cyclopentenyl, cyclohexenyl,
cyclooctenyl, cyclododecenyl, cycloicosenyl, in particular
cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.
[0028] C.sub.6-C.sub.14aryl is, for example, C.sub.6-C.sub.10aryl.
Examples are phenyl, naphthyl, biphenylyl, anthracyl or
phenanthryl, preferably phenyl or naphthyl, in particular
phenyl.
[0029] C.sub.7-C.sub.24arylalkyl is, for example,
C.sub.7-C.sub.16arylalky- l, C.sub.7-C.sub.11arylalkyl. The alkyl
radical in this group can either be linear or branched. Examples
are benzyl, phenylethyl, .alpha.-methylbenzyl, phenylpentyl,
phenylhexyl, .alpha.,.alpha.-dimethyl- benzyl, naphthylmethyl,
naphthylethyl, naphthyleth-1-yl or naphthyl-1-methyl-eth-1-yl, in
particular benzyl. Substituted C.sub.7-C.sub.24arylalkyl is
substituted one to four times, e.g. once, twice or three times, in
particular once or twice, on the aryl ring.
[0030] C.sub.8-C.sub.24arylcycloalkyl is e.g.
C.sub.9-C.sub.16arylcycloalk- yl, C.sub.9-C.sub.13arylcycloalkyl
and is cycloalkyl which is fused with one or more aryl rings.
Examples are 5
[0031] C.sub.1-C.sub.12alkylthio stands for linear or branched
radicals and is, for example, C.sub.1-C.sub.8alkylthio,
C.sub.1-C.sub.6alkylthio or C.sub.1-C.sub.4alkylthio. Examples are
methylthio, ethylthio, propylthio, isopropylthio, n-butylthio,
sec-butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio,
heptylthio, 2,4,4-trimethylpentylthio, 2-ethylhexylthio, octylthio,
nonylthio, decylthio or dodecylthio, in particular methylthio,
ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio,
isobutylthio, tert-butylthio, preferably methylthio.
[0032] C.sub.1-C.sub.8alkylthio is likewise linear or branched and
has, for example, the meanings given above apart from the
corresponding number of carbon atoms.
[0033] C.sub.1-C.sub.24alkylene is linear or branched and is, for
example, C.sub.1-C.sub.20alkylene, C.sub.1-C.sub.12alkylene,
C.sub.1-C.sub.8alkylene, C.sub.2-C.sub.8alkylene,
C.sub.1-C.sub.4alkylene- , for example methylene, ethylene,
propylene, isopropylene, n-butylene, sec-butylene, isobutylene,
tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene,
decylene, dodecylene, tetradecylene, heptadecylene, octadecylene,
icosylene or e.g. C.sub.1-C.sub.12alkylene, for example ethylene,
decylene, 6
[0034] C.sub.2-C.sub.18alkylene is also linear or branched, e.g.
C.sub.2-C.sub.8alkylene or C.sub.2-C.sub.4alkylene and has the
meanings given above apart from the corresponding number of carbon
atoms.
[0035] If C.sub.2-C.sub.18alkylene is interrupted once or more than
once by O, S, or NR.sub.14, then it is, for example, interrupted
1-9 times, e.g. 1-7 times or once or twice by O, S or NR.sub.14,
and, for example, structural units such as
--CH.sub.2--O--CH.sub.2--,
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--,
--[CH.sub.2CH.sub.2O].sub.z--, where z=1 to 9,
--(CH.sub.2CH.sub.2O).sub.7CH.sub.2CH.sub.2--,
--CH.sub.2--CH(CH.sub.3)--O--CH.sub.2--CH(CH.sub.3)--,
--CH.sub.2--S--CH.sub.2--,
--CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2CH.sub.2--,
--(CH.sub.2).sub.3--S--(CH.sub.2).sub.3--,
--CH.sub.2--(NR.sub.14)--CH.su- b.2-- or
--CH.sub.2CH.sub.2--(NR.sub.14)--CH.sub.2CH.sub.2-- arise. The
alkylene radicals can be linear or branched and, if the alkylene
radicals are interrupted by two or more O, S or NR.sub.14 groups,
then the O, S and NR.sub.14 are not consecutive, but in each case
are separated from one another by at least one methylene group.
[0036] C.sub.2-C.sub.24alkenylene is mono- or polyunsaturated and
linear or branched and e.g. C.sub.2-C.sub.18alkenylene or
C.sub.2-C.sub.8alkenylene. Examples are ethenylene, propenylene,
butenylene, pentenylene, hexenylene, octenylene, e.g.
1-propenylene, 1-butenylene, 3-butenylene, 2-butenylene, 1
,3-pentadienylene, 5-hexenylene or 7-octenylene.
[0037] C.sub.2-C.sub.24alkenylene, interrupted once or more than
once by O, S, NR.sub.14, is mono- or polyunsaturated and linear or
branched and is, for example, interrupted 1-9 times, e.g. 1-7 times
or once or twice, by O, S or NR.sub.14, where in the case of two or
more O, S or NR.sub.14, these are in each case separated from one
another by at least one methylene group. Here, the meanings for
C.sub.2-C.sub.24alkenylene are as defined above.
[0038] C.sub.4-C.sub.18cycloalkylene is linear or branched and can
be either an individual ring or bridged alkyl rings. It is e.g.
C.sub.4-C.sub.12cycloalkylene or C.sub.4-C.sub.8cycloalkylene, for
example cyclopentylene, cyclohexylene, cyclooctylene,
cyclododecylene, in particular cyclopentylene and cyclohexylene,
preferably cyclohexylene. However, C.sub.4-C.sub.18cycloalkylene
likewise stands for structural units such as 7
[0039] in which r and s independently of one another are 0-12 and
the sum r+s is .ltoreq.12, or 8
[0040] in which r and s independently of one another are 0-13 and
the sum r+s is .ltoreq.13.
[0041] C.sub.4-C.sub.18cycloalkylene interrupted once or more than
once by O, S or NR.sub.14 stands for cycloalkylene units as
described above which can be interrupted either in the ring unit or
in the side-chain unit e.g. 1-9 times, 1-7 times or once or twice,
by O, S or NR.sub.14.
[0042] C.sub.3-C.sub.24cycloalkenylene is linear or branched and
can be either a single ring or bridged rings and is mono- or
polyunsaturated. It is e.g. C.sub.3-C.sub.12cycloalkenylene or
C.sub.3-C.sub.8cycloalkenylene- , for example cyclopentenylene,
cyclohexenylene, cyclooctenylene, cyclododecenylene, in particular
cyclopentenylene and cyclohexenylene, preferably cyclohexenylene.
C.sub.3-C.sub.24cycloalkenylene also, however, stands for
structural units such as 9
[0043] in which r and s independently of another are 0-12 and the
sum r+s is .ltoreq.12, or 10
[0044] in which r and s independently of one another are 0-13 and
the sum r+s is .ltoreq.13.
[0045] C.sub.5-C.sub.18cycloalkenylene has the meanings given above
for C.sub.3-C.sub.24cycloalkenylene apart from the corresponding
number of carbon atoms.
[0046] C.sub.3-C.sub.24cycloalkenylene interrupted once or more
than once by O, S or NR.sub.14 stands for cycloalkenylene units as
described above which can be interrupted either in the ring unit or
in the side-chain unit e.g. 1-9 times, 1-7 times or once or twice
by O, S or NR.sub.14. Examples are 11
[0047] Halogen is fluorine, chlorine, bromine or iodine, in
particular fluorine, chlorine and bromine, preferably chlorine.
R.sub.1, R.sub.1', R.sub.2, R.sub.2', R.sub.3 and R.sub.3' as
halogen are, in particular, chlorine.
[0048] If in each case two of the radicals R.sub.1, R.sub.2,
R.sub.3, R.sub.4 or R.sub.5 or in each case two of the radicals
R.sub.1', R.sub.2', R.sub.3', R.sub.4' or R.sub.5' form
C.sub.1-C.sub.12alkylene, then, for example, the following
structures 12
[0049] As a(n) O-, S- or N-containing 5- or 6-membered heterocyclic
ring, Ar is e.g. furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or
pyridyl. Said heterocyclic radicals can be mono- or
polysubstituted, e.g. monosubstituted or disubstituted, by halogen,
linear or branched C.sub.1-C.sub.4alkyl, such as methyl, ethyl,
propyl, butyl, and/or C.sub.1-C.sub.4alkoxy. Examples thereof are
dimethylpyridyl, dimethylpyrrolyl or methylfuryl.
[0050] Ar is, for example, 2-methylnaphth-2-yl,
2-methoxynaphth-2-yl, 1,3-dimethyinaphth-2-yl,
2,8-dimethylnaphth-1-yl, 1,3-dimethoxynaphth-2-y- l,
1,3-dichloronaphth-2-yl, 2,8-dimethoxynaphth-1-yl,
2,4,6-trimethylpyrid-3-yl, 2,4-dimethoxyfuran-3-yl or
2,4,5-trimethylthien-3-yl.
[0051] Preference is given to compounds of the formula I in which
Ar is a radical 13
[0052] "Styryl" and "methylstyryl" are 14
[0053] "--N.dbd.C.dbd.A" is a group --NCO or --NCS.
[0054] Cycloalkyl substituted by --N.dbd.C.dbd.A and
C.sub.1-C.sub.4alkyl is for example isophoroneisocyanate. &p In
connection with the present application, the term "and/or" means
that not only one of the defined alternatives (substituents), but
likewise two or more different defined alternatives (substituents)
together, i.e. mixtures of different alternatives (substituents)
may be present. The term "at least" is intended to define one or
more than one, e.g. one or two or three, preferably one or two.
[0055] Of particular interest are compounds of the formula I, in
which R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, Cl or CF.sub.3, in
particular methyl or methoxy.
[0056] R.sub.1 and R.sub.2 are preferably identical.
[0057] R.sub.1 and R.sub.2 are preferably C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy.
[0058] R.sub.3, R.sub.4 and R.sub.5 in the compounds of the formula
I are, in particular, independently of one another hydrogen,
C.sub.1-C.sub.4alkyl, Cl or C.sub.1-C.sub.4alkoxy, in particular
hydrogen, methyl or methoxy. R.sub.3 is preferably
C.sub.1-C.sub.4alkyl, or C.sub.1-C.sub.4alkoxy, in particular
methyl, methoxy or hydrogen, and R.sub.4 and R.sub.5 are
hydrogen.
[0059] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 in the
compounds of the formula I are, in particular, independently of one
another hydrogen, C.sub.1-C.sub.12alkyl; OR.sub.11, phenyl or
halogen, preferably C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
phenyl or halogen. R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
in the compounds of the formula I are preferably hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, in particular
hydrogen.
[0060] R.sub.11 in the compounds of the formula I is, for example,
hydrogen, C.sub.1-C.sub.12alkyl, cyclopentyl, cyclohexyl, phenyl,
benzyl or C.sub.2-C.sub.12alkyl which is interrupted once or more
than once by O or S, preferably C.sub.1-C.sub.4alkyl, cyclopentyl,
cyclohexyl, phenyl or benzyl.
[0061] Compounds in which R.sub.12 and R.sub.13 are e.g. hydrogen,
C.sub.1-C.sub.4alkyl, phenyl or benzyl or C.sub.2-C.sub.12alkyl
which is interrupted once or more than once by nonconsecutive O
atoms and which is unsubstituted or is substituted by OH and/or SH;
or R.sub.12 and R.sub.13 together are piperidino, morpholino, or
piperazino are likewise of interest. R.sub.12 and R.sub.13 are
preferably C.sub.1-C.sub.4alkyl, or R.sub.12 and R.sub.13 are
together morpholino.
[0062] R.sub.14 in the compounds of the formula I is, in
particular, hydrogen, phenyl, C.sub.1-C.sub.4alkyl or
C.sub.2-C.sub.4alkyl which is interrupted once or more than once by
O or S and which is unsubstituted or is substituted by OH and/or
SH, preferably hydrogen and C.sub.1-C.sub.4alkyl.
[0063] M in the compounds of the formula I is preferably hydrogen
or Li, in particular Li.
[0064] Of particular interest are compounds of the formula I in
which
[0065] R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.12alkyl, OR.sub.11, CF.sub.3 or halogen;
[0066] R.sub.3, R.sub.4 and R.sub.5 independently of one another
are hydrogen, C.sub.1-C.sub.12alkyl, OR.sub.11 or halogen;
[0067] R.sub.6, R7, R.sub.8, R.sub.9 and R.sub.10 independently of
one another are hydrogen, C.sub.1-C.sub.12alkyl, OR.sub.11, phenyl
or halogen;
[0068] R.sub.11 is hydrogen, C.sub.1-C.sub.12alkyl, cyclohexyl,
cyclopentyl, phenyl or benzyl;
[0069] R.sub.14 is hydrogen or C.sub.1-C.sub.12alkyl; and
[0070] M is hydrogen or Li.
[0071] Examples of compounds of the formula I are
[0072] lithium 2,6-dimethylbenzoylphenylphosphine; lithium
2,6-diethylbenzoylphenylphosphine; lithium
2,4,6-trimethylbenzoylphenylph- osphine; lithium
2,3,4,5,6-pentamethylbenzoylphenylphosphine; lithium
2,3,5,6-tetramethylbenzoylphenylphosphine; lithium
2,4,6-triisopropylbenzoylphenylphosphine; lithium
2,4,5,6-tetramethylbenz- oylphenylphosphine; lithium
2,4,6-tri-tert-butylbenzoylphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoylphenylphosphine; lithium
2,6-diphenoxymethylbenzoylphenylphosphine; lithium
2,3,6-trimethylbenzoylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl- phenylphosphine; lithium
2-phenyl-6-methylbenzoylphenylphosphine; lithium
2,4,6-trimethoxybenzoylphenylphosphine; lithium
2,4-dimethoxybenzoylpheny- lphosphine; lithium
2,3,6-trimethoxybenzoylphenylphosphine; lithium
2,6-diethoxybenzoylphenylphosphine; lithium
2,6-dimethoxy-3,5-dimethylben- zoylphenylphosphine; lithium
2,6-dimethoxy-4-methylbenzoylphenylphosphine; lithium
2,6-dimethoxy-3-bromobenzoylphenylphosphine; lithium
2,6-dimethoxy-3-chlorobenzoylphenylphosphine; lithium
2,6-dimethoxy-3-chloro-5-bromobenzoylphenylphosphine; lithium
2,6-dimethoxy-3,5-dichlorobenzoylphenylphosphine; lithium
2,3,6-trimethoxy-5-bromobenzoylphenylphosphine; lithium
2,6-dichlorobenzoylphenylphosphine; lithium
2,4,6-trichlorobenzoylphenylp- hosphine; lithium
2,3,6-trichlorobenzoylphenylphosphine; lithium
2,3,5,6-tetrachlorobenzoylphenylphosphine; lithium
2,3,4,5,6-pentachlorobenzoylphenylphosphine; lithium
2,6-dichloro-3-methylbenzoylphenylphosphine; lithium
2-chloro-6-methylbenzoylphenylphosphine; lithium
2-methoxy-3,6-dichlorobe- nzoylphenylphosphine; lithium
2-methoxy-6-chlorobenzoylphenylphosphine; lithium
2,6-bis(trifluoromethyl)-benzoylphenylphosphine; lithium
2-chloro-6-methylthiobenzoylphenylphosphine; lithium
2,6-dibromobenzoylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-methy- lphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2-methylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dimethylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,6-dimethylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,5-dimethylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4,6-trimethylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,5-diisopropylphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-4-phenylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2-phenylphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-methoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-ethoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-propoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-butoxy-phenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-pentoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-hexoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-isopropoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-isobutoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-tert-butoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-(1-methylpropoxy)phenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-amyloxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-isopentoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-benzyloxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-phenyloxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-methoxyethoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dimethoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-diethoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dipropoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dibutoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dipentoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-dihexoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4-di(1-methylpropoxy)phenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-diamyloxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-diisopentoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-dibenzyloxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-diphenoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-dimethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4-diethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-trimethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-tripropoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-tributoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-tripentoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-trihexoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triisopropoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triisobutoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4,6-tri-tert-butoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4,6-tri(-methylpropoxy)phenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triamyloxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-(1
-methylpropoxy)phenylphosphine; lithium
2,4,6-trimethylbenzoyl-2-methyl-4-amyloxyphenylphosphine; lithium
2,4,6-trimethylbenzoyl-2-methyl-4-isopentoxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium 2,4,6-trimethylbenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2-methyl-4-methoxyethoxyphenylphosphine;
lithium
2,4,6-trimethylbenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-4-methylphenylphosphine; lithium
2,6-dimethylbenzoyl-2-methylphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dimethylphenylphosphine; lithium
2,6-dimethylbenzoyl-2,6-dimethylphenylphosphine; lithium
2,6-dimethylbenzoyl-2,5-dimethylphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-trimethylphenylphosphine; lithium
2,6-dimethylbenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine,
lithium 2,6-dimethylbenzoyl-2,5-diisopropylphenylphosphine; lithium
2,6-dimethylbenzoyl-4-phenylphenylphosphine; lithium
2,6-dimethylbenzoyl-2-phenylphenylphosphine; lithium
2,6-dimethylbenzoyl-4-methoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-ethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-propoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-butoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-pentoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-hexoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-isopropoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-isobutoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-tert-butoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,6-dimethylbenzoyl-4-(1-methylpropoxy)phenylphosphine; lithium
2,6-dimethylbenzoyl-4-amyloxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-isopentoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-benzyloxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-phenoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-methoxyethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dimethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dipropoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dibutoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dipentoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dihexoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-di(1-methylpropoxy)phenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diamyloxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diisopentoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dibenzyloxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diphenoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-dimethoxyethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4-diethoxyethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-trimethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-triethoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-tripropoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-tributoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-tripentoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-trihexoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-triisopropoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-triisobutoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-tri-tert-butoxyphenylphosphine; lithium
2,6-dimethylbenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2,6-dimethylbenzoyl-2,4,6-tri(1-methylpropoxy)phenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-triamyloxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,6-dimethylbenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphine;
lithium
2,6-dimethylbenzoyl-2-methyl-4-(1-methylpropoxy)phenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-amyloxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-isopentoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,6-dimethylbenzoyl-2-methyl-4-methoxyethoxyphenylphosphine;
lithium 2,6-dimethylbenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-4-methylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2-methylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dimethylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,6-dimethylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,5-dimethylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-trimethylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,5-diisopropylphenylphosphine;
lithium 2,6-dimethoxybenzoyl-4-phenylphenylphosphine; lithium
2,6-dimethoxybenzoyl-2-phenylphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-methoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-ethoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-propoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-butoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-pentoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-hexoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-isopropoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-isobutoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-tert-butoxy-phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-(1-methylpropoxy)phenylphosphine; lithium
2,6-dimethoxybenzoyl-4-amyloxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-isopentoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-benzyloxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-phenoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-methoxyethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dimethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dipropoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dibutoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dipentoxyphenyl-phosphine; lithium
2,6-dimethoxybenzoyl-2,4-dihexoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-di(2-ethylhexoxy)-phenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-di(1-methylpropoxy)-phenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4-diamyloxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diisopentoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dibenzyloxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diphenoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-dimethoxyethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4-diethoxyethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-trimethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-triethoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-tripropoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-tributoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-tripentoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-trihexoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-triisopropoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-triisobutoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-tri-tert-butoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2,4,6-tri(2-ethylhexoxy)-phenylphosphine;
lithium
2,6-dimethoxybenzoyl-2,4,6-tri(1-methylpropoxy)-phenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-triamyloxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2,6-dimethoxybenzoyl-2-methyl-4-isopropoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2-methyl-4-isobutoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2-methyl-4-tert-butoxyphenylphosphine; lithium
2,6-dimethoxybenzoyl-2-methyl-4-(2-ethylhexoxy)-phenylphosphine;
lithium
2,6-dimethoxybenzoyl-2-methyl-4-(1-methylpropoxy)-phenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-amyloxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-isopentoxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium 2,6-dimethoxybenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,6-dimethoxybenzoyl-2-methyl-4-methoxyethoxyphenylphosphine;
lithium
2,6-dimethoxybenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-methylphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-2-methylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dimethylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,5-dimethylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-trimethylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,5-diisopropylphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-phenylphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-2-phenylphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-methoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-ethoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-propoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-butoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-pentoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-hexoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-isopropoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-isobutoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-tert-butoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-(2-ethylhexoxy)-phenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-(1-methylpropoxy)-phenylphosphi-
ne; lithium
2,6-bis(trifluoromethyl)benzoyl-4-amyloxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-4-isopentoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-benzyloxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-4-phenoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-methoxyethoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-4-ethoxyethoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dimethoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diethoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dipropoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dibutoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dipentoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dihexoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diisopropoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diisobutoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-di-tert-butoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-di(2-ethylhexoxy)-phenylphosp-
hine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-di(1-methylpropoxy)-phen-
ylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diamyloxyphenylph- osphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-2,4-diisopentoxyphenylpho-
sphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dibenzyloxyphenylphosp- hine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diphenoxyphenylphosphine- ;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-dimethoxyethoxyphenylphosphi-
ne; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4-diethoxyethoxyphenylphosph-
ine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-trimethoxyphenylphosphi- ne;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-triethoxyphenylphosphine- ;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tripropoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tributoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tripentoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-trihexoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-triisopropoxyphenylphosphin-
e; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-triisobutoxyphenylphosphi-
ne; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tri-tert-butoxyphenylpho-
sphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tri(2-ethylhexoxy)-p-
henylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tri(1-methyl-
propoxy)-phenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-tr- iamyloxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-2,4,6-tri-
isopentoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-t-
ribenzyloxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,4,6-- triphenoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzoyl-2,4,6-t-
rimethoxyethoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2,-
4,6-triethoxyethoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoy-
l-2-methyl-4-methoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzo- yl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benzo-
yl-2-methyl-4-propoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benz- oyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)benz-
oyl-2-methyl-4-pentoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)ben- zoyl-2-methyl-4-hexoxyphenylphosphine;
lithium 2,6-bis(trifluoromethyl)ben-
zoyl-2-methyl-4-isopropoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl-
)benzoyl-2-methyl-4-isobutoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,6-bis(trifluoromethyl)benzoyl-2-methyl-4-(2-ethylhexoxy)-phenyl-
phosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-methyl-4-(1-methylpro-
poxy)-phenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-methyl-4--
amyloxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-methyl-4-
-isopentoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-meth-
yl-4-benzyloxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2-m-
ethyl-4-phenoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)benzoyl-2--
methyl-4-methoxyethoxyphenylphosphine; lithium
2,6-bis(trifluoromethyl)ben-
zoyl-2-methyl-4-ethoxyethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-methylphenylphosphine; lithium
2,6-dichlorobenzoyl-2-methylphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dimethylphenylphosphine; lithium
2,6-dichlorobenzoyl-2,6-dimethylphenylphosphine; lithium
2,6-dichlorobenzoyl-2,5-dimethylphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-trimethylphenylphosphine; lithium
2,6-dichlorobenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,5-diisopropylphenylphosphine; lithium
2,6-dichlorobenzoyl-4-phenylphenylphosphine; lithium
2,6-dichlorobenzoyl-2-phenylphenylphosphine; lithium
2,6-dichlorobenzoyl-4-methoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-ethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-propoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-butoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-pentoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-hexoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-isopropoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-isobutoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-tert-butoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,6-dichlorobenzoyl-4-(1-methylpropoxy)phenylphosphine; lithium
2,6-dichlorobenzoyl-4-amyloxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-isopentoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-benzyloxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-phenoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-methoxyethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dimethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dipropoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dibutoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dipentoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dihexoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-di(1-methylpropoxy)phenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diamyloxyphenylphosphine; lithium
2,6-di-chlorobenzoyl-2,4-diisopentoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dibenzyloxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diphenoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-dimethoxyethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4-diethoxyethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-trimethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-triethoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-tripropoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-tributoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-tripentoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-trihexoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-triisopropoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-triisobutoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-tri-tert-butoxyphenylphosphine; lithium
2,6-dichlorobenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2,6-dichlorobenzoyl-2,4,6-tri(1-methylpropoxy)phenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-triamyloxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,6-dichlorobenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphine;
lithium
2,6-dichlorobenzoyl-2-methyl-4-(1-methylpropoxy)phenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-amyloxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-isopentoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,6-dichlorobenzoyl-2-methyl-4-methoxyethoxyphenylphosphine;
lithium 2,6-dichlorobenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-methylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2-methylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,4-dimethylphen-ylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,6-dimethylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,5-dimethylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-trimethylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,5-diisopropylphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-phenylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2-phenylphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-methoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-ethoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-propoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-butoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-pentoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-hexoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-isopropoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-isobutoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-tert-butoxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-4-(2-ethylhexoxy)phenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-4-(1-methylpropoxy)phenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-amyloxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-isopentoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-benzyloxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-phenoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-methoxyethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-4-ethoxyethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dimethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dipropoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dibutoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dipentoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dihexoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diisopropoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diisobutoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4-di-tert-butoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4-di(1-methylpropoxy)phenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diamyloxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diisopentoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-dibenzyloxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4-diphenoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4-dimethoxyethoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4-diethoxyethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-trimethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-triethoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-tripropoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-tributoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-tripentoxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-trihexoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-triisopropoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-triisobutoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-tri-tert-butoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-tri(1-methylpropoxy)phenylphosph-
ine; lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-triamyloxyphenylphosphine; lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,3,4,6-tetramethylbenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosph-
ine; lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-(1-methylpropoxy)phenyl-
phosphine; lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-amyloxyphenylphos- phine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-isopentoxyphenylphosp- hine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-benzyloxyphenylphosphi- ne;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-methoxyethoxyphenylphosphin-
e;
[0073] lithium
2,3,4,6-tetramethylbenzoyl-2-methyl-4-ethoxyethoxyphenylpho-
sphine; lithium 2,4,6-trimethoxybenzoyl-4-methylphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dimethylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,6-dimethylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,5-dimethylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4 ,6-trimethylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,5-diisopropylphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-4-phenylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2-phenylphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-methoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-ethoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-propoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-butoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-pentoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-hexoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-isopropoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-isobutoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-tert-butoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-(1-methylpropoxy)phenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-amyloxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-isopentoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-benzyloxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-phenoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-methoxyethoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dimethoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-diethoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dipropoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dibutoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dipentoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-dihexoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4-di(1-methylpropoxy)phenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-diamyloxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-diisopentoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-dibenzyloxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-diphenoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-dimethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4-diethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-trimethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-tripropoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-tributoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-tripentoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-trihexoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triisopropoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triisobutoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4,6-tri-tert-butoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4,6-tri(1-methylpropoxy)phenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triamyloxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-(1-methylpropoxy)phenylphosphi-
ne; lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-amyloxyphenylphosphine; lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-isopentoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium 2,4,6-trimethoxybenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-methoxyethoxyphenylphosphine;
lithium
2,4,6-trimethoxybenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-methylphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2-methylphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dimethylphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethylphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,5-dimethylphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-trimethylphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine-
; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,5-diisopropylphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-phenylphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2-phenylphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-methoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-ethoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-propoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-butoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-pentoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-hexoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-isopropoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-isobutoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-tert-butoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-(2-ethylhexoxy)phenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-(1-methylpropoxy)phenylphosphi-
ne, lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-amyloxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-isopentoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-benzyloxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-4-phenoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-methoxyethoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-4-ethoxyethoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dimethoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-diethoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dipropoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dibutoxyphenylphosphine;
lithium
2,6-dimethyl-4-tertbutylbenzoyl-2,4-dipentoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dihexoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-diisopropoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-diisobutoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-di-tert-butoxyphenylphosphin-
e; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-di(2-ethylhexoxy)phenylpho-
sphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-di(1-methylpropoxy)ph-
enylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-diamyloxypheny- lphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2,4-diisopentoxypheny-
lphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dibenzyloxyphenyl- phosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2,4-diphenoxyphenylpho-
sphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-dimethoxyethoxyphenyl-
phosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4-diethoxyethoxyphen-
ylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-trimethoxyphen- ylphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-triethoxypheny-
lphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-tripropoxypheny- lphosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-tributoxyphenyl-
phosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-tripentoxyphenyl- phosphine;
lithium 2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-trihexoxyphenylp-
hosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-triisopropoxyphen-
ylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-triisobutoxyph-
enylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-tri-tert-but-
oxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-tri(2-e-
thylhexoxy)phenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6- -tri(methylpropoxy)
phenylphosphine; lithium 2,6-dimethyl-4-tert-butylbenz-
oyl-2,4,6-triamyloxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenz-
oyl-2,4,6-triisopentoxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylb-
enzoyl-2,4,6-tribenzyloxyphenylphosphine; lithium
2,6-dimethyl-4-tert-buty- lbenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium 2,6-dimethyl-4-tert-buty-
lbenzoyl-2,4,6-trioxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylben-
zoyl-2,4,6-triethoxyethoxyphenylphosphine; lithium 2,
6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2,6-dimethyl-
4-tert-butylbenzoyl-2-methyl-4-propoxyphenylphosphi- ne; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-butoxyphenylphosph-
ine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-pentoxyphenylphos-
phine; lithium 2,6-dimethyl- 4-tert-butylbenzoyl-2-methyl-
4-hexoxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methy-
l-4-isopropoxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2--
methyl-4-isobutoxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoy-
l-2-methyl-4-tert-butoxyphenylphosphine; lithium
2,6-dimethyl-4-tert-butyl-
benzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-(1-methylpropoxy)phenylphosph-
ine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-amyloxyphenylphos-
phine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-isopentoxypheny-
lphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-benzyloxyp-
henylphosphine;
[0074] lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-phenoxyphenylph-
osphine; lithium 2,6
dimethyl-4-tert-butylbenzoyl-2-methyl-4-methoxyethoxy-
phenylphosphine; lithium
2,6-dimethyl-4-tert-butylbenzoyl-2-methyl-4-ethox-
yethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-methylphenylpho- sphine; lithium
2-chloro-6-methylbenzoyl-2-methylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dimethylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,6-dimethylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,5-dimethylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4,6-trimethylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,5-diisopropylphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-4-phenylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2-phenylphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-methoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-ethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-propoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-butoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-pentoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-hexoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-isopropoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-isobutoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-tert-butoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-(1-methylpropoxy)phenylphosphine;
lithium 2-chloro-6-methylbenzoyl-4-amyloxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-isopentoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-benzyloxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-phenoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-methoxyethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dimethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-diethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dipropoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dibutoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dipentoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-dihexoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-di-tert-butoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4-di(1-methylpropoxy)phenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4-diamyloxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4-diisopentoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4-dibenzyloxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4-diphenoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4-dimethoxyethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4-diethoxyethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-trimethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-triethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-tripropoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-tributoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-tripentoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-trihexoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4,6-triisopropoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-triisobutoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4,6-tri-tert-butoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-tri(
-methylpropoxy)phenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4,6-triamyloxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium
2-chloro-6-methylbenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl -4-(2-ethylhexoxy)
phenylphosphine; lithium 2-chloro-6-methylbenzoyl- 2-methyl-4-(1
-methylpropoxy) phenylphosphine; lithium 2-chloro-6-methylbenzoyl-
2-methyl-4-amyloxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2-met- hyl-4-isopentoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-
-4-benzyloxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2-methyl-4-p- henoxyphenylphosphine;
lithium 2-chloro-6-methylbenzoyl-2-methyl-4-methoxy-
ethoxyphenylphosphine; lithium
2-chloro-6-methylbenzoyl-2-methyl-4-ethoxye- thoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-4-methylphenylphos- phine;
lithium 2-chloro-6-methoxybenzoyl-2-methylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dimethylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,6-dimethylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,5-dimethylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4,6-trimethylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,6-dimethyl-4-tert-butylphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,5-diisopropylphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-4-phenylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2-phenylphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-methoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-ethoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-propoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-butoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-pentoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-hexoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-isopropoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-isobutoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-tert-butoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-(2-ethylhexoxy)phenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-(1-methylpropoxy)phenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-4-amyloxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-isopentoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-benzyloxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-phenoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-methoxyethoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-4-ethoxyethoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dimethoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-diethoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dipropoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dibutoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dipentoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-dihexoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-diisopropoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-diisobutoxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4-di-tert-butoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4-di(2-ethylhexoxy)phenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4-di(1-methylpropoxy)phenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4-diamyloxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4-diisopentoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4-dibenzyloxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4-diphenoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4-dimethoxyethoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4-diethoxyethoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-trimethoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-triethoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-tripropoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-tributoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-tripentoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-trihexoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-triisopropoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-triisobutoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-tri-tert-butoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-tri(2-ethylhexoxy)phenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-tri(1-methylpropoxy)phenylphosphi-
ne; lithium
2-chloro-6-methoxybenzoyl-2,4,6-triamyloxyphenylphosphine; lithium
2-chloro-6-methoxybenzoyl-2,4,6-triisopentoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-tribenzyloxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2,4,6-triphenoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-trimethoxyethoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2,4,6-triethoxyethoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-methoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2-methyl-4-ethoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-propoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2-methyl-4-butoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-pentoxyphenylphosphine;
lithium 2-chloro-6-methoxybenzoyl-2-methyl-4-hexoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-isopropoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-isobutoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-tert-butoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-(2-ethylhexoxy)phenylphosphi-
ne; lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-(1-methylpropoxy)phenylph-
osphine; lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-amyloxyphenylphosphi- ne;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-isopentoxyphenylphosphine- ;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-benzyloxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-phenoxyphenylphosphine;
lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-methoxyethoxyphenylphosphine-
; lithium
2-chloro-6-methoxybenzoyl-2-methyl-4-ethoxyethoxyphenylphosphine- ,
lithium 1,3-dimethylnaphthoylphenylphosphine, lithium
2,8-dimethylnaphthoylphenylphosphine, lithium
1,3-dimethoxynaphthoylpheny- lphosphine, lithium 1
,3-dichloronaphthoylphenylphosphine, lithium
2,8-dimethoxynaphthoylphenylphosphine, lithium
2,4,6-trimethylpyridoylphe- nylphosphine, lithium
2,4-dimethoxyfuranoylphenylphosphine, lithium 1
,3-dimethylnaphthoylphenylphosphine, lithium
2,4,5-trimethylthienoylpheny- lphosphine.
[0075] The compounds of the formula I are, for example, selectively
obtained by reaction of acyl halides (IV) with dimetalated
arylphosphines (V): 15
[0076] Ar, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 have the
meanings described above. X is Cl or Br and M.sub.1 is Na, Li or
K.
[0077] The starting materials are advantageously reacted in the
molar ratio 1:1. A slight excess of one or other of the components,
e.g. up to 20%, is not, however, critical. In this case too the
desired product is formed, although the proportion of undesired
byproduct may be influenced.
[0078] The reaction is advantageously carried out in a solvent. In
particular, as solvents, it is possible to use ethers which are
liquid at atmospheric pressure and room temperature. Examples are
dimethyl ether, diethyl ether, methyl propyl ether,
1,2-dimethoxyethane, bis-(2-methoxyethyl) ether, dioxane or
tetrahydrofuran. Preference is given to using tetrahydrofuran.
[0079] The reaction temperatures are advantageously -60.degree. C.
to +120.degree. C., e.g. -40.degree. C. to 100.degree. C., for
example -20.degree. C. to +80.degree. C.
[0080] It is advisable to stir the reaction mixture.
[0081] It is advantageous to initially introduce the compound of
the formula V and to add dropwise the compound of the formula IV at
the temperatures given above.
[0082] Here, the compound of the formula IV can be added without a
diluent or else diluted with the reaction solvent.
[0083] If desired, the course of the reaction can be monitored
using methods customary in the art, for example NMR, for example
.sup.31P-NMR, chromatography (thin-layer, HPLC, GC) etc. In the
reactions described above, it is essential to work in an inert gas
atmosphere, e.g. with a protective gas such as argon or nitrogen,
in order to exclude atmospheric oxygen.
[0084] In order to prepare compounds of the formula I in which M is
hydrogen, the reaction given above is followed by a hydrolysis
step: 16
[0085] The procedure for such hydrolysis reactions is known to the
person skilled in the art and is carried out under generally
customary conditions. The hydrolysis of metalated primary and
secondary phosphines is described, for example, in Houben-Weyl,
XII/1, pages 56-57. Likewise conceivable is the preparation of
compounds of the formula (I) by reaction between a compound of the
formula (IV) and an alkylphosphine compound in the presence of an
acid-binding agent, such as barium carbonate, calcium carbonate or
potassium carbonate, as described, for example, in Houben-Weyl,
XII/1, pages 73-74 or in K. Issleib and R. Kummel, Z. Naturf. B
(1967), 22, 784.
[0086] The compounds of the formula I according to the invention
are identified by .sup.31P-NMR spectroscopy and are stable in the
solution under inert gas at room temperature for a number of
weeks.
[0087] The invention also provides a process for the selective
preparation of compounds of the formula I by
[0088] (1) reaction of an acyl halide of the formula IV 17
[0089] in which
[0090] Ar is as defined in claim 1, and
[0091] X is Cl or Br;
[0092] with a dimetalated arylphosphine of the formula V 18
[0093] in which
[0094] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as
defined in claim 1; and
[0095] M.sub.1 is Na, Li or K;
[0096] in the molar ratio 1:1; and
[0097] (2) where appropriate, subsequent hydrolysis if compounds of
the formula I in which M is hydrogen are to be obtained.
[0098] The acyl halides (IV) used as starting material are known
substances, some of which are available commercially, or can be
prepared by analogy with known compounds. The preparation of the
metalated arylphosphines (V) can, for example, be carried out by
reacting suitable phosphorus halides (preparation of which is known
and disclosed, for example, by W. Davies in J. Chem. Soc. (1935),
462 and J. Chem. Soc. (1944), 276 with the corresponding alkali
metal: 19
[0099] R.sub.6-R.sub.10 have the meaning given above.
[0100] Suitable as metal (M.sub.1) are lithium, sodium or
potassium. The use of mixtures of these metals is also possible. 4
to 8 molar equivalents of the alkaline metal are advantageously
used. The reaction is advantageously carried out in a solvent. In
particular, as solvents, it is possible to use ethers which are
liquid at atmospheric pressure and room temperature. Examples are
dimethyl ether, diethyl ether, methyl propyl ether,
1,2-dimethoxyethane, bis(2-methoxyethyl) ether, dioxane or
tetrahydrofuran. Preference is given to using tetrahydrofuran. The
reaction temperatures are advantageously -60.degree. C. to
+120.degree. C. The reaction is, where appropriate, carried out
with the addition of a catalyst. Suitable catalysts are aromatic
hydrocarbons with or without heteroatoms, for example naphthalene,
anthracene, phenanthrene, biphenyl, terphenyl, quaterphenyl,
triphenylene, trans-1,2-diphenylethene, pyrene, perylene,
acenaphthalene, decacyclene, quinoline, N-ethylcarbazole,
dibenzothiophene or dibenzofuran.
[0101] For the preparation of the compounds of the formula I
according to the invention in the process according to the
invention, the thus obtained compounds of the formulae (V) can be
further used without isolation.
[0102] Another conceivable method for the preparation of metalated
arylphosphines is, for example, the reaction of suitable
arylphosphines with the corresponding alkali metal hydride or an
alkyllithium compound with the exclusion of air in an inert solvent
at temperatures of e.g. -80.degree. C. to +120.degree. C.
Advantageously, 2 to 4 mol equivalents of the alkali metal hydrides
or alkyllithium compound are used. Suitable solvents are e.g.
ethers as described above, or inert solvents, such as alkanes,
cycloalkanes, or aromatic solvents such as toluene, xylene,
mesitylene.
[0103] Suitable aryl phosphines can be prepared by reduction of the
corresponding aryldichlorophosphines [Ar-P-Cl.sub.2],
arylphosphonic esters [Ar-P-O(OR').sub.2] and arylphosphonous
esters [Ar-P(OR').sub.2] using LiAlH.sub.4; SiHCl.sub.3;
Ph.sub.2SiH.sub.2 (Ph=phenyl); a) LiH, b) H.sub.2O; a)
Li/tetrahydrofuran, b) H.sub.2O or a) Na/toluene, b) H.sub.2O.
These methods are described, for example, in U.S. Pat. No.
6,020,528 (col. 5-6). Hydrogenations using LiAlH.sub.4 are given,
for example, in Helv. Chim. Acta 1966, No. 96, 842.
[0104] The compounds of the formula I are particularly suitable for
the preparation of unsymmetrical mono- and bisacylphosphines, mono-
and bisacylphosphine oxides, and mono- and bisacylphosphine
sulfides. "Unsymmetrical" means in this connection that in the
bisacylphosphines, bisacylphosphine oxides and bisacylphosphine
sulfides, two different acyl groups are present, and in the
monoacylphosphines, monoacylphosphine oxides and monoacylphosphine
sulfides, in addition to the acyl group, two different radicals are
bonded to the phosphorus atom.
[0105] Such "unsymmetrical" mono- and bisacylphosphines, mono- and
bisacylphosphine oxides, and mono- and bisacylphosphine sulfides
are, with a few exceptions, novel.
[0106] Accordingly, the invention also provides compounds of the
formula II 20
[0107] A is O or S;
[0108] x is 0 or 1;
[0109] Ar is a group 21
[0110] or Ar is cyclopentyl, cyclohexyl, naphthyl, biphenylyl,
anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, where the radicals cyclopentyl, cyclohexyl,
naphthyl, biphenylyl, anthracyl or an O-, S- or N-containing 5- or
6-membered heterocyclic ring are unsubstituted or substituted by
halogen, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
[0111] R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen;
[0112] R.sub.3, R.sub.4 and R5 independently of one another are
hydrogen, C.sub.1-C.sub.20alkyl, OR.sub.11 or halogen; or in each
case two of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4 and/or
R.sub.5 together form C.sub.1-C.sub.20alkylene which can be
interrupted by O, S or NR.sub.14;
[0113] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl;
C.sub.2-C.sub.20alkyl, which is interrupted once or more than once
by nonconsecutive O atoms and which can be substituted by OH and/or
SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
OR.sub.11, phenyl or halogen;
[0114] R.sub.11 is hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl
or C.sub.2-C.sub.20alkyl which is interrupted once or more than
once by nonconsecutive O atoms and which is unsubstituted or
substituted by OH and/or SH;
[0115] Y.sub.1 is C.sub.1-C.sub.18alkyl which is unsubstituted or
substituted by one or more phenyl; C.sub.1-C.sub.18-halogenoalkyl;
C.sub.2-C.sub.18alkyl which is interrupted once or more than once
by O or S and which can be substituted by OH and/or SH;
unsubstituted C.sub.3-C.sub.18cycloalkyl or
C.sub.3-C.sub.18cycloalkyl substituted by C.sub.1-C.sub.20alkyl,
OR.sub.11, CF.sub.3 or halogen; C.sub.2-C.sub.18alkenyl; naphthyl,
biphenylyl, anthracyl or an O-, S or N-containing 5- or 6-membered
heterocyclic ring, where the radicals naphthyl, biphenylyl,
anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring are unsubstituted or are substituted by halogen,
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
[0116] or Y.sub.1 is OR.sub.11, N(R.sub.16)(R.sub.17), 22
[0117] Y.sub.2 is a direct bond, C.sub.1-C.sub.18alkylene
optionally substituted by phenyl; unsubstituted
C.sub.4-C.sub.18-cycloalkylene or C.sub.4-C.sub.18cycloalkylene
substituted by C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or
phenyl; unsubstituted C.sub.5-C.sub.18cycloalke- nylene or
C.sub.5-C.sub.18cycloalkenylene substituted by
C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or phenyl;
unsubstituted phenylene or phenylene substituted one to four times
by C.sub.1-C.sub.12alkyl, OR.sub.11, halogen, --(CO)OR.sub.14,
--(CO)N(R.sub.12)(R.sub.13) and/or phenyl;
[0118] or Y.sub.2 is a radical 23
[0119] where these radicals are unsubstituted or are substituted
one to four times on one or both aromatic ring(s) by
C.sub.1-C.sub.12alkyl, OR.sub.11, halogen and/or phenyl;
[0120] Y.sub.3 is O, S, SO, SO.sub.2, CH.sub.2, C(CH.sub.3).sub.2,
CHCH.sub.3, C(CF.sub.3).sub.2, (CO), or a direct bond;
[0121] R.sub.12 and R.sub.13 independently of one another are
hydrogen, C.sub.1-C.sub.20alkyl, C.sub.3-C.sub.8cycloalkyl, phenyl,
benzyl or C.sub.2-C.sub.20alkyl which is interrupted once or more
than once by O or S and which is unsubstituted or substituted by OH
and/or SH; or R.sub.12 and R.sub.13 together are
C.sub.3-C.sub.5alkylene which can be interrupted by O, S or
NR.sub.14;
[0122] R.sub.14 is hydrogen, phenyl, C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by O or S and which can be substituted by OH and/or SH;
[0123] R.sub.1' and R.sub.2' independently of one another have the
same meanings as given for R.sub.1 and R.sub.2; and
[0124] R.sub.3', R.sub.4' and R.sub.5' independently of one another
have the same meanings as given for R.sub.3, R.sub.4 and
R.sub.5;
[0125] with the proviso that
[0126] if Y.sub.1 is a radical 24
[0127] naphthyl, biphenylyl, anthracyl or an O-, S- or N-containing
5- or 6-membered heterocyclic ring, this is not identical to the
other benzoyl group on the phosphorus atom.
[0128] In the compounds of the formula II, the preferred meanings
of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are analogous to
those given above for the compounds of the formula I. Preferred
R.sub.1', R.sub.2', R.sub.3', R.sub.4' and R.sub.5' likewise
correspond to those given for the radicals R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and
R.sub.10.
[0129] In the compounds of the formula II, x is preferably 1. In
particular, A is oxygen. Of particular importance are compounds of
the formula II in which Y1 is C.sub.1-C.sub.12alkyl, in particular
branched C.sub.1-C.sub.12alkyl; unsubstituted
C.sub.3-C.sub.18cycloalkyl or C.sub.3-C.sub.18cycloalkyl
substituted by C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or
halogen; or is 25
[0130] Y.sub.1 as C.sub.1-C.sub.12alkyl is preferably branched in
the .alpha.-position relative to the bond to the CO group. The
carbon atom in the .alpha.-position relative to the CO group is
preferably a tertiary carbon atom. The preferred meanings for
R.sub.1', R.sub.2', R.sub.3', R.sub.4' and R.sub.5' are analogous
to those preferred meanings of R.sub.1, R.sub.2, R.sub.3, R.sub.4
and R.sub.5 given above for formula I.
[0131] Also of interest are compounds of the formula II in which
R.sub.1, R.sub.2 and R.sub.3 are C.sub.1-C.sub.4alkyl, in
particular methyl; R.sub.1' and R.sub.2' are C.sub.1-C.sub.4alkoxy,
in particular methoxy, or chlorine; and R.sub.4, R.sub.5, R.sub.3',
R.sub.4' and R.sub.5' are hydrogen.
[0132] In preferred compounds of the formula II,
[0133] A is oxygen and x is 1;
[0134] R.sub.1 and R.sub.2 are C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, Cl or CF.sub.3;
[0135] R.sub.3 is hydrogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy;
[0136] R.sub.4 and R.sub.5 are hydrogen;
[0137] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.12alkyl;
OR.sub.11, phenyl or halogen;
[0138] R.sub.11 is hydrogen, C.sub.1-C.sub.12alkyl, cyclohexyl,
cyclopentyl, phenyl or benzyl;
[0139] Y.sub.1 is C.sub.1-C.sub.12alkyl which is unsubstituted or
substituted by one or more phenyl; or Y.sub.1 is 26
[0140] R.sub.12 and R.sub.13 independently of one another are,
C.sub.1-C.sub.12alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl or
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which is unsubstituted or substituted
by OH and/or SH; or R.sub.12 and R.sub.13 together are piperidino,
morpholino or piperazino;
[0141] R.sub.14 is hydrogen or C.sub.1-C.sub.12alkyl;
[0142] R.sub.1' and R.sub.2' have the same meanings as given for
R.sub.1 and R.sub.2; and
[0143] R.sub.3', R.sub.4' and R.sub.5' independently of one another
have the same meanings as given for R.sub.3, R.sub.4 and
R.sub.5.
[0144] Examples of preferred compounds of the formula II are
2,4,6-trimethylbenzoyl-2,6-dimethylbenzoylphenylphosphine oxide;
2,4,6-trimethylbenzoyl-2,6-diethylbenzoylphenylphosphine oxide;
2,4,6-trimethylbenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,4,6-triisopropylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,4,6-tri-tert-butylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-diphenoxymethylbenzoylphenylphosphine
oxide; 2,4,6-trimethylbenzoyl-2,3,6-trimethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,3,4,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2-phenyl-6-methylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,4,6-trimethoxybenzoylphenylphosphine
oxide; 2,4,6-trimethylbenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2,4,6-trimethylbenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosphin-
e oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphosphin-
e oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylphosphi-
ne oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphen-
ylphosphine oxide;
2,4,6-trimethylbenzoyl-2,6-dimethoxy-3,5-dichlorobenzoy-
lphenylphosphine oxide;
2,4,6-trimethylbenzoyl-2,3,6-trimethoxy-5-bromoben-
zoylphenylphosphine oxide;
2,4,6-trimethylbenzoyl-2,6-dichlorobenzoylpheny- lphosphine oxide;
2,4,6-trimethylbenzoyl-2,4,6-trichlorobenzoylphenylphosp- hine
oxide; 2,4,6-trimethylbenzoyl-2,3,6-trichlorobenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-dichloro-3-methylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2-chloro-6-methylbenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2-methoxy-3,6-dichlorobenzoylphenylphosphin-
e oxide;
2,4,6-trimethylbenzoyl-2-methoxy-6-chlorobenzoylphenylphosphine
oxide;
2,4,6-trimethylbenzoyl-2,6-bis(trifluoromethyl)benzoylphenylphosph-
ine oxide;
2,4,6-trimethylbenzoyl-2-chloro-6-methylthiobenzoylphenylphosph-
ine oxide; 2,4,6-trimethylbenzoyl-2,6-dibromobenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,6-dimethylbenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,6-diethylbenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,4,6-triisopropylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,4,6-tri-tert-butylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-diphenoxymethyl-benzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,3,6-trimethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,3,4,6-tetramethylbenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2-phenyl-6-methylbenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,4,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphenylph-
osphine oxide;
2,6-dimethoxybenzoyl-2,6-dimethoxy-3,5-dichlorobenzoylpheny-
lphosphine oxide;
2,6-dimethoxybenzoyl-2,3,6-trimethoxy-5-bromobenzoylphen-
ylphosphine oxide;
2,6-dimethoxybenzoyl-2,6-dichlorobenzoylphenylphosphine oxide;
2,6-dimethoxybenzoyl-2,4,6-trichlorobenzoylphenylphosphine oxide;
2,6-dimethoxybenzoyl-2,3,6-trichlorobenzoylphenylphosphine oxide;
2,6-dimethoxybenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-dichloro-3-methylbenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2-chloro-6-methylbenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2-methoxy-3,6-dichlorobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2-methoxy-6-chlorobenzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2,6-bis(trifluoromethyl)benzoylphenylphosphine
oxide;
2,6-dimethoxybenzoyl-2-chloro-6-methylthiobenzoylphenylphosphine
oxide; 2,6-dimethoxybenzoyl-2,6-dibromobenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,6-dimethylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,6-diethylbenzoylphenylphosphine oxide;
2,6-dichlorobenzoyl-2,4,6-trimethylbenzoylphenylphosphine oxide;
2,6-dichlorobenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,4,6-triisopropylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,4,6-tri-tert-butylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-diphenoxymethylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,3,6-trimethylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,3,4,6-tetramethylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2-phenyl-6-methylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,4,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphenylpho-
sphine oxide;
2,6-dichlorobenzoyl-2,6-dimethoxy-3,5-dichlorobenzoylphenylp-
hosphine oxide;
2,6-dichlorobenzoyl-2,3,6-trimethoxy-5-bromobenzoylphenylp-
hosphine oxide;
2,6-dichlorobenzoyl-2,4,6-trichlorobenzoylphenylphosphine oxide;
2,6-dichlorobenzoyl-2,3,6-trichlorobenzoylphenylphosphine oxide;
2,6-dichlorobenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-dichloro-3-methylbenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2-chloro-6-methylbenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2-methoxy-3,6-dichlorobenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2-methoxy-6-chlorobenzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2,6-bis(trifluoromethyl)benzoylphenylphosphine
oxide;
2,6-dichlorobenzoyl-2-chloro-6-methylthiobenzoylphenylphosphine
oxide; 2,6-dichlorobenzoyl-2,6-dibromobenzoylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethylbenzoylphenylphosphine
oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-diethylbenzoylphenylphosphine
oxide;
2,6-bis(trifluoromethyl)benzoyl-2,4,6-trimethylbenzoylphenylphosphine
oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,4,5,6-pentamethylbenzoylphenyl-
phosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,5,6-tetramethylbenzoy-
lphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,4,6-triisopropyl-
benzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,4,5,6-tetr-
amethylbenzoylphenylphosphine oxide;
2,6-bistrifluoromethylbenzoyl-tert-be- nzoylphenylphosphine
oxide(trifluoromethyl)benzoyl-2,6-tri-tert-butylbenzo-
ylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-diphenoxymeth-
ylbenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,6-trim-
ethylbenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,4,6- -tetramethyl benzoylphenyl
phosphine oxide; 2,6 -bis(trifluoromethyl)benzo- yl-2-phenyl-6-
methylbenzoylphenylphosphine oxide; 2,6-bis(trifluoromethyl-
)benzoyl-2,4,6-trimethoxybenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,6-trimethoxybenzoylphenylphosp-
hine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-diethoxybenzoylphenylphosp-
hine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethoxy-3,5-dimethylbenz-
oylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethoxy-4--
methylbenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-di-
methoxy-3-bromobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzo-
yl-2,6-dimethoxy-3-chlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphen-
ylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dimethoxy-3,5-dichl-
orobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,6-tri-
methoxy-5-bromobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzo-
yl-2,6-dichlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzo-
yl-2,4,6-trichlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)be-
nzoyl-2,3,6-trichlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl-
)benzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosphi-
ne oxide;
2,6-bis(trifluoromethyl)benzoyl-2,6-dichloro-3-methylbenzoylphen-
ylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2-chloro-6-methylbenzoy-
lphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2-methoxy-3,6-dich-
lorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2-methox-
y-6-chlorobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)benzoyl-2--
chloro-6-methylthiobenzoylphenylphosphine oxide;
2,6-bis(trifluoromethyl)b- enzoyl-2,6-dibromobenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,6-di- ethylbenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,4,6-trimethylbenz- oylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,3,4,5,6-pentamethylbenzoyl-
phenylphosphine oxide;
2,6-dimethylbenzoyl-2,3,5,6-tetramethylbenzoylpheny- lphosphine
oxide; 2,6-dimethylbenzoyl-2,4,6-triisopropylbenzoylphenylphosp-
hine oxide;
2,6-dimethylbenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,4,6-tri-tert-butylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylphosphin-
e oxide;
2,6-dimethylbenzoyl-2,6-diphenoxymethylbenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,3,6-trimethylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,3,4,6-tetramethylbenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2-phenyl-6-methylbenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,4,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphenylpho-
sphine oxide;
2,6-dimethylbenzoyl-2,6-dimethoxy-3,5-dichlorobenzoylphenylp-
hosphine oxide;
2,6-dimethylbenzoyl-2,3,6-trimethoxy-5-bromobenzoylphenylp-
hosphine oxide;
2,6-dimethylbenzoyl-2,6-dichlorobenzoylphenylphosphine oxide;
2,6-dimethylbenzoyl-2,4,6-trichlorobenzoylphenylphosphine oxide;
2,6-dimethylbenzoyl-2,3,6-trichlorobenzoylphenylphosphine oxide;
2,6-dimethylbenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-dichloro-3-methylbenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2-chloro-6-methylbenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2-methoxy-3,6-dichlorobenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2-methoxy-6-chlorobenzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2,6-bis(trifluoromethyl)benzoylphenylphosphine
oxide;
2,6-dimethylbenzoyl-2-chloro-6-methylthiobenzoylphenylphosphine
oxide; 2,6-dimethylbenzoyl-2,6-dibromobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethylbenzoylphenylphosphine
oxide; 2,3,4,6-tetramethylbenzoyl-2,6-diethylbenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,4,6-trimethylbenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphi-
ne oxide;
2,3,4,6-tetramethylbenzoyl-2,4,6-triisopropylbenzoylphenylphosph-
ine oxide;
2,3,4,6-tetramethylbenzoyl-2,4,5,6-tetramethylbenzoylphenylphos-
phine oxide;
2,3,4,6-tetramethylbenzoyI-2,4,6-tri-tert-butylbenzoylphenylp-
hosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethyl-4-tert-butylbenzoy-
lphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-diphenoxymethylbenz-
oylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,3,6-trimethylbenzoy- lphenylphosphine
oxide; 2,3,4,6-tetramethylbenzoyl-2,3,4,6-tetramethylbenz-
oylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2-phenyl-6-methylbenz-
oylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,4,6-trimethoxybenzo- ylphenylphosphine
oxide; 2,3,4,6-tetramethylbenzoyl-2,4-dimethoxybenzoylph-
enylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,3,6-trimethoxybenzoylphe- nylphosphine
oxide; 2,3,4,6-tetramethylbenzoyl-2,6-diethoxybenzoylphenylph-
osphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethoxy-2,5-dimethylbenzoy-
lphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethoxy-4-methylb-
enzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethoxy-3-br-
omobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimethoxy--
3-chlorobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dimet-
hoxy-3-chloro-3-bromobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenz-
oyl-2,6-dimethoxy-3,5-dichlorobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,3,6-trimethoxy-5-bromobenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dichlorobenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,4,6-trichlorobenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,3,6-trichlorobenzoylphenylphosphine
oxide;
2,3,4,6-tetramethylbenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphi-
ne oxide;
2,3,4,6-tetramethylbenzoyl-2,3,4,5,6-pentachlorobenzoylphenylpho-
sphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dichloro-3-methylbenzoylpheny-
lphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2-chloro-6-methylbenzoylpheny-
lphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2-methoxy-3,6-dichlorobenzoyl-
phenylphosphine oxide;
2,3,4,6-tetramethylbenzoyI-2-methoxy-6-chlorobenzoy-
lphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-bis(trifluoromethyl-
)benzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyI-2-chloro-6-methy-
lthiobenzoylphenylphosphine oxide;
2,3,4,6-tetramethylbenzoyl-2,6-dibromob- enzoylphenylphosphine
oxide; 2,4,6-trimethoxybenzoyl-2,6-dimethylbenzoylph- enylphosphine
oxide; 2,4,6-trimethoxybenzoyl-2,6-diethylbenzoylphenylphosp- hine
oxide;
2,4,6-trimethoxybenzoyl-2,4,6-trimethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphin-
e oxide;
2,4,6-trimethoxybenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,4,6-triisopropylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,4,6-tri-tertbutylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylphos-
phine oxide;
2,4,6-trimethoxybenzoyl-2,6-diphenoxymethylbenzoylphenylphosp- hine
oxide;
2,4,6-trimethoxybenzoyl-2,3,6-trimethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,3,4,6-tetramethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2-phenyl-6-methylbenzoylphenylphosphine
oxide; 2,4,6-trimethoxybenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2,4,6-trimethoxybenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosphi-
ne oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphosph-
ine oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylphos-
phine oxide;
2,4,6-trimethoxybenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoyl-
phenylphosphine oxide;
2,4,6-methoxybenzoyl-2,6-dimethoxy-3,5-dichlorobenz-
oylphenylphosphine oxide;
2,4,6-trimethoxybenzoyl-2,3,6-trimethoxy-5-bromo-
benzoylphenylphosphine oxide;
2,4,6-trimethoxybenzoyl-2,6-dichlorobenzoylp- henylphosphine oxide;
2,4,6-trimethoxybenzoyl-2,4,6-trichlorobenzoylphenyl- phosphine
oxide; 2,4,6-trimethoxybenzoyl-2,3,6-trichlorobenzoylphenylphosp-
hine oxide;
2,4,6-trimethoxybenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosph- ine
oxide;
2,4,6-trimethoxybenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosp-
hine oxide;
2,4,6-trimethoxybenzoyl-2,6-dichloro-3-methylbenzoylphenylphos-
phine oxide;
2,4,6-trimethoxybenzoyl-2-chloro-6-methylbenzoylphenylphosphi- ne
oxide;
2,4,6-trimethoxybenzoyl-2-methoxy-3,6-dichlorobenzoylphenylphosp-
hine oxide;
2,4,6-trimethoxybenzoyl-2-methoxy-6-chlorobenzoylphenylphosphi- ne
oxide;
2,4,6-trimethoxybenzoyl-2,6-bis(trifluoromethyl)benzoylphenylpho-
sphine oxide;
2,4,6-trimethoxybenzoyl-2-chloro-6-methylthiobenzoylphenylph-
osphine oxide;
2,4,6-trimethoxybenzoyl-2,6-dibromobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethylbenzoylphenylphosphin-
e oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-diethylbenzoylphenylphosphin-
e oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-trimethylbenzoylphenylphos-
phine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,4,5,6-pentamethylbenzoyl-
phenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,5,6-tetramethy-
lbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,4,6-trii-
sopropylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,4-
,5,6-tetramethylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylben-
zoyl-2,4,6-tri-tert-butylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylph-
osphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-diphenoxymethylbenzoyl-
phenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,6-trimethylben-
zoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,4,6-tetram-
ethylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2-phen-
yl-6-methylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl--
2,4,6-trimethoxybenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylben-
zoyl-2,4-dimethoxybenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylb-
enzoyl-2,3,6-trimethoxybenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethoxy-3,5-dimethylbenzoyl-
phenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethoxy-4-me-
thylbenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dim-
ethoxy-3-bromobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzo-
yl-2,6-dimethoxy-3-chlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethoxy-3-chloro-5-bromobenzoylphe-
nylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dimethoxy-3,5-dic-
hlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,6--
trimethoxy-5-bromobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylb-
enzoyl-2,6-dichlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butyl-
benzoyl-2,4,6-trichlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,3,6-trichlorobenzoylphenylphosphine
oxide; 2,6-dimethyl -4-tert-butylbenzoyl-
2,3,5,6-tetrachlorobenzoylpheny- lphosphine oxide; 2,6-dimethyl-
4-tert-butylbenzoyl-2,3,4,5,6-pentachlorob- enzoylphenylphosphine
oxide;oxide; 2,6-dimethyl- 4-tert-butylbenzyl-2, 6-dichloroxidetyl
phenylphosphine; 2,6-dimethyl -4-tert-butylbenzoyl-2,6-- methyl
benzoylphenylphosphine oxide;
ethyl-4-tert-butylbenzoyl-2-methoxy-3-
,6-dichlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl--
2-methoxy-6-chlorobenzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylb-
enzoyl-2,6-bis(trifluoromethyl)benzoylphenylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2-chloro-6-methylthiobenzoylphenylphosph-
ine oxide;
2,6-dimethyl-4-tert-butylbenzoyl-2,6-dibromobenzoylphenylphosph-
ine oxide;
2-chloro-6-methylbenzoyl-2,6-dimethylbenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,6-diethylbenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,4,6-trimethylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,3,4,5,6-pentamethylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,3,5,6-tetramethylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,4,6-triisopropylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,4,5,6-tetramethylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,4,6-tri-tert-butylbenzoylphenylphosphin-
e oxide;
2-chloro-6-methylbenzoyl-2,6-dimethyl-4-tert-butylbenzoylphenylph-
osphine oxide;
2-chloro-6-methylbenzoyl-2,6-diphenoxymethylbenzoylphenylph-
osphine oxide;
2-chloro-6-methylbenzoyl-2,3,6-trimethylbenzoylphenylphosph- ine
oxide;
2-chloro-6-methylbenzoyl-2,3,4,6-tetramethylbenzoylphenylphosph-
ine oxide;
2-chloro-6-methylbenzoyl-2-phenyl-6-methylbenzoylphenylphosphin- e
oxide;
2-chloro-6-methylbenzoyl-2,4,6-trimethoxybenzoylphenylphosphine
oxide; 2-chloro-6-methylbenzoyl-2,4-dimethoxybenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,3,6-trimethoxybenzoylphenylphosphine
oxide; 2-chloro-6-methylbenzoyl-2,6-diethoxybenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylphenylphosphine
oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-4-methylbenzoylphenylphosph-
ine oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-3-bromobenzoylphenylphos-
phine oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-3-chlorobenzoylphenylp-
hosphine oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-3-chloro-5-bromoben-
zoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,6-dimethoxy-3,5-dich-
lorobenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,3,6-trimethox-
y-5-bromobenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,6-dichlo- robenzoylphenylphosphine
oxide; 2-chloro-6-methylbenzoyl-2,4,6-trichlorobe-
nzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,3,6-trichlorobenzoy- lphenylphosphine
oxide; 2-chloro-6-methylbenzoyl-2,3,5,6-tetrachlorobenzoy-
lphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,3,4,5,6-pentachlorobenz-
oylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,6-dichloro-3-methylbe-
nzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2-methoxy-3,6-dichlor-
obenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2-methoxy-6-chloro- benzoylphenylphosphine
oxide; 2-chloro-6-methylbenzoyl-2,6-bis(trifluorome-
thyl)benzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2-chloro-6-met-
hylthiobenzoylphenylphosphine oxide;
2-chloro-6-methylbenzoyl-2,6-dibromob- enzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethylbenzoyl- phenylphosphine
oxide; 2-chloro-6-methoxybenzoyl-2,6-diethylbenzoylphenylp-
hosphine oxide;
2-chloro-6-methoxybenzoyl-2,4,6-trimethylbenzoylphenylphos- phine
oxide;
2-chloro-6-methoxybenzoyl-2,3,4,5,6-pentamethylbenzoylphenylp-
hosphine oxide;
2-chloro-6-methoxybenzoyl-2,3,5,6-tetramethylbenzoylphenyl-
phosphine oxide;
2-chloro-6-methoxybenzoyl-2,4,6-triisopropylbenzoylphenyl-
phosphine oxide;
2-chloro-6-methoxybenzoyl-2,4,5,6-tetramethylbenzoylpheny-
lphosphine oxide;
2-chloro-6-methoxybenzoyl-2,4,6-tri-tert-butylbenzoylphe-
nylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethyl-4-tert-butylben-
zoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-diphenoxymethylbe-
nzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,3,6-trimethylbenzo- ylphenylphosphine
oxide; 2-chloro-6-methoxybenzoyl-2,3,4,6-tetramethylbenz-
oylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2-phenyl-6-methylbenzo- ylphenylphosphine
oxide; 2-chloro-6-methoxybenzoyl-2,4,6-trimethoxybenzoyl-
phenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,4-dimethoxybenzoylpheny- lphosphine
oxide; 2-chloro-6-methoxybenzoyl-2,3,6-trimethoxybenzoylphenylp-
hosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-diethoxybenzoylphenylphosphi- ne
oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethoxy-3,5-dimethylbenzoylpheny-
lphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethoxy-4-methylbenzoylp-
henylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethoxy-3-bromobenzo-
ylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethoxy-3-chlorob-
enzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dimethoxy-3-chl-
oro-5-bromobenzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dim-
ethoxy-3,5-dichlorobenzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-
-2,3,6-trimethoxy-5-bromobenzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dichlorobenzoylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,4,6-trichlorobenzoylphenylphosphine
oxide;
2-chloro-6-methoxybenzoyl-2,3,6-trichlorobenzoylphenylphosphine
oxide;
2-chloro-6-methoxybenzoyl-2,3,5,6-tetrachlorobenzoylphenylphosphine
oxide;
2-chloro-6-methoxybenzoyl-2,3,4,5,6-pentachlorobenzoylphenylphosph-
ine oxide;
2-chloro-6-methoxybenzoyl-2,6-dichloro-3-methylbenzoylphenylpho-
sphine oxide;
2-chloro-6-methoxybenzoyl-2-chloro-6-methylbenzoylphenylphos- phine
oxide;
2-chloro-6-methoxybenzoyl-2-methoxy-3,6-dichlorobenzoylphenyl-
phosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-bis(trifluoromethyl)benzoyl-
phenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2-chloro-6-methylthiobenz-
oylphenylphosphine oxide;
2-chloro-6-methoxybenzoyl-2,6-dibromobenzoylphen- ylphosphine
oxide.
[0145] The compounds of the formula II where x=0 (formula II') are
obtained by reacting an arylacrylphosphine of the formula I with an
acid halide of the formula (IV): 27
[0146] The meanings of the radicals Ar, R.sub.6-R.sub.10, M, X, A,
x and Y.sub.1 are as described above.
[0147] The starting materials are advantageously reacted in a molar
ratio of 1:1. A slight excess of one or other of the components,
e.g. up to 20%, is, however, not critical. The desired product
forms in this case too, although the portion of undesired byproduct
can be influenced. The reaction conditions for this reaction
correspond to those given above in connection with the preparation
of the compounds of the formula I.
[0148] Compounds of the formula II where x=1 and A is oxygen are
prepared by oxidation of the compounds of the formula (II'), and
compounds of the formula II where A is sulfur are prepared by
sulfurization of the compounds of the formula II': 28
[0149] Prior to the oxidation or sulfurization, the phosphine II'
can be isolated by customary separation methods familiar to the
person skilled in the art, although the reaction can also be
carried out immediately after the previous reaction step without
isolation of the phosphine. During the preparation of the oxide,
the oxidation of the phosphine is carried out using oxidizing
agents customary in the art. Suitable oxidizing agents are
primarily hydrogen peroxide and organic peroxy compounds, for
example peracetic acid or t-butyl hydroperoxide, air or pure
oxygen.
[0150] The oxidation is advantageously carried out in solution.
Suitable solvents are aromatic hydrocarbons, for example benzene,
toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or
aliphatic hydrocarbons, e.g. alkanes and alkane mixtures, such as
petroleum ether, hexane or cyclohexane. Further suitable examples
are dimethyl ether, diethyl ether, methyl propyl ether,
1,2-dimethoxyethane, bis(2-methoxyethyl) ether, dioxane or
tetrahydrofuran. Preference is given to using toluene.
[0151] The reaction temperature during the oxidation is
advantageously kept between 0.degree. and 120.degree. C.,
preferably between 20.degree. and 80.degree. C.
[0152] The reaction products of the formula (II) can be isolated
and purified by customary processing measures familiar to the
person skilled in the art.
[0153] The preparation of the respective sulfide is carried out by
reaction with sulfur. The bisacylphosphines (II') are here reacted
with an equimolar to 2-fold molar amount of elemental sulfur e.g.
without a diluent or optionally in a suitable inert organic
solvent. Examples of suitable solvents are those described for the
oxidation reaction. It is, however, also possible to use, for
example, aliphatic or aromatic ethers, for example dibutyl ether,
dioxane, diethylene glycol dimethyl ether or diphenyl ether at
temperatures of from 20.degree. to 250.degree. C., preferably
60.degree. to 120.degree. C. The resulting bisacylphosphine
sulfide, or its solution is advantageously freed from any elemental
sulfur which may still be present by filtration. Following removal
of the solvent, the bisacylphosphine sulfide can be isolated in
pure form by distillation, recrystallization or chromatographic
separation methods.
[0154] It is advantageous to carry out all of the reactions
described above with the exclusion of air in an inert gas
atmosphere, e.g. under nitrogen or argon gas. Moreover, stirring of
the respective reaction mixture is advantageously appropriate.
[0155] The invention likewise provides a process for the
preparation of the compounds of the formula II, from compounds of
the formula I as starting materials, by
[0156] (1) reaction of an acyl halide of the formula IV 29
[0157] in which
[0158] Ar is as defined above, and
[0159] X is Cl or Br;
[0160] with a dimetalated arylphosphine of the formula V 30
[0161] in which
[0162] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as
defined above; and
[0163] M.sub.1 is Na, Li or K;
[0164] in the molar ratio of approximately 1:1;
[0165] (2) subsequent reaction of the product with an acyl halide
of the formula IVa 31
[0166] in which
[0167] Y.sub.1 is as defined above; and
[0168] X is as defined above;
[0169] with the proviso that the acyl halide of the formula IV is
not identical to the acyl halide of the formula IVa;
[0170] in the molar ratio of approximately 1:1; and,
[0171] (3) if compounds of the formula II in which A is oxygen or
sulfur are to be obtained, subsequent oxidation or sulfurization of
the resulting phosphine compounds.
[0172] Furthermore, the compounds of the formula II can also be
prepared by reacting the compound of the formula I with phosgene,
analogously to the description in "W. A. Henderson et al., J. Am.
Chem. Soc. 1960, 82, 5794" or "GB 904 086" or in "Organic
Phosphorous Compounds, Editors: R. M. Kosolapoff and L. Maier,
Wiley-Interscience 1972, Vol.1, page 28" or "Houben-Weyl, Methoden
der Organischen Chemie, Vol. XII/1, page 201", to give the
corresponding phosphinechloride (Ii). Compounds of the formula (Ii)
can, as described in "Organic Phosphorous Compounds, Editors: R. M.
Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.4, pages
268-269", be reacted with alcohols to give compounds of the formula
(Iii), which are then reacted directly with an acyl halide of the
formula IVa, in analogy with the description in U.S. Pat. No.
4,324,744 (by Michaelis-Arbuzov reaction), to give compounds of the
formula II. In this case, the oxidation step is superfluous. 32
[0173] Ar and Y.sub.1 are as defined in claims 1 and 2, although Ar
and Y.sub.1 are not the same radical; X is Cl or Br; M and R.sub.6
are likewise as defined in claim 1, and R is any alcohol radical,
e.g. C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.8cycloalkyl, for example
cyclopentyl or cyclohexyl, or benzyl.
[0174] Compounds of the formula (Iii) can be oxidized using
suitable oxidizing agents, such as peroxo acids, hydrogen peroxide
or hydrogen peroxide/urea, to give the corresponding phosphinic
esters (Iiiii): 33
[0175] This preparation process is novel.
[0176] The invention thus also provides a process for the
preparation of compounds of the formula II in which A is oxygen and
x is 1, by
[0177] (1) reaction of the compounds of the formula (I), 34
[0178] in which
[0179] Ar, M, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
as defined above, with phosgene to give the corresponding phosphine
chloride (Ii) 35
[0180] (2) subsequent reaction with an alcohol to give the compound
of the formula (Iii) 36
[0181] R is the radical of an alcohol, in particular
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.8cycloalkyl or benzyl; and
[0182] (3) reaction of the resulting compound of the formula (Iii)
with an acyl halide 37
[0183] in which
[0184] Y.sub.1 is as defined above, but is not identical to Ar from
the formula (I), and
[0185] X is Cl or Br,
[0186] to give the compound of the formula II.
[0187] As already mentioned, slightly unsymmetrical
monoacylphosphines, monoacylphosphine oxides or monoacylphosphine
sulfides can also be obtained from the compounds of the formula
I.
[0188] The invention thus also provides compounds of the formula
III 38
[0189] in which
[0190] A is O or S;
[0191] x is O or 1;
[0192] Ar is a group 39or Ar is cyclopentyl, cyclohexyl, naphthyl,
biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered
heterocyclic ring, where the radicals cyclopentyl, cyclohexyl,
naphthyl, biphenylyl, anthracyl or O-, S- or N-containing 5- or
6-membered heterocyclic ring are unsubstituted or are substituted
by halogen, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
[0193] R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.20alkyl, OR.sub.11, CF.sub.3 or halogen;
[0194] R.sub.3, R.sub.4 and R.sub.5 independently of one another
are hydrogen, C.sub.1-C.sub.20alkyl, OR.sub.11 or halogen or in
each case two of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4
and/or R.sub.5 together form a C.sub.1-C.sub.20alkylene which can
be interrupted by O, S or NR.sub.14;
[0195] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.20alkyl;
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which is unsubstituted or substituted
by OH and/or SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
are OR.sub.11; halogen or unsubstituted phenyl or phenyl
substituted once or more than once by C.sub.1-C.sub.4alkyl;
[0196] R.sub.11 is hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl
or C.sub.2-C.sub.20alkyl which is interrupted once or more than
once by nonconsecutive O atoms and which is unsubstituted or
substituted by OH and/or SH;
[0197] Z.sub.1 is C.sub.1-C.sub.24alkyl which is unsubstituted or
substituted once or more than once by OR.sub.15,
[0198] SR.sub.15, N(R.sub.16)(R.sub.17), phenyl, halogen, CN, NCO,
40
[0199] and/or 41
[0200] or Z.sub.1 is C.sub.2-C.sub.24alkyl which is interrupted
once or more than once by O, S or NR.sub.14 and which is
unsubstituted or substituted by OR.sub.15, SR.sub.15,
N(R.sub.16)(R.sub.17), phenyl, halogen, 42
[0201] and/or 43
[0202] or Z, is C.sub.1-C.sub.24alkoxy, which is substituted once
or more than once by phenyl, CN, NCO, 44
[0203] and/or 45
[0204] or Z.sub.1 46
[0205] or Z.sub.1 is unsubstituted C.sub.3-C.sub.24-cycloalkyl or
C.sub.3-C.sub.24cycloalkyl substituted by C.sub.1-C.sub.20alkyl,
OR.sub.11, CF3 or halogen; unsubstituted C.sub.2-C.sub.24alkenyl or
C.sub.2-C.sub.24-alkenyl substituted by C.sub.6-C.sub.12aryl, CN,
(CO)OR.sub.15 or (CO)N(R.sub.18).sub.2; or Z.sub.1 is
C.sub.3-C.sub.24cycloalkenyl or is one of the radicals 47
[0206] (w); or Z.sub.1 is C.sub.1-C.sub.24alkylthio, in which the
alkyl radical is uninterrupted or is interrupted once or more than
once by nonconsecutive O or S, and is unsubstituted or substituted
by OR.sub.15, SR.sub.15 and/or halogen;
[0207] A.sub.1 is O, S or NR.sub.18a;
[0208] Z.sub.2 is C.sub.1-C.sub.24alkylene;
C.sub.2-C.sub.24alkylene interrupted once or more than once by O,
S, or NR.sub.14;
[0209] C.sub.2-C.sub.24alkenylene; C.sub.2-C.sub.24alkenylene
interrupted once or more than once by O, S, or NR.sub.14;
C.sub.3-C.sub.24cycloalkyle- ne; C.sub.3-C.sub.24cycloalkylene
interrupted once or more than once by O, S, or NR.sub.14;
C.sub.3-C.sub.24cycloalkylene; C.sub.3-C.sub.24cycloalke- nylene
interrupted once or more than once by O, S, or NR.sub.14;
[0210] where the radicals C.sub.1-C.sub.24alkylene,
C.sub.2-C.sub.24alkylene, C.sub.2-C.sub.24alkenylene,
C.sub.3-C.sub.24cycloalkylene and C.sub.3-C.sub.24cycloalkenylene
are unsubstituted or are substituted by OR.sub.11, SR.sub.11,
N(R.sub.12)(R.sub.13) and/or halogen; or Z.sub.2 is one of the
radicals 48
[0211] where these radicals are unsubstituted or are substituted on
the aromatic by C.sub.1-C.sub.20alkyl; C.sub.2-C.sub.20alkyl which
is interrupted once or more than once by non-consecutive O atoms
and which is unsubstituted or substituted by OH and/or SH;
OR.sub.11, SR.sub.11, N(R.sub.12)(R.sub.13), phenyl, halogen,
NO.sub.2, CN, (CO)--OR.sub.18, (CO)--R.sub.18,
(CO)--N(R.sub.18).sub.2, SO.sub.2R.sub.24, OSO.sub.2R.sub.24,
CF.sub.3 and/or CCl.sub.3; or Z.sub.2 is a group 49
[0212] Z.sub.3 is CH.sub.2, CHCH.sub.3 or C(CH.sub.3).sub.2;
[0213] Z.sub.4 is S, O, CH.sub.2, C.dbd.O, NR.sub.14 or a direct
bond;
[0214] Z.sub.5 is S, O, CH.sub.2, CHCH.sub.3, C(CH.sub.3).sub.2,
C(CF.sub.3).sub.2, CO, SO, SO.sub.2;
[0215] Z.sub.6 and Z.sub.7 independently of one another are
CH.sub.2, CHCH.sub.3 or C(CH.sub.3).sub.2;
[0216] r is 0, 1 or 2;
[0217] s is a number from 1 to 12;
[0218] q is a number from 0 to 50;
[0219] t and p are each a number from 0 to 20;
[0220] E, G, G.sub.3 and G.sub.4 independently of one another are
unsubstituted C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkyl
substituted by halogen, or are unsubstituted phenyl or phenyl
substituted by one or more C.sub.1-C.sub.4alkyl;
[0221] R.sub.11a is C.sub.1-C.sub.20alkyl substituted once or more
than once by OR.sub.15, halogen or 50
[0222] or is C.sub.2-C.sub.20alkyl interrupted once or more than
once by nonconsecutive O atoms and which optionally is substituted
once or more than once by OR.sub.15, halogen or 51
[0223] or is C.sub.2-C.sub.20alkenyl or C.sub.3-C.sub.12alkynyl; or
is C.sub.3-C.sub.12cycloalkyl substituted once or more than once by
C.sub.1-C.sub.6alkyl or halogen; or is C.sub.6-C.sub.12aryl
optionally substituted once or more than once by halogen, NO.sub.2,
C.sub.1-C.sub.6alkyl, OR.sub.11 or C(O)OR.sub.18; or is
C.sub.7-C.sub.16arylalkyl or C.sub.8-C.sub.16arylcycloalkyl;
[0224] R.sub.14 is hydrogen, phenyl, C.sub.1-C.sub.12alkoxy,
C.sub.1-C.sub.12alkyl or C.sub.2-C.sub.12alkyl which is interrupted
once or more than once by O or S and which is unsubstituted or
substituted by OH and/or SH;
[0225] R.sub.15 has one of the meanings given for R.sub.11 or is a
radical 52
[0226] R.sub.16 and R.sub.17 independently of one another have one
of the meanings given for R.sub.12 or are a radical 53
[0227] R.sub.18 is hydrogen, C.sub.1-C.sub.24alkyl,
C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl;
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH;
[0228] R.sub.18a and R.sub.18b independently of one another are
hydrogen, C.sub.1-C.sub.20alkyl which is substituted once or more
than once by OR.sub.15, halogen, styryl, methylstyryl,
--N.dbd.C.dbd.A or 54
[0229] or are C.sub.2-C.sub.20alkyl which is interrupted once or
more than once by nonconsecutive O atoms and which optionally is
substituted once or more than once by OR.sub.15, halogen, styryl,
methylstyryl or 55
[0230] or are C.sub.2-C.sub.12alkenyl; or are
C.sub.5-C.sub.12cycloalkyl substituted by --N.dbd.C.dbd.A or
--CH.sub.2--N.dbd.C.dbd.A and optionally additionally once or more
than once substituted by C.sub.1-C.sub.4alkyl; or are
C.sub.6-C.sub.12aryl optionally once or more than once substituted
by halogen, NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.4alkenyl,
OR.sub.11, --N.dbd.C.dbd.A, --CH.sub.2--N.dbd.C.dbd.A or
C(O)OR.sub.18; or are C.sub.7-C.sub.16arylalkyl; or both groups
R.sub.18a and R.sub.18b together are
C.sub.8-C.sub.16arylcycloalkyl; or R.sub.18a and R.sub.18b
independently of one another are 56
[0231] Y.sub.3 is O, S, SO, SO.sub.2, CH.sub.2, C(CH.sub.3).sub.2,
CHCH.sub.3, C(CF.sub.3).sub.2, (CO), or a direct bond;
[0232] R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 have one
of the meanings given for R.sub.6 or are NO.sub.2, CN,
SO.sub.2R.sub.24, OSO.sub.2R.sub.24, CF.sub.3, CCl.sub.3 or
halogen;
[0233] R.sub.24 is C.sub.1-C.sub.12alkyl, halogen-substituted
C.sub.1-C.sub.12alkyl, phenyl, or phenyl substituted by OR.sub.15
and/or SR.sub.15;
[0234] with the proviso that
[0235] if Z.sub.1 is a radical 57
[0236] this is not identical to the other aromatic radical 58
[0237] on the phosphorus atom.
[0238] In the compounds of the formula III, the preferred meanings
of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are analogous to
those given above for the compounds of the formula I.
[0239] Preferred R.sub.19, R.sub.20, R.sub.21, R.sub.22 and
R.sub.23 are defined identically to the preferred R.sub.6, R.sub.7,
R.sub.8, R.sub.9 and R.sub.10 in formula I.
[0240] A in formula III is, in particular, oxygen and x is
preferably 1.
[0241] Preference is given to compounds of the formula III in which
A is O; and x is 1; R.sub.1 and R.sub.2 independently of one
another are C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, CF.sub.3
or halogen; R.sub.3, R.sub.4 and R.sub.5 independently of one
another are hydrogen, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy
or halogen; R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.12alkyl;
C.sub.2-C.sub.12alkyl which is interrupted once or more than once
by nonconsecutive O atoms and which is unsubstituted or substituted
by OH and/or SH; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
are OR.sub.11, SR.sub.11, N(R.sub.12)(R.sub.13), phenyl or halogen;
R.sub.11 is C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.8cycloalkyl,
phenyl, benzyl or C.sub.2-C.sub.12alkyl which is interrupted once
or more than once by nonconsecutive O atoms and which is
unsubstituted or substituted by OH and/or SH; R.sub.12 and R.sub.13
independently of one another are hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.3-C.sub.6cycloalkyl, phenyl, benzyl or C.sub.2-C.sub.12alkyl
which is interrupted once or more than once by O or S and which is
unsubstituted or substituted by OH and/or SH; or R.sub.12 and
R.sub.13 together are piperidino, morpholino or piperazino; Z.sub.1
is C.sub.1-C.sub.18alkyl which is unsubstituted or mono- or
polysubstituted by OR.sub.15, SR.sub.15, N(R.sub.16)(R.sub.17),
phenyl, halogen, CN, NCO, 59
[0242] and/or 60
[0243] or Z.sub.1 is C.sub.2-C.sub.18alkyl which is interrupted
once or more than once by O, S or NR.sub.14 and which is
unsubstituted or substituted by OR.sub.15, SR.sub.15,
N(R.sub.16)(R.sub.17), phenyl, halogen, 61
[0244] and/or 62
[0245] or Z.sub.1 is C.sub.1-C.sub.18alkoxy which is substituted
once or more than once by phenyl, CN, NCO, 63
[0246] and/or 64
[0247] or Z.sub.1 is 65
[0248] or Z.sub.1 is unsubstituted C.sub.3-C.sub.12cycloalkyl or
C.sub.3-C.sub.12cycloalkyl substituted by C.sub.1-C.sub.20alkyl,
OR.sub.11, CF.sub.3 or halogen; unsubstituted
C.sub.2-C.sub.12alkenyl or C.sub.2-C.sub.12alkenyl substituted by
phenyl, naphthyl, biphenylyl; or is C.sub.3-C.sub.12cycloalkenyl,
or Z.sub.1 is one of the radicals (f), (g), (h), (i), (k), (l),
(m), (n), (o), (p) (q) or (t); Z.sub.2 is C.sub.1-C.sub.18alkylene;
C.sub.2-C.sub.12alkylene interrupted once or more than once by O,
S, or NR.sub.14, C.sub.2-C.sub.12alkenylene;
C.sub.2-C.sub.12alkenylene interrupted once or more than once by O,
S, or NR.sub.14; C.sub.3-C.sub.12cycloalkylene;
C.sub.3-C.sub.12cycloalkylene interrupted once or more than once by
O, S, or NR.sub.14; C.sub.3-C.sub.12cycloalkylene;
C.sub.3-C.sub.12cycloalkenylene interrupted once or more than once
by O, S, or NR.sub.14; where the radicals C.sub.1-C.sub.18alkylene,
C.sub.2-C.sub.12alkylene, C.sub.2-C.sub.12alkenylene,
C.sub.3-C.sub.12cycloalkylene and C.sub.3-C.sub.12cycloalkenylene
are unsubstituted or are substituted by OR.sub.11, SR.sub.11,
N(R.sub.12)(R.sub.13) and/or halogen; or Z.sub.2 is one of the
radicals 66
[0249] these radicals being unsubstituted or substituted on the
aromatic by C.sub.1-C.sub.12alkyl; C.sub.2-C.sub.12alkyl which is
interrupted once or more than once by nonconsecutive O atoms and
which is unsubstituted or substituted by OH and/or SH; OR.sub.11,
SR.sub.11, N(R.sub.12)(R.sub.13), phenyl, halogen, NO.sub.2, CN,
(CO)--OR.sub.18, (CO)--R.sub.18, (CO)--N(R.sub.18).sub.2,
SO.sub.2R.sub.24, and/or CF.sub.3; or Z.sub.2 is a group (r);
Z.sub.3 is CH.sub.2, CHCH.sub.3 or C(CH.sub.3).sub.2; Z.sub.4 is S,
0, CH.sub.2, C=O, NR.sub.14 or a direct bond; Z.sub.5 is S, O,
CH.sub.2, CHCH.sub.3, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, CO, SO,
SO.sub.2; Z.sub.6 and Z.sub.7 independently of one are CH.sub.2,
CHCH.sub.3 or C(CH.sub.3).sub.2; r is 0, 1 or 2; s is a number from
1 to 12; q is a number from 0 to 50; t and p are in each case a
number from 0 to 20; E, G, G.sub.3 and G.sub.4 independently of one
another are C.sub.1-C.sub.12alkyl, or are unsubstituted phenyl or
phenyl substituted by one or more C.sub.1-C.sub.4alkyl; R.sub.14 is
hydrogen, phenyl, C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy,
R.sub.15 has one of the meanings given for R.sub.1, or is a radical
67
[0250] R.sub.16 and R.sub.17 independently of one another have one
of the meanings given for R.sub.12 or are a radical 68
[0251] R.sub.18 is hydrogen, C.sub.1-C.sub.24alkyl,
C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl;
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by O or S and which is unsubstituted or substituted by OH;
R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 have one of the
meanings given for R.sub.6 or are NO.sub.2, CN, SO.sub.2R.sub.24,
CF.sub.3, or halogen; R.sub.24 is C.sub.1-C.sub.12alkyl substituted
C.sub.1-C.sub.12alkyl, phenyl, or is phenyl substituted by
OR.sub.15 and/or SR,.sub.5.
[0252] In the compounds of the formula III, R.sub.6, R.sub.7,
R.sub.8, R.sub.9 and R.sub.10 are preferably hydrogen,
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy or chlorine, in
particular hydrogen.
[0253] R.sub.12 and R.sub.13 in the compounds of the formula III
are preferably C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or
R.sub.12 and R.sub.13 together form a morpholino ring.
[0254] Also of interest are compounds of the formula III in which A
is O; and x is 1; R.sub.1 and R.sub.2 independently of one another
are C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, CF.sub.3 or
halogen; R.sub.3, R.sub.4 and R.sub.5 independently of one another
are hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy or
chlorine; R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently of one another are hydrogen, C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.6alkyl; or R.sub.6, R.sub.7, R.sub.8, R.sub.9 and
R.sub.10 are phenyl or halogen; R.sub.11 is C.sub.1-C.sub.8alkyl,
cyclopentyl, cyclohexyl, phenyl, benzyl or C.sub.2-C.sub.6alkyl
which is interrupted once or twice by nonconsecutive O atoms and
which is unsubstituted or substituted by OH; Z.sub.1 is
C.sub.1-C.sub.12alkyl which is unsubstituted or is mono- or
polysubstituted by OR.sub.15, SR.sub.15, N(R.sub.16)(R.sub.17),
phenyl, halogen, CN, NCO, 69
[0255] and/or 70
[0256] or Z.sub.1 is C.sub.2-C.sub.12alkyl which is interrupted
once or more than once by O, S or NR.sub.14 and which is
unsubstituted or substituted by OR.sub.15, SR.sub.15, N(R.sub.16)(
R.sub.17), phenyl, halogen, 71
[0257] and/or 72
[0258] or Z.sub.1 C.sub.1-C.sub.12alkoxy which is mono- or
polysubstituted by phenyl, CN, NCO, 73
[0259] and/or 74
[0260] or Z.sub.1 is in each case unsubstituted or
C.sub.1-C.sub.20alkyl-, OR.sub.11-, CF.sub.3- or
halogen-substituted cyclopentyl or cyclohexyl; or Z.sub.1 is
unsubstituted C.sub.2-C.sub.12alkenyl or C.sub.2-C.sub.12alkenyl
substituted by phenyl, biphenylyl or naphthyl; or
C.sub.5-C.sub.12cycloalkenyl is or stands for one of the radicals
(f), (g), (h), (i), (k), (l), (m), (n), (o), (p) (q) or (t);
Z.sub.2 is C.sub.1-C.sub.12alkylene; C.sub.2-C.sub.12alkenyl
interrupted once or more than once by 0;
C.sub.2-C.sub.12alkenylene; C.sub.2-C.sub.12alkenyle- ne
interrupted once or than once by O; C.sub.5-C.sub.8cycloalkylene;
C.sub.3-C.sub.5cycloalkylene interrupted by O, S, or NR.sub.14;
C.sub.5-C.sub.8cycloalkenylene; C.sub.3-C.sub.5cycloalkenylene
interrupted by O, S, or NR.sub.14; where the radicals
C.sub.1-C.sub.12alkylene, C.sub.2-C.sub.12alkylene,
C.sub.2-C.sub.12alkenylene, C.sub.5-C.sub.8-cycloalkylene and
C.sub.3-C.sub.8-cycloalkenylene are unsubstituted or are
substituted by OR.sub.11; or Z.sub.2 is one of the radicals 75
[0261] where these radicals are unsubstituted or are substituted on
the aromatic by C.sub.1-C.sub.4alkyl, OR.sub.11, phenyl,
(CO)--OR.sub.18, (CO)--R.sub.18 and/or (CO)-N(R.sub.18).sub.2; or
Z.sub.2 is a group (r); Z.sub.3 is CH.sub.2, CHCH.sub.3 or
C(CH.sub.3).sub.2; Z.sub.4 is S, O, CH.sub.2, C.dbd.O, NR.sub.14 or
a direct bond; Z.sub.5 is O, CH.sub.2, CHCH.sub.3,
C(CH.sub.3).sub.2, C(CF.sub.3).sub.2; Z.sub.6 and Z.sub.7
independently of one another are CH.sub.2, CHCH.sub.3 or
C(CH.sub.3).sub.2; r is 0, 1 or 2; s is a number from 1 to 12; q is
a number from 0 to 50; t and p are in each case a number from 0 to
20; E, G, G.sub.3 and G.sub.4 independently of one another are
C.sub.1-C.sub.12alkyl, or are unsubstituted phenyl or phenyl
substituted by one or more C.sub.1-C.sub.4alkyl; R.sub.14 is
hydrogen, phenyl or C.sub.1-C.sub.4alkyl; R.sub.15 has one of the
meanings given for R.sub.11 or is a radical 76
[0262] R.sub.16 and R.sub.17 independently of one another have one
of the meanings given for R.sub.12 or are a radical 77
[0263] R.sub.18 is hydrogen, C.sub.1-C.sub.24alkyl,
C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.8cycloalkyl, phenyl, benzyl,
C.sub.2-C.sub.20alkyl which is interrupted once or more than once
by O or S and which is optionally substituted by OH; R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 have one of the meanings
given for R.sub.6, or are NO.sub.2, CN, CF.sub.3 or halogen.
[0264] Examples of compounds of the formula III according to the
invention are 2,4,6-trimethylbenzoylphenylmethylphosphine oxide;
2,4,6-trimethylbenzoylphenylethylphosphine oxide;
2,4,6-trimethylbenzoylp- henylpropylphosphine oxide;
2,4,6-trimethylbenzoylphenylbutylphosphine oxide;
2,4,6-trimethylbenzoylphenylpentylphosphine oxide;
2,4,6-trimethylbenzoylphenylhexylphosphine oxide;
2,4,6-trimethylbenzoylp- henylheptylphosphine oxide;
2,4,6-trimethylbenzoylphenyloctylphosphine oxide;
2,4,6-trimethylbenzoylphenyldodecylphosphine oxide;
2,4,6-trimethylbenzoylphenylisopropylphosphine oxide;
2,4,6-trimethylbenzoylphenylisobutylphosphine oxide;
2,4,6-trimethylbenzoylphenylamylphosphine oxide;
2,4,6-trimethylbenzoylph- enyl-2-ethylhexylphosphine oxide;
2,4,6-trimethylbenzoylphenyl-tert-butyl-- phosphine oxide;
2,4,6-trimethylbenzoylphenyl-1-methylpropylphosphine oxide;
2,4,6-trimethylbenzoylphenylisopentylphosphine oxide;
2,4,6-trimethylbenzoylphenylmethoxyethoxy-phosphine oxide;
2,4,6-trimethylbenzoylphenylbenzylphosphine oxide;
2,4,6-trimethylbenzoylphenyl-2,4,4-trimethylpentylphosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propionic methyl ester phosphine
oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic ethyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic propyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic
butyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propionic pentyl ester phosphine
oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic hexyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic octyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic
decyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propionic dodecyl ester phosphine
oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic isopropyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic isobutyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic
amyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propionic 2-ethylhexyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic
tert-butyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propionic 1-methylpropyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic isopentyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenyl-2-propionic
methoxyethoxy ester phosphine oxide;
2,4,6-trimethylbenzoylphenyl-2-propi- onic benzyl ester phosphine
oxide; 2,4,6-trimethylbenzoylphenyl-2-propioni- c
2,4,4-trimethylpentyl ester phosphine oxide;
2,4,6-trimethylbenzoylpheny- lacetic methyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic ethyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic propyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic butyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic pentyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic hexyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic octyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic decyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic dodecyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic isopropyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic isobutyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic amyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic 2-ethylhexyl ester phosphine
oxide; 2,4,6-trimethylbenzoylphenylacetic tert-butyl ester
phosphine oxide; 2,4,6-trimethylbenzoylphenylacetic 1-methyl propyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenylacetic isopentyl
ester phosphine oxide; 2,4,6-trimethylbenzoylphenylacetic
methoxyethoxy ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic benzyl ester phosphine oxide;
2,4,6-trimethylbenzoylphenylacetic 2,4,4-trimethylpentyl ester
phosphine oxide; 2,6-dimethylbenzoylphenylmethylphosphine oxide;
2,6-dimethylbenzoylphenylethylphosphine oxide;
2,6-dimethylbenzoylphenylp- ropylphosphine oxide;
2,6-dimethylbenzoylphenylbutylphosphine oxide;
2,6-dimethylbenzoylphenylpentylphosphine oxide;
2,6-dimethylbenzoylphenyl- hexylphosphine oxide;
2,6-dimethylbenzoylphenylheptylphosphine oxide;
2,6-dimethylbenzoylphenyloctylphosphine oxide; 2,6-dimethylbenzoy
lphenyldodecylphosphine oxide;
2,6-dimethylbenzoylphenylisopropylphosphin- e oxide;
2,6-dimethylbenzoylphenylisobutylphosphine oxide;
2,6-dimethylbenzoylphenylamylphosphine oxide;
2,6-dimethylbenzoylphenyl-2- -ethylhexylphosphine oxide;
2,6-dimethylbenzoylphenyl-tert-butylphosphine oxide;
2,6-dimethylbenzoylphenyl-s -methylpropylphosphine oxide;
2,6-dimethylbenzoylphenyl-isopentylphosphine oxide;
2,6-dimethylbenzoylphenylmethoxyethoxyphosphine oxide;
2,6-dimethylbenzoylphenylbenzylphosphine oxide;
2,6-dimethylbenzoylphenyl 2,4,4-trimethylpentylphosphine oxide;
2,6-dimethylbenzoylphenyl-2-propion- ic methyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic ethyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic propyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic butyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic pentyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic hexyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic octyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic decyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic dodecyl ester
phosphine oxide; 2,6-dimethylbenzoylphenyl-2-propionic isopropyl
ester phosphine oxide; 2,6-dimethylbenzoylphenyl-2-propionic
isobutyl ester phosphine oxide;
2,6-dimethylbenzoylphenyl-2-propionic amyl ester phosphine oxide;
2,6-dimethylbenzoylphenyl-2-propionic 2-ethylhexyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic tert-butyl ester
phosphine oxide; 2,6-dimethylbenzoylphenyl-2-propionic 1
-methylpropyl ester phosphine oxide;
2,6-dimethylbenzoylphenyl-2-propionic isopentyl ester phosphine
oxide; 2,6-dimethylbenzoylphenyl-2-propionic methoxyethoxy ester
phosphine oxide; 2,6-dimethylbenzoylphenyl-2-propioni- c benzyl
ester phosphine oxide; 2,6-dimethylbenzoylphenyl-2-propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dimethylbenzoylphenylace- tic methyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic ethyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic propyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic butyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic pentyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic hexyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic octyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic decyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic dodecyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic isopropyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic isobutyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic amyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic 2-ethylhexyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic tert-butyl ester phosphine oxide;
2,6-dimethylbenzoylphenylacetic 1 -methylpropyl ester phosphine
oxide; 2,6-dimethylbenzoylphenylacetic isopentyl ester phosphine
oxide; 2,6-dimethylbenzoylphenylacetic methoxyethoxy ester
phosphine oxide; 2,6-dimethylbenzoylphenylacetic benzyl ester
phosphine oxide; 2,6-dimethylbenzoylphenylacetic
2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dimethoxybenzoylphenylmethylphosphine oxide;
2,6-dimethoxybenzoylphenylethylphosphine oxide;
2,6-dimethoxybenzoylpheny- lpropylphosphine oxide;
2,6-dimethoxybenzoylphenylbutylphosphine oxide;
2,6-dimethoxybenzoylphenylpentylphosphine oxide;
2,6-dimethoxybenzoylphen- ylhexylphosphine oxide;
2,6-dimethoxybenzoylphenylheptylphosphine oxide;
2,6-dimethoxybenzoylphenyloctylphosphine oxide;
2,6-dimethoxybenzoylpheny- ldodecylphosphine oxide;
2,6-dimethoxybenzoylphenylisopropylphosphine oxide;
2,6-dimethoxybenzoylphenylisobutylphosphine oxide;
2,6-dimethoxybenzoylphenylamylphosphine oxide;
2,6-dimethoxybenzoylphenyl- -2-ethylhexylphosphine oxide;
2,6-dimethoxybenzoylphenyl-tert-butylphosphi- ne oxide;
2,6-dimethoxybenzoylphenyl-1-methylpropylphosphine oxide;
2,6-dimethoxybenzoylphenyl-isopentylphosphine oxide;
2,6-dimethoxybenzoylphenylmethoxyethoxyphosphine oxide;
2,6-dimethoxybenzoylphenylbenzylphosphine oxide;
2,6-dimethoxybenzoylphen- yl-2,4,4-trimethylpentylphosphine oxide;
2,6-dimethoxybenzoylphenyl-2-prop- ionic methyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenyl-2-propionic ethyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenyl-2-propionic propyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic butyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic pentyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic hexyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic octyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic decyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic
dodecyl ester phosphine oxide;
2,6-dimethoxybenzoylphenyl-2-propionic isopropyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenyl-2-propionic isobutyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic amyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic
2-ethylhexyl ester phosphine oxide;
2,6-dimethoxybenzoylphenyl-2-propionic tert-butyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenyl-2-propionic 1 -methylpropyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propion- ic isopentyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenyl-2-propionic
methoxyethoxy ester phosphine oxide;
2,6-dimethoxybenzoylphenyl-2-propion- ic benzyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenyl-2-propionic 2,4,4-trimethylpentyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenylac- etic methyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenylacetic ethyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic propyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic butyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic pentyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic hexyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic octyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic decyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic dodecyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic isopropyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic isobutyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic amyl ester
phosphine oxide; 2,6-dimethoxybenzoylphenylacetic 2-ethylhexyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenylacetic tert-butyl
ester phosphine oxide; 2,6-dimethoxybenzoylphenylacetic
1-methylpropyl ester phosphine oxide;
2,6-dimethoxybenzoylphenylacetic isopentyl ester phosphine oxide;
2,6-dimethoxybenzoylphenylacetic methoxyethoxy ester phosphine
oxide; 2,6-dimethoxybenzoylphenylacetic benzyl ester phosphine
oxide; 2,6-dimethoxybenzoylphenylacetic 2,4,4-trimethylpentyl ester
phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylmethylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylethylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylpropylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylbutylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylpentylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylhexylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylheptylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyloctylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyldodecylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylisopropylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylisobutylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylamylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-ethylhexylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-tert-butylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-1 -methylpropylphosphine
oxide; 2,6-bis(trifluoromethyl)benzoylphenylisopentylphosphine
oxide; 2,6-bis(trifluoromethyl)benzoylphenylmethoxyethoxyphosphine
oxide; 2,6-bis(trifluoromethyl)benzoylphenylbenzylphosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2,4,4-trimethylpentylphosphine
oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic methyl
ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic ethyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic
propyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-pro- pionic butyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl--
2-propionic pentyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylp- henyl-2-propionic hexyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)ben-
zoylphenyl-2-propionic octyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic decyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic
dodecyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic isopropyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2--
propionic isobutyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylp- henyl-2-propionic amyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benz-
oylphenyl-2-propionic 2-ethylhexyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic tert-butyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic
1-methylpropyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphen- yl-2-propionic isopentyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)be-
nzoylphenyl-2-propionic methoxyethoxy ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic benzyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenyl-2-propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benz- oylphenylacetic methyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benz- oylphenylacetic
ethyl ester phosphine oxide; 2,6-bis(trifluoromethyl)benzo-
ylphenylacetic propyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzo- ylphenylacetic butyl ester phosphine
oxide; 2,6-bis(trifluoromethyl)benzoy- lphenylacetic pentyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoy- lphenylacetic
hexyl ester phosphine oxide; 2,6-bis(trifluoromethyl)benzoyl-
phenylacetic octyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylp- henylacetic decyl ester phosphine
oxide; 2,6-bis(trifluoromethyl)benzoylph- enylacetic dodecyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylp- henylacetic
isopropyl ester phosphine oxide; 2,6-bis(trifluoromethyl)benzo-
ylphenylacetic isobutyl ester phosphine oxide;
2,6-bis(trifluoromethyl)ben- zoylphenylacetic amyl ester phosphine
oxide; 2,6-bis(trifluoromethyl)benzo- ylphenylacetic 2-ethylhexyl
ester phosphine oxide; 2,6-bis(trifluoromethyl-
)benzoylphenylacetic tert-butyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylacetic 1-methyl-propyl ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylphenylacetic
isopentyl ester phosphine oxide;
2,6-bis(trifluoromethyl)benzoylphenylacetic methoxyethoxy ester
phosphine oxide; 2,6-bis(trifluoromethyl)benzoylpheny- lacetic
benzyl ester phosphine oxide; 2,6-bis(trifluoromethyl)benzoylpheny-
lacetic 2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dichlorobenzoylphenylmethylphosphine oxide;
2,6-dichlorobenzoylphenyl- ethylphosphine oxide;
2,6-dichlorobenzoylphenylpropylphosphine oxide;
2,6-dichlorobenzoylphenylbutylphosphine oxide;
2,6-dichlorobenzoylphenylp- entylphosphine oxide;
2,6-dichlorobenzoylphenylhexylphosphine oxide;
2,6-dichlorobenzoylphenylheptylphosphine oxide;
2,6-dichlorobenzoylphenyl- octylphosphine oxide;
2,6-dichlorobenzoylphenyldodecylphosphine oxide;
2,6-dichlorobenzoylphenylisopropylphosphine oxide;
2,6-dichlorobenzoylphenylisobutylphosphine oxide;
2,6-dichlorobenzoylphen- ylamylphosphine oxide;
2,6-dichlorobenzoylphenyl-2-ethylhexylphosphine oxide;
2,6-dichlorobenzoylphenyl-tert-butylphosphine oxide;
2,6-dichlorobenzoylphenyl-1-methylpropylphosphine oxide;
2,6-dichlorobenzoylphenylisopentylphosphine oxide;
2,6-dichlorobenzoylphenylmethoxyethoxy-phosphine oxide;
2,6-dichlorobenzoylphenylbenzylphosphine oxide;
2,6-dichlorobenzoylphenyl- -2,4,4-trimethylpentylphosphine oxide;
2,6-dichlorobenzoylphenyl-2-propion- ic methyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic ethyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic propyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic butyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic pentyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic hexyl ester phosphine
oxide; 2,6-dichlorobenzoylpheny l-2-propionic octyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic decyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic dodecyl ester
phosphine oxide; 2,6-dichlorobenzoylphenyl-2-propionic isopropyl
ester phosphine oxide; 2,6-dichlorobenzoylphenyl-2-propionic
isobutyl ester phosphine oxide;
2,6dichlorobenzoylphenyl-2-propionic amyl ester phosphine oxide;
2,6-dichlorobenzoylphenyl- 2-propionic 2-ethylhexyl ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propionic tert-butyl ester
phosphine oxide; 2,6-dichlorobenzoylphenyl-2-propionic
1-methylpropyl ester phosphine oxide;
2,6-dichlorobenzoylphenyl-2-propion-
ic isopentyl ester phosphine oxide;
2,6-dichlorobenzoylphenyl-2-propionic methoxyethoxy ester phosphine
oxide; 2,6-dichlorobenzoylphenyl-2-propioni- c benzyl ester
phosphine oxide; 2,6-dichlorobenzoylphenyl -2-propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dichlorobenzoylphenylace- tic methyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic ethyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic propyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic butyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic pentyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic hexyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic octyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic decyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic dodecyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic isopropyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic isobutyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic amyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic 2-ethylhexyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic tert-butyl ester phosphine oxide;
2,6-dichlorobenzoylphenylacetic 1 -methylpropyl ester phosphine
oxide; 2,6-dichlorobenzoylphenylacetic isopentyl ester phosphine
oxide; 2,6-dichlorobenzoylphenylacetic methoxyethoxy ester
phosphine oxide; 2,6-dichlorobenzoylphenylacetic benzyl ester
phosphine oxide; 2,6-dichlorobenzoylphenylacetic
2,4,4-trimethylpentyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylmethylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylethylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylpropylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylbutylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylpentylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylhexylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylheptylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyloctylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyidodecylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylisopropylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylisobutylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylamylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2-ethylhexylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-tert-butyl-phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-1-methylpropylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylisopentylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-methoxyethoxyphosphine oxide;
2,3,4,6-tetramethylbenzoylphenylbenzylphosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2,4,4-trimethylpentylphosphine
oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic methyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic ethyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic
propyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2-propionic butyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic pentyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic hexyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic
octyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2-propionic decyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic dodecyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propion- ic
isopropyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2-pro- pionic isobutyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-- propionic
amyl ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-p-
ropionic 2-ethylhexyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphe- nyl-2-propionic tert-butyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzo- ylphenyl-2-propionic
1-methylpropyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl 2-propionic isopentyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic
methoxyethoxy ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenyl-2-propionic benzyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenyl-2-propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylph- enylacetic methyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenyla- cetic ethyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic propyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic butyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic
pentyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacetic hexyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacetic octyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacetic decyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacetic dodecyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenylacetic isopropyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic isobutyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic amyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic
2-ethylhexyl ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacetic tert-butyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenylacetic 1 -methylpropyl ester
phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacet- ic isopentyl
ester phosphine oxide; 2,3,4,6-tetramethylbenzoylphenylacetic
methoxyethoxy ester phosphine oxide;
2,3,4,6-tetramethylbenzoylphenylacet- ic benzyl ester phosphine
oxide; 2,3,4,6-tetramethylbenzoylphenylacetic 2,4,4-trimethylpentyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylpheny-
lmethylphosphine oxide; 2,4,6-trimethoxybenzoylphenylethylphosphine
oxide; 2,4,6-trimethoxybenzoylphenylpropylphosphine oxide;
2,4,6-trimethoxybenzoylphenylbutylphosphine oxide;
2,4,6-trimethoxybenzoylphenylpentylphosphine oxide;
2,4,6-trimethoxybenzoylphenylhexylphosphine oxide;
2,4,6-trimethoxybenzoylphenylheptylphosphine oxide;
2,4,6-trimethoxybenzoylphenyloctylphosphine oxide;
2,4,6-trimethoxybenzoylphenyldodecylphosphine oxide;
2,4,6-trimethoxybenzoylphenylisopropylphosphine oxide;
2,4,6-trimethoxybenzoylphenylisobutylphosphine oxide;
2,4,6-trimethoxybenzoylphenylamylphosphine oxide;
2,4,6-trimethoxybenzoyl- phenyl-2-ethylhexylphosphine oxide;
2,4,6-trimethoxybenzoylphenyl-tert-but- ylphosphine oxide;
2,4,6-trimethoxybenzoylphenyl-1-methylpropylphosphine oxide;
2,4,6-trimethoxybenzoylphenyl-isopentylphosphine oxide;
2,4,6-trimethoxybenzoylphenylmethoxyethoxyphosphine oxide;
2,4,6-trimethoxybenzoylphenylbenzylphosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2,4,4-trimethylpentylphosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-propionic methyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic ethyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic propyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic
butyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-propionic pentyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic hexyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic octyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic
decyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-propionic dodecyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic isopropyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic isobutyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic
amyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-propionic 2-ethylhexyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-propionic
tert-butyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-propionic 1-methylpropyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2-pro- pionic
isopentyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenyl-2-pr- opionic methoxyethoxy ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenyl- -2-propionic benzyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylphenyl-2- -propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic methyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic ethyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic propyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic butyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic pentyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic hexyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic octyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic decyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic dodecyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic isopropyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenylacetic isobutyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenylacetic amyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenylacetic 2-ethylhexyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenylacetic tert-butyl
ester phosphine oxide; 2,4,6-trimethoxybenzoylphenylacetic
1-methylpropyl ester phosphine oxide;
2,4,6-trimethoxybenzoylphenylacetic isopentyl ester phosphine
oxide; 2,4,6-trimethoxybenzoylphenylacetic methoxyethoxy ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenylacetic benzyl ester
phosphine oxide; 2,4,6-trimethoxybenzoylphenylacetic
2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylmethylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylethylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylpropylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylbutylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylpentylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylhexylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylheptylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyloctylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyldodecylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylisopropylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylisobutylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylamylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-ethylhexylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-tert-butylphosphine oxide;
2,6-dimethyl-4-tert-butyl-benzoylphenyl-1-methylpropylphosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylisopentylphosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylmethoxyethoxyphosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylbenzylphosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2,4,4-trimethylpentylphosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic methyl
ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic ethyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic
propyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-pr- opionic butyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylpheny-
l-2-propionic pentyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzo- ylphenyl-2-propionic hexyl ester
phosphine oxide; 2,6-dimethyl-4-tert-buty-
lbenzoylphenyl-2-propionic octyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic decyl ester
phosphine oxide; 2,6-dimethyl4-tert-butylbenzoylphenyl-2-propionic
dodecyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic isopropyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphenyl-2-
-propionic isobutyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoy- lphenyl-2-propionic amyl ester
phosphine oxide; 2,6-dimethyl-
4-tert-butylbenzoylphenyl-2-propionic 2-ethylhexyl ester phosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic
tert-butyl ester phosphine oxide; 2,6-dimethyl
-4-tert-butylbenzoylphenyl- 2-propionic 1-methylpropyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphe-
nyl-2-propionic isopentyl ester phosphine oxide;
2,6-dimethyl-4-tert-butyl- benzoylphenyl-2-propionic methoxyethoxy
ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenyl-2-propionic benzyl ester
phosphine oxide; 2,6-dimethyl- 4-tert-butylbenzoylphenyl
-2-propionic 2,4,4-trimethylpentyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylben- zoylphenylacetic methyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbe- nzoylphenylacetic
ethyl ester phosphine oxide; 2,6-dimethyl-4-tert-butylbe-
nzoylphenylacetic propyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylb- enzoylphenylacetic butyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylb- enzoyl phenylacetic
pentyl ester phosphine oxide; 2,6-di
methyl-4-tert-butylbenzoylphenylacetic hexyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylacetic octyl ester phosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylacetic decyl ester
phosphine oxide; 2,6-dimethyl -4-tert-butylbenzoylphenylacetic
dodecyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylacetic isopropyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylacetic
isobutyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoylphenylacetic amyl ester phosphine
oxide; 2,6-dimethyl- 4-tert-butylbenzoylphenylacetic 2-ethylhexyl
ester phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylpheny-
lacetic tert-butyl ester phosphine oxide;
2,6-dimethyl-4-tert-butylbenzoyl phenylacetic 1-methylpropyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylacetic
isopentyl ester phosphine oxide; 2,6-dimethyl-
4-tert-butylbenzoylphenylacetic methoxyethoxy ester phosphine
oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylacetic benzyl ester
phosphine oxide; 2,6-dimethyl-4-tert-butylbenzoylphenylacetic
2,4,4-trimethylpentyl ester phosphine oxide;
2-chloro-6-methylbenzoylphen- ylmethylphosphine oxide;
2-chloro-6-methylbenzoylphenylethylphosphine oxide;
2-chloro-6-methylbenzoylphenylpropylphosphine oxide;
2-chloro-6-methylbenzoylphenylbutylphosphine oxide;
2-chloro-6-methylbenzoylphenylpentylphosphine oxide;
2-chloro-6-methylbenzoylphenylhexylphosphine oxide;
2-chloro-6-methylbenzoylphenylheptylphosphine oxide;
2-chloro-6-methylbenzoylphenyloctylphosphine oxide;
2-chloro-6-methylbenzoylphenyldodecylphosphine oxide;
2-chloro-6-methylbenzoylphenylisopropylphosphine oxide;
2-chloro-6-methylbenzoylphenylisobutylphosphine oxide;
2-chloro-6-methylbenzoylphenylamylphosphine oxide;
2-chloro-6-methylbenzoylphenyl-2-ethylhexylphosphine oxide;
2-chloro-6-methylbenzoylphenyl-tert-butylphosphine oxide;
2-chloro-6-methylbenzoylphenyl-1 -methylpropylphosphine oxide;
2-chloro-6-methylbenzoylphenylisopentylphosphine oxide;
2-chloro-6-methylbenzoylphenylmethoxyethoxyphosphine oxide;
2-chloro-6-methylbenzoylphenyl-benzylphosphine oxide;
2-chloro-6-methylbenzoylphenyl-2,4,4-trimethylpentylphosphine
oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic methyl ester
phosphine oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic ethyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic
propyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenyl-2-propionic butyl ester phosphine
oxide; 2-chloro-6-ethyl benzoylphenyl-2-propionic pentyl ester
phosphine oxide; 2- chloro-6-methylbenzoylphenyl-2-propionic hexyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic
octyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenyl-2-propionic decyl ester phosphine
oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic dodecyl ester
phosphine oxide; 2-chloro-6-methyl benzoylphenyl-2-propionic
isopropyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenyl-2-propionic isobutyl ester phosphine
oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic amyl ester
phosphine oxide; 2-chloro-6-methylbenzoylphenyl-2-propionic
2-ethylhexyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenyl-2-propionic tert-butyl ester
phosphine oxide; 2-chloro-6-methylbenzoylphenyl-2-propio- nic
1-methylpropyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenyl-2- -propionic isopentyl ester
phosphine oxide; 2-chloro-6-methylbenzoylphenyl- -2-propionic
methoxyethoxy ester phosphine oxide; 2-chloro-6-methylbenzoyl-
phenyl-2-propionic benzyl ester phosphine oxide;
2-chloro-6-methylbenzoylp- henyl-2-propionic 2,4,4-trimethylpentyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic methyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic ethyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic propyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic butyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic pentyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic hexyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic octyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic decyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic dodecyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic
isopropyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenylacetic isobutyl ester phosphine
oxide; 2-chloro-6-methylbenzoylphenylacetic amyl ester phosphine
oxide; 2-chloro-6-methylbenzoylphenylacetic 2-ethylhexyl ester
phosphine oxide;
2-chloro-6-methylbenzoylphenylacetic tert-butyl ester phosphine
oxide; 2-chloro-6-methylbenzoylphenylacetic 1-methylpropyl ester
phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic isopentyl
ester phosphine oxide; 2-chloro-6-methylbenzoylphenylacetic
methoxyethoxy ester phosphine oxide;
2-chloro-6-methylbenzoylphenylacetic benzyl ester phosphine oxide;
2-chloro-6-methylbenzoylphenylacetic 2,4,4-trimethylpentyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenylmethylphosphine
oxide; 2-chloro-6-methoxybenzoylphenylethylphosphine oxide;
2-chloro-6-methoxybenzoylphenylpropylphosphine oxide;
2-chloro-6-methoxybenzoylphenylbutylphosphine oxide;
2-chloro-6-methoxybenzoylphenylpentylphosphine oxide;
2-chloro-6-methoxybenzoylphenylhexylphosphine oxide;
2-chloro-6-methoxybenzoylphenylheptylphosphine oxide;
2-chloro-6-methoxybenzoylphenyloctylphosphine oxide;
2-chloro-6-methoxybenzoylphenyidodecylphosphine oxide;
2-chloro-6-methoxybenzoylphenylisopropylphosphine oxide;
2-chloro-6-methoxybenzoylphenylisobutylphosphine oxide;
2-chloro-6-methoxybenzoylphenylamylphosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-ethylhexylphosphine oxide;
2-chloro-6-methoxybenzoylphenyl-tert-butylphosphine oxide;
2-chloro-6-methoxybenzoylphenyl-1 -methylpropylphosphine oxide;
2-chloro-6-methoxybenzoylphenylisopentylphosphine oxide;
2-chloro-6-methoxybenzoylphenylmethoxyethoxyphosphine oxide;
2-chloro-6-methoxybenzoylphenylbenzylphosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2,4,4-trimethylpentylphosphine
oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic methyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic ethyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic
propyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-propionic butyl ester phosphine
oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic pentyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic hexyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic
octyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-propionic decyl ester phosphine
oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic dodecyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic
isopropyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-propionic isobutyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic amyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic
2-ethylhexyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-pro- pionic tert-butyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2- -propionic
1-methylpropyl ester phosphine oxide; 2-chloro-6-methoxybenzoyl-
phenyl-2-propionic isopentyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenyl-2-propionic methoxyethoxy ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic benzyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenyl-2-propionic
2,4,4-trimethylpentyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic methyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic ethyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic propyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic butyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic pentyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic hexyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic octyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic decyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic dodecyl ester phosphine
oxide; 2-chloro-6-methoxybenzoylphenylacetic isopropyl ester
phosphine oxide; 2-chloro-6-methoxybenzoylphenylacetic isobutyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenylacetic amyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenylacetic
2-ethylhexyl ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylacetic tert-butyl ester phosphine
oxide; 2-chloro-6-methoxybenzoyl phenylacetic 1-methylpropyl ester
phosphine oxide; 2- chloro-6- methoxybenzoylphenylacetic isopentyl
ester phosphine oxide; 2-chloro-6-methoxybenzoylphenylacetic
methoxyethoxy ester phosphine oxide;
2-chloro-6-methoxybenzoylphenylaceti- c benzyl ester phosphine
oxide; 2-chloro-6-methoxybenzoylphenylacetic 2,4,4-trimethylpentyl
ester phosphine oxide.
[0265] The compounds of the formula III are obtained by reaction of
a corresponding compound of the formula I with a compound Z,-X
(VI), where firstly the compound of the formula III in which x=0
(III&50 ) is prepared: 78
[0266] Ar, M, X, and R.sub.6-R.sub.10 are as defined above and in
the claims. Z.sub.1 is as defined in claim 3, with the exception of
the groups (v), (w) and C.sub.1-C.sub.24alkylthio. (The preparation
of compounds in which Z.sub.1 is a group (v) or (w) or
C.sub.1-C.sub.24alkylthio is described below.) If compounds of the
formula III where A=O or S are to be prepared, an oxidation or
sulfurization of the compound of the formula (III') is then carried
out, either after the compounds of the formula (III') have been
separated off by customary methods, or without isolation thereof.
The conditions for such reactions are analogous to those described
for the preparation of the compounds of the formula II.
[0267] If a compound of the formula (III) in which Z.sub.1 is a
radical (v) or (w), or in which Z.sub.1 is
C.sub.1-C.sub.24alkylthio is desired, then the compound of the
formula (I) is reacted with a compound of the formula
Z.sub.1--SO.sub.2--X, where, without an intermediate stage, a
compound of the formula (III) where A=0 and x=1 is directly
obtained. (Z.sub.1 is defined as above, X is defined as in the
claims.) The carrying out of the oxidation step is therefore
unnecessary.
[0268] Similar reactions are described, for example, in
Houben-Weyl, E2, Methoden der Organischen Chemie, 4.sup.th edition,
pages 222-225.
[0269] If compounds of the formula (III) in which Z.sub.1 is a
radical (v) or (w) or C.sub.1-C.sub.24alkylthio and in which A is
sulfur are to be prepared, then it is, for example, possible to
convert the corresponding oxide compound as described above into
the sulfide. This is possible, for example, by reacting the
corresponding phosphine oxide with an excess of P.sub.2S.sub.5 or
elemental sulfur in a high-boiling solvent. Such reactions, i.e.
reactions in which a P.dbd.O bond is converted into a P.dbd.S bond,
are described, for example, in L. Horner et al., Chem. Ber. 92,
2088 (1959) and U.S. Pat. No. 2,642,461. In principle, it is also
possible to firstly reduce the corresponding phosphine oxide
compound to give the respective phosphine and then to sulfurize the
phosphine. I.e. the P.dbd.O bond is reduced to give the phosphine
using a suitable reducing agent, and is then sulfurized with
elemental sulfur to give the P.dbd.S bond. Reducing agents which
may be used are, for example, LiAlH.sub.4, Ca(AlH.sub.4).sub.2,
CaH.sub.2 AlH.sub.3, SiHCl.sub.3, PhSiH.sub.3 and the agents as
described in "Organic Phosphorous Compounds, Wiley-Interscience
1972, Vol. 1, pages 45-46 and Vol.3, pages 408-413".
[0270] Compounds of the formula II, wherein A.sub.1 is NR.sub.18a,
are for example prepared by reacting compounds of formula I with
carbodiimides: 79
[0271] The invention provides a process for the preparation of
compounds of the formula III from the novel starting materials of
the formula I.
[0272] (1) by reaction of an acyl halide of the formula IV 80
[0273] in which
[0274] Ar is as defined above, and
[0275] X is Cl or Br;
[0276] with a dimetalated arylphosphine of the formula V 81
[0277] (V), in which
[0278] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as
defined above; and
[0279] M.sub.1 is Na, Li or K;
[0280] In the molar ratio of approximately 1:1;
[0281] (2) subsequent reaction of the product with a compound of
the formula VI Z.sub.1--X (VI), in which
[0282] Z.sub.1 is as defined above, with the exception of the
groups (v), (w) and C.sub.1-C.sub.24alkylthio; and
[0283] X is as defined above;
[0284] with the proviso that, if Z.sub.1 is a radical 82
[0285] this radical is not identical to the radical 83
[0286] of the formula V;
[0287] in the molar ratio of approximately 1:1; and,
[0288] (3) if compounds of the formula III in which A is oxygen or
sulfur are to be obtained, subsequent oxidation or sulfurization of
the resulting phosphine compounds.
[0289] The compounds of the formula III in which Z.sub.1 is
C.sub.2-C.sub.24alkyl can, furthermore, be obtained by
[0290] (1) reaction of an acyl halide of the formula IV 84
[0291] in which
[0292] Ar is as defined above, and
[0293] X is Cl or Br;
[0294] with an unsymmetrical phosphine of the formula VII 85
[0295] in which
[0296] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are as
defined above, and
[0297] Z.sub.1' is C.sub.1-C.sub.24alkyl;
[0298] in the molar ratio of approximately 1:1, in the presence of
a base, to give the corresponding acylphosphine; and
[0299] (2) subsequent oxidation or sulfurization of the
acylphosphine thus obtained.
[0300] This preparation process is novel and likewise provided by
the invention.
[0301] Suitable bases for this process are, for example,
organolithium compounds, such as butyllithium, or organic nitrogen
bases, for example tertiary amines or pyridine.
[0302] Furthermore, the compounds of the formula III can also be
prepared by reacting the compound of the formula I with phosgene,
analogous to the description in "W. A. Henderson et al., J. Am.
Chem. Soc. 1960, 82, 5794" or "GB 904 086" or in "Organic
Phosphorous Compounds, Editors: R. M. Kosolapoff and L. Maier,
Wiley-Interscience 1972, Vol.1, page 28" or "Houben-Weyl, Methoden
der Organischen Chemie, Vol. XII/1, page 201" to give the
corresponding phosphine chloride (Ii). Compounds of the formula
(Ii) can, as described in "Organic Phosphorous Compounds, Editors:
R. M. Kosolapoff and L. Maier, Wiley-Interscience 1972, Vol.4,
pages 268-269", be reacted with alcohols to give compounds of the
formula (Iii), which are then directly reacted with an organohalide
of the formula VI, in analogy to "K. Sasse in Houben-Weyl, Methoden
der Organischen Chemie, Vol XII/1, page 433" (by Michaelis-Arbuzov
reaction), to give compounds of the formula II. In this case, the
oxidation or sulfurization step is superfluous. 86
[0303] Ar is as described in claim 1 and Z.sub.1 is as described in
claim 3; X is Cl or Br; R.sub.6 and M are likewise defined as in
claim 1, and R is any alcohol radical, e.g. C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.8cycloalkyl, for example cyclopentyl or cyclohexyl,
or benzyl.
[0304] Compounds of the formula (Iii) can be oxidized using
suitable oxidizing agents, such as peroxo acids, hydrogen peroxide
or hydrogen peroxide/urea to give the corresponding phosphinic
esters (Iiii): 87
[0305] The invention thus also provides a process for the
preparation of compounds of the formula III in which A is oxygen
and x is 1, by
[0306] (1) reaction of a compound of the formula (I), according to
claim 1 88
[0307] in which
[0308] Ar, M, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
as defined above, with phosgene to give corresponding phosphine
chloride (Ii) 89
[0309] (2) subsequent reaction with an alcohol to give the compound
of the formula (Iii) 90
[0310] in which
[0311] R is the radical of an alcohol; and
[0312] (3) reaction of the resulting compound of the formula (Iii)
with an organohalide Z.sub.1--X, in which
[0313] Z.sub.1 is as defined above, but is not identical to Ar from
the formula (I), and
[0314] X is Cl or Br,
[0315] to give the compound of the formula III.
[0316] It is also conceivable to obtain the compounds of the
formula III according to the invention by another method. E.g.
processes as described in U.S. Pat. No. 4,298,738 or U.S. Pat. No.
4,324,744 could be used.
[0317] The invention provides for the use of compounds of the
formula I as starting materials for the preparation of mono- or
bisacylphosphines, mono- or bisacylphosphine oxides or mono- or
bisacylphosphine sulfides.
[0318] Also preferred are compounds of the formulae I, II and III,
91
[0319] Ar is a group 92
[0320] R.sub.1 and R.sub.2 independently of one another are
C.sub.1-C.sub.4alkyl, Cl-C.sub.4alkoxy or halogen;
[0321] R.sub.3, R.sub.4 and R.sub.9 independently of one another
are hydrogen or C.sub.1-C.sub.4alkyl;
[0322] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
hydrogen, C.sub.1-C.sub.4alkyl, OR.sub.11 or phenyl;
[0323] R.sub.11 is C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.8alkenyl or
benzyl;
[0324] M is hydrogen or Li;
[0325] A is O or S;
[0326] x is 1;
[0327] Y.sub.1 is C.sub.1-C.sub.4alkyl which is unsubstituted or
substituted by one or more phenyl; or Y.sub.1 is naphthyl,
anthracyl, OR.sub.11, N(R.sub.16)(R.sub.17), OR.sub.11a,
N(R.sub.18a)(R.sub.18b), 93
[0328] Y.sub.2 is unsubstituted phenylene or phenylene substituted
one to four times by C.sub.1-C.sub.4alkyl; R.sub.1' and R.sub.2'
independently of one another have the same meanings as given for
R.sub.1 and R.sub.2; and
[0329] R.sub.3', R.sub.4' and R.sub.5' independently of one another
have the same meanings as given for R.sub.3, R.sub.4 and
R.sub.5;
[0330] with the proviso that
[0331] if Y.sub.1 is a radical 94
[0332] naphthyl or anthracyl, this is not identical to the other
benzoyl group on the phosphorus atom;
[0333] Z.sub.1 is C.sub.1-C.sub.12alkyl; C.sub.1-C.sub.4alkyl which
is substituted by phenyl, halogen or 95
[0334] or
[0335] Z.sub.1 is unsubstituted C.sub.2-C.sub.8alkenyl or
C.sub.2-C.sub.8alkenyl substituted by C.sub.6-C.sub.12aryl, CN,
(CO)OR.sub.15 or (CO)N(R.sub.18).sub.2 or is 96
[0336] with the proviso that
[0337] if Z.sub.1 is a radical 97
[0338] this is not identical to the other aromatic radical 98
[0339] on the phosphorus atom;
[0340] Z.sub.3 is CH.sub.2;
[0341] Z.sub.4 is S;
[0342] r is 0;
[0343] s is a number from 1 to 4;
[0344] q is a number from 0 to 4;
[0345] E, G, G.sub.3 and G.sub.4 independently of one another are
unsubstituted C.sub.1-C.sub.4alkyl or are C1-C.sub.4alkyl
substituted by chlorine;
[0346] R.sub.11a is C.sub.1-C.sub.8alkyl, substituted by OR.sub.15,
halogen or 99
[0347] or is C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6cycloalkyl or
C.sub.7-C.sub.12arylalkyl; or is C.sub.6-C.sub.10aryl optionally
once or more than once substituted by C1-C.sub.4alkyl;
[0348] R.sub.15 is C.sub.1-C.sub.8alkyl or (CO)R.sub.18;
[0349] R.sub.16 and R.sub.17 independently of one another are
hydrogen, C.sub.1-C.sub.8alkyl; C.sub.2-C.sub.6alkenyl,
C.sub.3-C.sub.6cycloalkyl, phenyl or benzyl; or R.sub.16 and
R.sub.17 together are C.sub.3-C.sub.5alkylene optionally
interrupted by O, S or NR.sub.18;
[0350] R.sub.18 is C.sub.1-C.sub.8alkyl or
C.sub.1-C.sub.8alkenyl;
[0351] R.sub.18a and R.sub.18b independently of one another are
C.sub.1-C.sub.8alkyl, substituted by OR15, halogen,
--N.alpha.C.dbd.A or 100
[0352] or are C.sub.2-C.sub.8alkenyl; or are
C.sub.5-C.sub.12cycloalkyl substituted by --N.dbd.C.dbd.A or
--CH.sub.2--N.dbd.C.dbd.A and optionally additionally once or more
than once substituted by methyl; or are C.sub.6-C.sub.10aryl
optionally substituted by C.sub.1-C.sub.4alkyl and/or
--N.dbd.C.dbd.A; or are C.sub.7-C.sub.12arylalkyl;
[0353] R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are
hydrogen, CF.sub.3, CCl.sub.3 or halogen.
[0354] Likewise of interest are compounds of the formulae I, II and
III in which
[0355] R.sub.1 and R.sub.2 independently of one another are methyl,
methoxy or chlorine;
[0356] R.sub.3, R.sub.4 and R.sub.5 independently of one another
are hydrogen or methyl;
[0357] R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
hydrogen;
[0358] M is Li;
[0359] A is O;
[0360] x is 1;
[0361] Y.sub.1 is C.sub.1-C.sub.4alkyl; or Y.sub.1 is one of the
radicals 101
[0362] Y.sub.2 is phenylene;
[0363] R.sub.1' and R.sub.2' independently of one another have the
same meanings as given for R.sub.1 and R.sub.2; and
[0364] R.sub.3', R.sub.4' and R.sub.5' independently of one another
have the same meanings as given for R.sub.3, R.sub.4 and
R.sub.5;
[0365] with the proviso that
[0366] if Y.sub.1 is a radical 102
[0367] this is not identical to the other benzoyl group on the
phosphorus atom;
[0368] Z.sub.1 is C.sub.1-C.sub.12alkyl; C.sub.1-C.sub.4alkyl which
is substituted by 103
[0369] or Z.sub.1 is one of the radicals 104
[0370] Z.sub.3 is CH.sub.2;
[0371] Z.sub.4 is S;
[0372] r is 0;
[0373] s is a number from 1 to 4;
[0374] q is 0;
[0375] E, G, G.sub.3 and G.sub.4 independently of one another are
unsubstituted or chlorine-substituted C.sub.1-C.sub.4alkyl;
[0376] R.sub.18 is C.sub.1-C.sub.8alkyl;
[0377] R.sub.19, R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are
hydrogen, CF.sub.3, CCl.sub.3 or halogen.
[0378] According to the invention, the compounds of the formulae II
and III can be used as photoinitiators for the photopolymerization
of ethylenically unsaturated compounds or mixtures which comprise
such compounds.
[0379] This use can also take place in combination with another
photoinitiator and/or other additives.
[0380] The invention thus also relates to photopolymerizable
compositions comprising
[0381] (a) at least one ethylenically unsaturated
photopolymerizable compound and
[0382] (b) as photoinitiator, at least one compound of the formula
If and/or III, where the composition, in addition to the component
(b), can also comprise other photoinitiators (c) and/or other
additives (d).
[0383] Preference is given to using in these compositions compounds
of the formula II or III in which x is 1, in particular those
compounds in which x is 1 and A is oxygen.
[0384] The unsaturated compounds can contain one or more olefinic
double bonds. They can be of low molecular weight (monomeric) or
relatively high molecular weight (oligomeric). Examples of monomers
with a double bond are alkyl or hydroxyalkyl acrylates or
methacrylates, for example methyl acrylate, ethyl acrylate, butyl
acrylate, 2-ethylhexyl acrylate or 2-hydroxyethyl acrylate,
isobornyl acrylate, methyl methacrylate or ethyl methacrylate. Also
of interest are silicon- or fluorine-modified resins, e.g. silicone
acrylates. Further examples are acrylonitrile, acrylamide,
methacrylamide, N-substituted (meth)acrylamides, vinyl esters, such
as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether,
styrene, alkyl- and halostyrenes, N-vinylpyrrolidone, vinyl
chloride or vinylidene chloride.
[0385] Examples of monomers having two or more double bonds are
ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl
glycol diacrylate, hexamethylene glycol diacrylate or bisphenol A
diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane,
trimethylolpropane triacrylate, pentaerythritol triacrylate or
tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate,
diallyl phthalate, triallyl phosphate, triallyl isocyanurate or
tris(2-acryloylethyl) isocyanurate.
[0386] Examples of higher molecular weight (oligomeric)
polyunsaturated compounds are acrylicized epoxy resins,
polyurethanes, polyethers and polyesters which are acrylicized or
contain vinyl ether or epoxy groups. Further examples of
unsaturated oligomers are unsaturated polyester resins which are
mostly prepared from maleic acid, phthalic acid and one or more
diols and have molecular weights of from about 500 to 3,000. In
addition, it is also possible to use vinyl ether monomers and
oligomers, and maleate-terminated oligomers having polyester,
polyurethane, polyether, polyvinyl ether and epoxy main chains. In
particular, combinations of oligomers which carry vinyl ether
groups and polymers as described in WO 90/01512 are highly
suitable. However, copolymers of vinyl ether and maleic
acid-functionalized monomers are also suitable. Such unsaturated
oligomers may also be referred to as prepolymers.
[0387] Examples of particularly suitable compounds are esters of
ethylenically unsaturated carboxylic acids and polyols or
polyepoxides, and polymers containing ethylenically unsaturated
groups in the chain or in side-groups, for example unsaturated
polyesters, polyamides and polyurethanes and copolymers thereof,
alkyd resins, polybutadiene and butadiene copolymers, polyisoprene
and isoprene copolymers, polymers and copolymers containing
(meth)acrylic groups in side chains, and mixtures of one or more
such polymers.
[0388] Examples of unsaturated carboxylic acids are acrylic acid,
methacrylic acid, crotonic acid, itaconic acid, cinnamic acid,
unsaturated fatty acids such as linolenic acid or oleic acid.
Preference is given to acrylic acid and methacrylic acid.
[0389] Suitable polyols are aromatic and, in particular, aliphatic
and cycloaliphatic polyols. Examples of aromatic polyols are
hydroquinone, 4,4'-dihydroxydiphenyl,
2,2-di(4-hydroxyphenyl)propane, and also novolaks and resols.
Examples of polyepoxides are those based on said polyols,
particularly aromatic polyols and epichlorohydrins. In addition,
polymers and copolymers which contain hydroxyl groups in the
polymer chain or in side groups, for example polyvinyl alcohol and
copolymers thereof or hydroxyalkyl polymethacrylates or copolymers
thereof, are also suitable as polyols. Further suitable polyols are
oligoesters containing hydroxyl end-groups.
[0390] Examples of aliphatic and cycloaliphatic polyols are
alkylenediols having, preferably, 2 to 12 carbon atoms, such as
ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or
1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol,
diethylene glycol, triethylene glycol, polyethylene glycols having
molecular weights of, preferably, 200 to 1,500,
1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,
1,4-dihydroxymethylcyclohexane, glycerol,
tris(.beta.-hydroxyethyl)amine, trimethylolethane,
trimethylolpropane, pentaerythritol, dipentaerythritol and
sorbitol.
[0391] The polyols may be partially or completely esterified using
one or different unsaturated carboxylic acids, where the free
hydroxyl groups in partial esters may be modified, e.g. etherified
or esterified with other carboxylic acids.
[0392] Examples of esters are:
[0393] trimethylolpropane triacrylate, trimethylolethane
triacrylate, trimethylolpropane trimethacrylate, trimethylolethane
trimethacrylate, tetramethylene glycol dimethacrylate, triethylene
glycol dimethacrylate, tetraethylene glycol diacrylate,
pentaerythritol diacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
dipentaerythritol triacrylate, dipentaerythritol tetraacrylate,
dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
tripentaerythritol octaacrylate, pentaerythritol dimethacrylate,
pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate,
dipentaerythritol tetramethacrylate, tripentaerythritol
octamethacrylate, pentaerythritol diitaconate, dipentaerythritol
trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol
hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol
diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol
diitaconate, sorbitol triacrylate, sorbitol tetraacrylate,
pentaerythritol-modified triacrylate, sorbitol tetramethacrylate,
sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates
and methacrylates, glycerol di- and triacrylate, 1,4-cyclohexane
diacrylate, bisacrylates and bismethacrylates of polyethylene
glycol having molecular weights of from 200 to 1,500, or mixtures
thereof.
[0394] Also suitable as component (a) are the amides of identical
or different unsaturated carboxylic acids of aromatic,
cycloaliphatic and aliphatic polyamines having, preferably, 2 to 6,
particularly 2 to 4, amino groups. Examples of such polyamines are
ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or
1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine,
octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane,
isophoronediamine, phenylenediamine, bisphenylenediamine,
di-p-aminoethyl ether, diethylenetriamine, triethylenetetramine,
di(.beta.-aminoethoxy)ethane or di(.beta.-aminopropoxy)ethane.
Further suitable polyamines are polymers and copolymers with or
without additional amino groups in the side chain and oligoamides
containing amino end groups. Examples of such unsaturated amides
are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide,
diethylenetriaminetrismethacrylamide,
bis(methacrylamidopropoxy)ethane, .beta.-methacrylamidoethyl
methacrylate, N[(.beta.-hydroxyethoxy)ethyl]ac- rylamide.
[0395] Suitable unsaturated polyesters and polyamides are derived,
for example, from maleic acid and diols or diamines. Some of the
maleic acid may be replaced by other dicarboxylic acids. They can
be used together with ethylenically unsaturated comonomers, e.g.
styrene. The polyesters and polyamides may also be derived from
dicarboxylic acids and ethylenically unsaturated diols or diamines,
particularly from relatively long chain compounds containing, for
example, 6 to 20 carbon atoms. Examples of polyurethanes are those
constructed from saturated or unsaturated diisocyanates and
unsaturated or saturated diols.
[0396] Polybutadiene and polyisoprene and copolymers thereof are
known. Suitable comonomers are, for example, olefins, such as
ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile,
styrene or vinyl chloride. Polymers containing (meth)acrylate
groups in the side chain are likewise known. These may, for
example, be products of the reaction of novolak-based epoxy resins
with (meth)acrylic acid, homo- or copolymers of vinyl alcohol or
hydroxyalkyl derivatives thereof which have been esterified using
(meth)acrylic acid, or homo- and copolymers of (meth)acrylates
which have been esterified using hydroxyalkyl (meth)acrylates.
[0397] The photopolymerizable compounds may be used on their own or
in any desired mixtures. Preference is given to using mixtures of
polyol (meth)acrylates.
[0398] It is also possible to add binders to the compositions
according to the invention; this is particularly advantageous if
the photopolymerizable compounds are liquid or viscose substances.
The amount of binder may, for example, be 5-95% by weight,
preferably 10-90% by weight and particularly 40-90% by weight,
based on the total solids. The binder is chosen depending on the
field of application and on the properties required therefore, such
as the facility for development in aqueous or organic solvent
systems, adhesion to substrates and sensitivity to oxygen.
[0399] Examples of suitable binders are polymers having a molecular
weight of from about 5,000-2,000,000, preferably 10,000-1,000,000.
Examples are: homo- and copolymeric acrylates and methacrylates,
e.g. copolymers of methyl methacrylate/ethyl acrylate/methacrylic
acid, poly(alkyl methacrylates), poly(alkyl acrylates); cellulose
esters and cellulose ethers, such as cellulose acetate, cellulose
acetate butyrate, methylcellulose, ethylcellulose;
polyvinylbutyral, polyvinylformal, cyclized rubber, polyethers,
such as polyethylene oxide, polypropylene oxide,
polytetrahydrofuran; polystyrene, polycarbonate, polyurethane,
chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl
chloride/vinylidene chloride, copolymers of vinylidene chloride
with acrylonitrile, methyl methacrylate and vinyl acetate,
polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as
polycaprolactam and poly(hexamethyleneadipamide), and polyesters
such as poly(ethylene glycol terephthalate) and poly(hexamethylene
glycol succinate).
[0400] The unsaturated compounds can also be used in mixtures with
non-photopolymerizable film-forming components. These may, for
example, be physically drying polymers or solutions thereof in
organic solvents, for example nitrocellulose or cellulose
acetobutyrate. However, they may also be chemically or thermally
curable resins, for example polyisocyanates, polyepoxides or
melamine resins. The co-use of thermally curable resins is of
importance for use in so-called hybrid systems, which are
photopolymerized in a first stage and are crosslinked by thermal
aftertreatment in a second stage.
[0401] The photoinitiators according to the invention are also
suitable as initiators for the curing of oxidatively drying
systems, as are described, for example, in Lehrbuch der Lacke und
Beschichtungen Volume 111, 296-328, Verlag W. A. Colomb in
Heenemann GmbH, Berlin-Oberschwandorf (1976).
[0402] Apart from the photoinitiator, the photopolymerizable
mixtures can also contain various additives (d). Examples thereof
are thermal inhibitors, which are intended to prevent premature
polymerization, for example hydroquinone, hydroquinone derivatives,
p-methoxyphenol, naphthol or sterically hindered phenols, for
example 2,6-di(tert-butyl)-p-cresol. To increase the storage
stability in the dark it is possible, for example, to use copper
compounds, such as copper naphthenate, stearate or octoate,
phosphorus compounds, for example triphenylphosphine,
tributylphosphine, triethyl phosphite, triphenyl phosphite or
tribenzyl phosphite, quaternary ammonium compounds, for example
tetramethylammonium chloride or trimethylbenzylammonium chloride,
or hydroxylamine derivatives, for example N-diethylhydroxylamine.
In order to exclude atmospheric oxygen during the polymerization,
it is possible to add paraffin or similar wax-like substances which
migrate to the surface at the start of the polymerization due to
their lack of solubility in the polymers, and form a transparent
surface layer which prevents the entry of air. It is likewise
possible to apply an oxygen-impermeable layer. Light protection
agents which may be used are UV absorbers, for example those of the
hydroxyphenylbenzotriazol, hydroxyphenylbenzophenone, oxalamide or
hydroxyphenyl-s-triazine type. The compounds can be used
individually or as mixtures, with or without the use of sterically
hindered amines (HALS).
[0403] Examples of such UV absorbers and light protection agents
are
[0404] 1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hy- droxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole- ,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hyd- roxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'--
hydroxyphenyl)benzotriazole, mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2--
octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylet-
hyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-metho-
xycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-oc-
tyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylh-
exyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl
phenol]; transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycar-
bonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol
300; [R--CH.sub.2CH.sub.2--COO(CH.sub.2).sub.3].sub.2-- where
R=3'-tert-butyl 4'-hydroxy-5'-2H-benzotriazol-2-yl phenyl.
[0405] 2. 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0406] 3. Esters of unsubstituted or substituted benzoic acids, for
example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoylresorcinol,
bis(4-tertbutylbenzoyl)resorcinol, benzoylresorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxyben- zoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0407] 4. Acrylates, for example ethyl and isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl and butyl
.alpha.-cyano-.beta.-meth- yl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline.
[0408] 5. Sterically hindered amines, for example
bis(2,2,6,6-tetramethylp- iperidyl) sebacate,
bis(2,2,6,6-tetramethylpiperidyl) succinate,
bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,
bis(1,2,2,6,6-pentamethylpi- peridyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the product of
the condensation of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidin- e and
succinic acid, the product of the condensation of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,
tris(2,2,6,6-tetramethyl- -4-piperidyl) nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-
-1,2,3,4-butanetetraoate,
1,1'-(1,2-ethanediyl)bis-(3,3,5,5-tetramethylpip- erazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpipe- ridyl)
2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis( 1 -octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the product
of the condensation of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylen- e-diamine
and 4-morpholino-2,6-dichloro-1,3,5-triazine, the product of the
condensation of
2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperid-
yl)1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the
product of the condensation of
2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylp-
iperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4--
dione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
2,4-bis[N-( 1
-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylam-
ino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, the product of the
condensation of 2,4-bis[1
-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-y-
l)butylamino]-6-chloro-s-triazine and
N,N'-bis(3-aminopropyl)ethylenediami- ne.
[0409] 6. Oxalamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide,
2-ethoxy-2'-ethyloxanilide- ,
N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyl- oxanilide and mixtures thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert-butylox- anilide, and mixtures of o-
and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.
[0410] 7. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1
,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,5-dimethylphenyl)-1
,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl- )-1
,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-- 1
,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphen- yl)-1
,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-
-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-o-
ctyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
and
2-[4-dodecyl/tridecyloxy(2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,4-
-dimethylphenyl)-1,3,5-triazine.
[0411] 8. Phosphites and phosphonites, for example triphenyl
phosphite, diphenyl alkylphosphites, phenyl dialkylphosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearyl pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol
diphosphite, bisisodecyloxy-pentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,
bis(2,4,6-tri-tertbutylphenyl) pentaerythritol diphosphite,
tristearylsorbitol triphosphite,
tetrakis-(2,4-di-tertbutylphenyl)-4,4'-b- iphenylenediphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-diben-
z[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8, 1
0-tetra-tert-butyl-1 2-methyl-dibenz-[d,g]-1,3,2-dioxaphosphocine,
bis(2,4-di-tert-butyl-6-met- hylphenyl) methylphosphite, and
bis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphite.
[0412] Examples of UV absorbers and light protection agents
suitable as component (d) are also "Krypto-UVA", as are described,
for example, in EP 180548. It is also possible to use latent UV
absorbers, as described, for example, by Hida et al. in RadTech
Asia 97, 1997, page 212.
[0413] It is also possible to use additives customary in the art,
for example antistats, levelling auxiliaries and adhesion
improvers.
[0414] To accelerate the photopolymerization it is possible to add,
as further additives (d), a large number of amines, for example
triethanolamine, N-methyldiethanolamine, ethyl
p-dimethylaminobenzoate or Michlers ketone. The action of the
amines can be intensified by the addition of aromatic ketones, e.g.
of the benzophenone type. Examples of amines which can be used as
oxygen scavengers are substituted N,N-dialkylanilines, as described
in EP 339841. Other accelerators, coinitiators and autoxidators are
thiols, thioethers, disulfides and phosphines, as described, for
example, in EP 438123 and GB 2180358.
[0415] It is also possible to add chain transfer reagents customary
in the art to the compositions according to the invention. Examples
thereof are mercaptans, amines and benzothiazols.
[0416] The photopolymerization can also be accelerated by the
addition of photosensitizers as further additives (d); these shift
and/or broaden the spectral sensitivity. These are, in particular,
aromatic carbonyl compounds, for example benzophenone,
thioxanthone, in particular also isopropylthioxanthone,
anthraquinone and 3-acylcoumarin derivatives, terphenyls, styryl
ketones, and 3-(aroylmethylene)thiazolines, camphorquinone, but
also eosin, rhodamine and erythrosine dyes.
[0417] As photosensitizers, it is also possible, for example, to
consider the amines given above. Further examples of such
photosensitizers are
[0418] 1. Thioxanthones
[0419] thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,
2-dodecylthioxanthone, 2,4-diethylthioxanthone,
2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone,
2-ethoxycarbonylthioxanthone,
3-(2-methoxyethoxycarbonyl)thioxanthone,
4-butoxycarbonylthioxanthone,
3-butoxycarbonyl-7-methylthioxanthone,
1-cyano-3-chlorothioxanthone,
1-ethoxycarbonyl-3-chlorothioxanthone,
1-ethoxycarbonyl-3-ethoxythioxanth- one,
1-ethoxycarbonyl-3-aminothioxanthone,
1-ethoxycarbonyl-3-phenylsulfur- ylthioxanthone,
3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1
-ethoxycarbonyl-3-(1-methyl-1 -morpholinoethyl)thioxanthone,
2-methyl-6-dimethoxymethylthioxanthone,
2-methyl-6-(1,1-dimethoxybenzyl)t- hioxanthone,
2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylth-
ioxanthone, n-allylthioxanthone-3,4-dicarboximide,
n-octylthioxanthone-3,4- -dicarboximide,
N-(1,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboximide- , 1
-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone,
6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethylene
glycol ester,
2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)N,N,N-trime-
thyl-1 -propanaminium chloride;
[0420] 2. Benzophenones
[0421] benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone,
4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone,
4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone,
4,4'-diethylaminobenzophenone, 4-methylbenzophenone,
2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)benzophenone,
3,3'-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate,
4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone,
4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride,
2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium
chloride monohydrate,
4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)benzophenone,
4-benzoyl-N,N-dimethyl-N-[2-(1
-oxo-2-propenyl)oxy]ethylbenzenemethanamin- ium chloride;
[0422] 3. 3-Acylcoumarins
[0423] 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin,
3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichlorocoumarin,
3-benzoyl-6-chlorocoumarin,
3,3'-carbonylbis[5,7-di(propoxy)coumarin],
3,3'-carbonylbis(7-methoxycoumarin),
3,3'-carbonylbis(7-diethylaminocouma- rin), 3-isobutyroylcoumarin,
3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin,
3-benzoyl-5,7-dibutoxycoumarin,
3-benzoyl-5,7-di(methoxyethoxy)coumarin,
3-benzoyl-5,7-di(allyloxy)coumar- in,
3-benzoyl-7-dimethylaminocoumarin,
3-benzoyl-7-diethylaminocoumarin,
3-isobutyroyl-7-dimethylaminocoumarin,
5,7-dimethoxy-3-(1-naphthoyl)couma- rin, 5,7-dimethoxy-3-(1
-naphthoyl)coumarin, 3-benzoylbenzo[f]coumarin,
7-diethylamino-3-thienoylcoumarin,
3-(4-cyanobenzoyl)-5,7-dimethoxycoumar- in;
[0424] 4. 3-(Aroylmethylene)thiazolines
[0425] 3-Methyl-2-benzoylmethylene-p-naphthothiazoline,
3-methyl-2-benzoylmethylenebenzothiazoline,
3-ethyl-2-propionylmethylene-- .beta.-naphthothiazoline;
[0426] 5. Other carbonyl compounds
[0427] Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone,
benzil, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone,
9-fluorenone, dibenzosuberone, xanthone,
2,5-bis(4-diethylaminobenzylidene)cyclopentano- ne,
.alpha.-(para-dimethylaminobenzylidene) ketones, such as
2-(4-dimethylaminobenzylidene)indan-1-one or
3-(4-dimethylaminophenyl)-1 -indan-5-ylpropenone,
3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)-
phthalimide.
[0428] The curing process can also be aided, in particular, by
pigmented compositions (e.g. with titanium dioxide), also by the
addition as additional additive (d) of a component which forms the
radicals under thermal conditions, for example an azo compound,
such as 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), a
triazene, diazo sulfide, pentazadiene or a peroxy compound, for
example hydroperoxide or peroxycarbonate, e.g. t-butyl
hydroperoxide, as described, for example, in EP 245639.
[0429] As further additive (d), the compositions according to the
invention can also comprise a photoreproducible dye, for example
xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine,
porphyrin or acridine dyes, and/or a radiation-cleavable
trihalomethyl compound. Similar compositions are described, for
example, in EP 445624.
[0430] Depending on the intended use, further customary additives
(d) are optical brighteners, fillers, pigments, both white and
coloured pigments, dyes, antistats, wetting agents or levelling
auxiliaries.
[0431] For the curing of thick and pigmented coatings, the addition
of microglass beads or pulverized glass fibres, as described, for
example, in U.S. Pat. No. 5,013,768, is suitable.
[0432] The formulations can also comprise dyes and/or white or
coloured pigments. Depending on the intended use, it is possible to
use both inorganic and organic pigments. Such additives are known
to the person skilled in the art, examples being titanium dioxide
pigments, e.g. of the rutile or anatase type, carbon black, zinc
oxide, such as zinc white, iron oxides, such as iron oxide yellow,
iron oxide red, chromium yellow, chromium green, nickel titanium
yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium
yellow or cadmium red. Examples of organic pigments are mono- or
bisazo pigments, and metal complexes thereof, phthalocyanine
pigments, polycyclic pigments, for example perylene, anthraquinone,
thioindigo, quinacridone or triphenylmethane pigments, and
diketopyrrolopyrrole, isoindolinone, e.g. tetrachloroisoindolinone,
isoindoline, dioxazine, benzimidazolone and quinophthalone
pigments. The pigments can be used individually or else as mixtures
in the formulations.
[0433] Depending on the intended use, the pigments are added to the
formulations in amounts customary in the art, for example in an
amount of from 0.1 to 60% by weight, 0.1 to 30% by weight or 10 to
30% by weight, based on the total composition.
[0434] The formulations can, for example, also comprise organic
dyes from very diverse classes. Examples are azo dyes, methine
dyes, anthraquinone dyes or metal complex dyes. Customary
concentrations are, for example, 0.1 to 20%, in particular 1 to 5%,
based on the total compositions.
[0435] Depending on the formulation used, compounds can also
neutralize the acids, in particular amines are used as stabilizers.
Suitable systems are described, for example, in JP-A 11-199610.
Examples are pyridine and derivatives thereof, N-alkylanilines or
N,N-dialkylanilines, pyrazine derivatives, pyrrol derivatives,
etc.
[0436] The choice of additives depends on the field of application
in question and the properties desired for this field. The
above-described additives (d) are customary in the art and are
accordingly used in amounts customary in the art.
[0437] The invention also provides compositions comprising, as
components (a), at least one ethylenically unsaturated
photopolymerizable compound which is emulsified or dissolved in
water.
[0438] Such radiation-curable aqueous prepolymer dispersions are
available commercially in many variations. This is understood as
meaning a dispersion of water and at least one prepolymer dispersed
therein. The concentration of the water in these systems is, for
example, 2 to 80% by weight, in particular 30 to 60% by weight. The
radiation-curable prepolymers or prepolymer mixture is present, for
example, in concentrations of from 95 to 20% by weight, in
particular 70 to 40% by weight. In these compositions, the total of
the percentages given for water and prepolymers is in each case
100, the auxiliaries and additives being added in varying amounts,
depending on the intended use.
[0439] The radiation-curable film-forming prepolymers which are
dispersed, and often also dissolved, in water are mono- or
polyfunctional ethylenically unsaturated prepolymers which can be
initiated by free radicals and are known per se for aqueous
prepolymer dispersions, which have, for example, a content of from
0.01 to 1.0 mol per 100 g of prepolymer of polymerizable double
bonds, and also an average molecular weight of, for example, at
least 400, in particular from 500 to 10,000. However, depending on
the intended use, prepolymers with higher molecular weights are
also suitable.
[0440] Polyesters containing polymerizable C--C double bonds and
having an acid number of at most 10, polyethers containing
polymerizable C--C double bonds, hydroxyl-containing products of
the reaction of a polyepoxide containing at least two epoxide
groups per molecule with at least one .alpha.,.beta.-ethylenically
unsaturated carboxylic acid, polyurethane (meth)acrylates, and
acrylic copolymers containing .alpha.,.beta.-ethylenically
unsaturated acrylic radicals, as are described in EP 12339.
Mixtures of these prepolymers can likewise be used. Also suitable
are the polymerizable prepolymers described in EP 33896, which are
thioether adducts of polymerizable prepolymers having an average
molecular weight of at least 600, a carboxyl group content of from
0.2 to 15% and a content of from 0.01 to 0.8 mol of polymerizable
C--C double bonds per 100 g of prepolymer. Other suitable aqueous
dispersions based on specific (meth)acrylic alkyl ester polymers
are described in EP 41125, and suitable water-dispersible,
radiation-curable prepolymers of urethane acrylates can be found in
DE 2936039.
[0441] As further additives, these radiation-curable aqueous
prepolymer dispersions can also comprise the above-described
additional additives (d), i.e., for example, dispersion
auxiliaries, emulsifiers, antioxidants, light stabilizers, dyes,
pigments, fillers, e.g. talc, gypsum, silica, rutile, carbon black,
zinc oxide, iron oxides, reaction accelerators, levelling agents,
lubricants, wetting agents, thickeners, matting agents, antifoams
and other auxiliaries customary in surface coating technology.
Suitable dispersion auxiliaries are water-soluble high molecular
weight organic compounds having polar groups, for example polyvinyl
alcohols, polyvinylpyrrolidone or cellulose ethers. Emulsifiers
which may be used are nonionic, and, where appropriate, also ionic,
emulsifiers.
[0442] The photoinitiators of the formula II or III according to
the invention can also be dispersed as such in aqueous solutions
and added in this dispersed form to the mixtures to be cured.
Treated with suitable nonionic or, where appropriate, also ionic,
emulsifiers, the compounds of the formula II or III according to
the invention can be incorporated by mixing and e.g. binding into
water. This produces stable emulsions which can be used as such as
photoinitiators, in particular for aqueous photocurable mixtures as
described above.
[0443] In certain cases, it may be advantageous to use mixtures of
two or more of the photoinitiators according to the invention. It
is of course also possible to use mixtures with known
photoinitiators, e.g. mixtures with camphorquinone, benzophenone,
benzophenone derivatives, acetophenone, acetophenone derivatives,
for example .alpha.-hydroxycycloalkyl phenyl ketones or
2-hydroxy-2-methyl-1 -phenylpropanone, dialkoxyacetophenones,
.alpha.-hydroxy or .alpha.-aminoacetophenones, for example
4-methylthiobenzoyl-1-methyl-1-mo- rpholinoethane,
4-morpholinobenzoyl-1-benzyl-1-dimethylaminopropane,
4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, for
example benzil dimethyl ketal, phenyl glyoxalates and derivatives
thereof, dimeric phenyl glyoxalates, peresters, e.g.
benzophenonetetracarboxylic peresters, as described, for example,
in EP 126541, monoacylphosphine oxides, for example
(2,4,6-trimethylbenzoyl)phe- nylphosphine oxide, bisacylphosphine
oxides, for example bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpent-1
-yl)phosphine oxide, bis-(2,4,6-trimethylbenzoyl)phenylphosphine
oxide or bis(2,4,6-trimethylbenzoyl)-(2,4-dipentoxyphenyl)phosphine
oxide, trisacylphosphine oxides, halomethyltriazines, e.g.
2-[2-(4-methoxyphenyl)vinyl]-4,6-bistrichloromethyl-[1,3,5]triazine,
2-(4-methoxyphenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,
2-(3,4-dimethoxyphenyl)-4,6-bistrichloromethyl-[1,3,5]triazine,
2-methyl-4,6-bistrichloromethyl-[1,3,5]triazine,
hexaarylbisimidazole/coi- nitiator systems, e.g.
ortho-chlorohexaphenylbisimidazole in combination with
2-mercaptobenzothiazole; ferrocenium compounds or titanocenes, for
example
dicyclopentadienylbis-(2,6-difluoro-3-pyrrolophenyl)titanium.
Coinitiators which may also be used are borate compounds.
[0444] In the case of the use of the photoinitiators according to
the invention in hybrid systems, in this connection mixtures of
free-radically and cationically curing systems are thus intended,
in addition to the free-radical curing agents according to the
invention, cationic photoinitiators, for example benzoyl peroxide
(other suitable peroxides are described in U.S. Pat. No. 4,950,581,
column 19, lines 17-25), aromatic sulfonium, phosphonium or
iodonium salts, as described, for example in U.S. Pat. No.
4,950,581, column 18, line 60 to column 19, line 10, or
cyclopentadienylareneiron(II) complex salts, e.g.
(.eta..sup.6-isopropylbenzene)(.eta..sup.5-cyclopentadienyl)iron(III)
hexafluorophosphate, are used.
[0445] The invention also provides compositions in which the
additional photoinitiators (c) are compounds of the formula VIII,
IX, X, XI or mixtures thereof, 105
[0446] in which
[0447] R.sub.25 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18alkoxy, --OCH.sub.2CH.sub.2--OR.sub.29, morpholino,
SCH.sub.3, group 106
[0448] or a group 107
[0449] n has a value from 2 to 10;
[0450] G.sub.1 and G.sub.2 independently of one another are
end-groups of the polymeric unit, in particular hydrogen or
CH.sub.3;
[0451] R.sub.26 is hydroxyl, C.sub.1-C.sub.16alkoxy, morpholino,
dimethylamino or
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16alkyl;
[0452] R.sub.27 and R.sub.28 independently of one another are
hydrogen, C.sub.1-C.sub.6alkyl, phenyl, benzyl,
C.sub.1-C.sub.16alkoxy or
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16alkyl, or R.sub.27
and R.sub.28 together with the carbon atom to which they are bonded
form a cyclohexyl ring;
[0453] m is a number from 1-20;
[0454] where R.sub.26, R.sub.27 and R.sub.28 are not all
C.sub.1-C.sub.16alkoxy or
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16a- lkyl at the same
time, and
[0455] R.sub.29 is hydrogen, 108
[0456] R.sub.30 and R.sub.32 independently of one another are
hydrogen or methyl;
[0457] R.sub.31 is hydrogen, methyl or phenylthio, where the phenyl
ring of the phenylthio radical is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl in the 4-, 2-, 2,4- or 2,4,6-position;
[0458] R.sub.33 and R.sub.34 independently of one another are
C.sub.1-C.sub.20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or
biphenyl, where these radicals are unsubstituted or are substituted
by halogen, C.sub.1-C.sub.12alkyl and/or C.sub.1-C.sub.12-alkoxy,
or R.sub.33 is an S- or N-containing 5- or 6-membered heterocyclic
ring, or are 109
[0459] R.sub.35 is cyclohexyl, cyclopentyl, phenyl, naphthyl or
biphenyl, these radicals being unsubstituted or substituted by
halogen, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy, or
R.sub.35 is an S- or N-containing 5- or 6-membered heterocyclic
ring;
[0460] R.sub.36 and R.sub.37 independently of one another are
unsubstituted cyclopentadienyl or cyclopentadienyl substituted
once, twice or three times by C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18alkoxy, cyclopentyl, cyclohexyl or halogen; and
[0461] R.sub.38 and R.sub.39 independently of one another are
phenyl which is substituted in at least one of the two ortho
positions relative to the titanium-carbon bond by fluorine atoms or
CF.sub.3, and which on the aromatic ring may contain, as further
substituents, unsubstituted pyrrolinyl or pyrrolinyl substituted by
one or two C.sub.1-C.sub.12alkyl,
di(C.sub.1-C.sub.12alkyl)aminomethyl, morpholinomethyl,
C.sub.2-C.sub.4alkenyl, methoxymethyl, ethoxymethyl,
trimethylsilyl, formyl, methoxy or phenyl; or polyoxaalkyl,
[0462] or R.sub.38 and R.sub.39 are 110
[0463] R.sub.40, R.sub.41 and R.sub.42 independently of one another
are hydrogen, halogen, C.sub.2-C.sub.12alkenyl,
C.sub.1-C.sub.12alkoxy, C.sub.2-C.sub.12alkoxy interrupted by one
to four O atoms, cycylohexyloxy, cyclopentyloxy, phenoxy,
benzyloxy, unsubstituted phenyl or phenyl substituted by
C.sub.1-C.sub.4alkoxy, halogen, phenylthio or
C.sub.1-C.sub.4-alkylthio; or biphenyl,
[0464] where R.sub.40 and R.sub.42 are not both hydrogen at the
same time and in the radical 111
[0465] at least one radical R.sub.40 or R.sub.42 is
C.sub.1-C.sub.12alkoxy, C.sub.2-C.sub.12alkoxy interrupted by one
to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or
benzyloxy;
[0466] E.sub.1 is O, S or NR.sub.43; and
[0467] R.sub.43 is C.sub.1-C.sub.8alkyl, phenyl or cyclohexyl.
[0468] R.sub.25 as C.sub.1-C.sub.18alkyl can have the same meanings
as described for the compounds of the formulae I, II or III. Also,
R.sub.27 and R.sub.28 as C.sub.1-C.sub.6alkyl and R.sub.26 as
C.sub.1-C.sub.4alkyl can have the same meanings as described above
apart from the respective number of carbon atoms.
[0469] C.sub.1-C.sub.18alkoxy is, for example, branched or
unbranched alkoxy, for example methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy,
hexyloxy, heptyloxy, octyloxy, 2,4,4-trimethylpent-1-yloxy,
2-ethylhexyloxy, nonyloxy, decyloxy, dodecyloxy or
octadecyloxy.
[0470] C.sub.2-C.sub.12alkoxy has the meanings given above apart
from the corresponding number of carbon atoms.
[0471] C.sub.1-C.sub.16alkoxy has the same meanings as described
above apart from the corresponding number of carbon atoms, and
decyloxy, methoxy and ethoxy are preferred, in particular methoxy
and ethoxy.
[0472] The radical
--O(CH.sub.2CH.sub.2O).sub.m--C.sub.1-C.sub.16alkyl stands for 1 to
20 consecutive ethylene oxide units whose chain ends with a
C.sub.1-C.sub.16alkyl. Preferably, m is 1 to 10, e.g. 1 to 8, in
particular 1 to 6 Preferably, the ethylene oxide unit chain is
terminated with a C.sub.1-C.sub.10alkyl, e.g. C.sub.1-C.sub.8alkyl,
in particular with a C.sub.1-C.sub.4alkyl.
[0473] R.sub.31 as a substituted phenylthio ring is, preferably,
p-tolylthio.
[0474] R.sub.33 and R.sub.34 as C.sub.1-C.sub.20alkyl are linear or
branched and are, for example, C.sub.1-C.sub.12alkyl,
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.4alkyl.
Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl,
2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl.
Preferably, R.sub.33 as alkyl is C.sub.1-C.sub.8alkyl.
[0475] R.sub.33, R.sub.34 and R.sub.36 as substituted phenyl are
mono- to pentasubstituted, e.g. mono-, di- or trisubstituted, in
particular tri- or disubstituted, on the phenyl ring. Substituted
phenyl, naphthyl or biphenyl are substituted e.g. with a linear or
branched C.sub.1-C.sub.4alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, s-butyl or t-butyl or with a linear
or branched C.sub.1-C.sub.4alkoxy such as methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy or t-butoxy,
preferably with methyl or methoxy.
[0476] If R.sub.33, R.sub.34 and R.sub.35 are an S- or N-containing
5- or 6-membered heterocyclic ring, they are, for example, thienyl,
pyrrolyl or pyridyl.
[0477] In the expression di(C.sub.1-C.sub.12alkyl)aminomethyl,
C.sub.1-C.sub.12alkyl has the same meanings as given above.
[0478] C.sub.2-C.sub.12alkenyl is linear or branched, can be mono-
or polyunsaturated and is, for example, allyl, methallyl,
1,1-dimethylallyl, 1-butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl
or 1-octenyl, in particular allyl.
[0479] C.sub.1-C.sub.4alkylthio is linear or branched and is, for
example, methylthio, ethylthio, n-propylthio, isopropylthio,
n-butylthio, isobutylthio, s-butylthio or t-butylthio, preferably
methylthio.
[0480] C.sub.2-C.sub.4alkenyl is, for example, allyl, methallyl, 1
-butenyl or 2-butenyl.
[0481] Halogen is fluorine, chlorine, bromine and iodine,
preferably, fluorine, chlorine and bromine.
[0482] The term polyoxaalkyl includes C.sub.2-C.sub.20alkyl
interrupted by 1 to 9 O atoms and stands, for example, for
structural units such as CH.sub.3--O--CH.sub.2--,
CH.sub.3CH.sub.2--O--CH.sub.2CH.sub.2--,
CH.sub.3O[CH.sub.2CH.sub.2O].sub.y--, where y=1-9,
--(CH.sub.2CH.sub.2O).sub.7CH.sub.2CH.sub.3,
--CH.sub.2--CH(CH.sub.3)--O-- -CH.sub.2--CH.sub.2CH.sub.3.
[0483] Preference is given to compositions in which
[0484] R.sub.25 is hydrogen, --OCH.sub.2CH.sub.2--OR.sub.29,
morpholino, SCH.sub.3, a group 112
[0485] or a group 113
[0486] R.sub.26 is hydroxyl, C.sub.1-C.sub.16alkoxy, morpholino or
dimethylamino;
[0487] R.sub.27 and R.sub.28 independently of one another are
C.sub.1-C.sub.4alkyl, phenyl, benzyl or C.sub.1-C.sub.16alkoxy,
or
[0488] R.sub.27 and R.sub.28 together with the carbon atom to which
they are bonded form a cyclohexyl ring;
[0489] R.sub.29 is hydrogen or 114
[0490] R.sub.30, R.sub.3, and R.sub.32 are hydrogen;
[0491] R.sub.33 is C.sub.1-C.sub.12alkyl, unsubstituted phenyl or
phenyl substituted by C.sub.1-C.sub.12alkyl and/or
C.sub.1-C.sub.12alkoxy;
[0492] R.sub.34 is 115
[0493] and
[0494] R.sub.35 is phenyl which is substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy.
[0495] Preferred compounds of the formulae VIII, IX, X and XI are
.alpha.-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1
-phenylpropanone,
(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,
(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, benzil
dimethyl ketal, (2,4,6-trimethylbenzoyl)phenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl-pent-1-yl)phosphine
oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or
bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide and
dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolo)titanium.
[0496] Preference is also given to compositions in which, in the
formula VIII R.sub.27 and R.sub.28 independently of one another are
C.sub.1-C.sub.6alkyl, or together with the carbon atom to which
they are bonded form a cyclohexyl ring, and R.sub.26 is
hydroxyl.
[0497] The proportion of compounds of the formula II and/or III
(photoinitiator component (b)) in the mixture with compounds of the
formulae VIII, IX, X and/or XI (=photoinitiator component (c)) is 5
to 99%, e.g. 20-80%, preferably 25 to 75%.
[0498] Also important are compositions in which, in the compounds
of the formula VII, R.sub.27 and R.sub.28 are identical and are
methyl, and R.sub.26 is hydroxyl or isopropoxy.
[0499] Likewise preferred are compositions comprising compounds of
the formula II and/or III and compounds of the formula X in
which
[0500] R.sub.33 is unsubstituted or mono- to tri-
C.sub.1-C.sub.12alkyl- and/or C.sub.1-C.sub.12alkoxy-substituted
phenyl or C.sub.1-C.sub.12alkyl;
[0501] R.sub.34 is the group 116
[0502] or phenyl; and
[0503] R.sub.35 is phenyl substituted by one to three
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy.
[0504] Of particular interest are compositions as described above
which comprise photoinitiator mixtures of the formulae II, III,
VIII, IX, X and/or XI and are liquid at room temperature.
[0505] The preparation of the compounds of the formulae VIII, IX, X
and XI is generally known to the person skilled in the art and some
of the compounds are available commercially. The preparation of
oligomeric compounds of the formula VII is described, for example,
in EP 161463. A description of the preparation of compounds of the
formula IX can, for example, be found in EP 209831. The preparation
of compounds of the formula X is disclosed, for example, in EP
7508, EP 184095 and GB 2259704. The preparation of compounds of the
formula XI is described, for example, in EP 318894, EP 318893 and
EP 565488.
[0506] The photopolymerizable compositions advantageously comprise
the photoinitiator in an amount of from 0.05 to 20% by weight, e.g.
0.05 to 15% by weight, preferably 0.1 to 5% by weight, based on the
composition. The amount of photoinitiator stated is based on the
total of all added photoinitiators if mixtures thereof are used,
i.e. both on the photoinitiator (b) and on the photoinitiators
(b)+(c).
[0507] Compounds according to the invention in which Z.sub.1 or
Z.sub.2 are siloxane-containing radicals are particularly suitable
as photoinitiators for surface coatings, in particular vehicle
paints. These photoinitiators are not distributed as homogeneously
as possible in the formulation to be cured, but enriched in a
targeted manner on the surface of the coating to be cured, i.e. a
targeted orientation of the initiator to the surface of the
formulation takes place.
[0508] The photopolymerizable compositions can be used for various
purposes, for example as printing inks, such as screen printing
inks, flexographic printing inks or offset printing inks, as
clearcoats, as colour coats, as white coats, e.g. for wood or
metal, as powder coatings, as paints, inter alia for paper, water,
metal or plastic, as daylight-curable coatings for marking
buildings and roads, for photographic reproduction processes, for
holographic recording materials, for image recording processes or
for the production of printing plates which can be developed using
organic solvents or aqueous-alkaline media, for the production of
masks for screen printing, as dental filling materials, as
adhesives, as pressure-sensitive adhesives, as laminating resins,
as photoresists, e.g. galvanoresists, etch or permanent resists,
both liquid and dry films, as photostructurable dielectrics, and as
solder stopping masks for electronic circuits, as resists for the
preparation of colour filters for any type of screen or for
producing structures in the production process of plasma displays
and electroluminescence displays, for the production of optical
switches, optical gratings (interference gratings), for the
preparation of three-dimensional objects by mass curing (UV curing
in transparent moulds) or by the stereolithography process, as is
described, for example, in U.S. Pat. No. 4,575,330, for the
preparation of composite materials (e.g. styrenic polyesters which
may contain glass fibres and/or other fibres and other auxiliaries)
and other thick-layer materials, for the coating or sealing of
electronic components or as coatings for optical fibres. The
compositions are also suitable for the preparation of optical
lenses, e.g. contact lenses and Fresnel lenses, and for the
preparation of medical instruments, auxiliaries or implants.
[0509] The compositions are also suitable for the preparation of
gels having thermotropic properties. Such gels are described, for
example, in DE 19700064 and EP 678534.
[0510] Furthermore, the compositions can be used in dry-film
paints, as are described, for example, in Paint & Coatings
Industry, April 1997, 72 or Plastics World, Volume 54, No. 7, page
48(5).
[0511] The compounds according to the invention can also be used as
initiators for emulsion, bead or suspension polymerizations or as
initiators of a polymerization for the fixing of ordered states of
liquid-crystalline mono- and oligomers, or as initiators for the
fixing of dyes to organic materials.
[0512] In surface coatings, mixtures of a prepolymer with
polyunsaturated monomers are often used which also contain a
monounsaturated monomer. The prepolymer here is primarily
responsible for the properties of the coating film, and variation
thereof allows the person skilled in the art to influence the
properties of the cured film. The polyunsaturated monomer functions
as a crosslinking agent which renders the coating film insoluble.
The monounsaturated monomer functions as a reactive diluent, by
means of which the viscosity is reduced without the need to use a
solvent.
[0513] Unsaturated polyester resins are mostly used in
two-component systems together with a monounsaturated monomer,
preferably with styrene. For photoresists, specific one-component
systems are often used, for example polymaleimides, polychalcones
or polyimides, as are described in DE 2308830.
[0514] The compounds according to the invention and mixtures
thereof may also be used as free-radical photoinitiators or
photoinitiating systems for radiation-curable powder coatings. The
powder coatings may be based on solid resins and monomers
containing reactive double bonds, for example maleates, vinyl
ethers, acrylates, acrylamides and mixtures thereof. A
free-radically UV-curable powder coating can be formulated by
mixing unsaturated polyester resins with solid acrylamides (e.g.
methyl methacrylamide glycolate) and with a free-radical
photoinitiator according to the invention, as described, for
example, in the paper "Radiation Curing of Powder Coating",
Conference Proceedings, Radtech Europe 1993 by M. Wittig and Th.
Gohmann. Similarly, free-radically UV-curable powder coatings can
be formulated by mixing unsaturated polyester resins with solid
acrylates, methacrylates or vinyl ethers and with a photoinitiator
(or photoinitiator mixture) according to the invention. The powder
coatings can also comprise binders, as described, for example, in
DE 4228514 and EP 636669. The UV-curable powder coatings can also
comprise white or coloured pigments. Thus, for example, preferably
rutile titanium dioxide may be used in concentrations of up to 50%
by weight in order to obtain a cured powder coating with good
coverage. The process normally involves electrostatic or
tribostatic spraying of the powder onto the substrate, for example
metal or wood, melting the powder by heating and, after a smooth
film has formed, radiation-curing of the coating with ultraviolet
and/or visible light, e.g. using medium-pressure mercury lamps,
metal halide lamps or xenon lamps. A particular advantage of the
radiation-curable powder coatings compared with their thermally
curable counterparts is that the flow time after the melting of the
powder particles can be extended as desired in order to ensure the
formation of a smooth, high-gloss coating. In contrast to thermally
curable systems, radiation-curable powder coatings can be
formulated without the desired effect of a reduction in their
service life such that they melt at relatively low temperatures.
For this reason, they are also suitable as coatings for
heat-sensitive substrates, for example wood or plastics. In
addition to the photoinitiators according to the invention, the
powder coating formulations can also comprise UV absorbers.
Appropriate examples have been listed above under points 1 -8.
[0515] The photocurable compositions according to the invention are
suitable, for example, as coating substances for substrates of all
kinds, e.g. wood, textiles, paper, ceramic, glass, plastics such as
polyesters, polyethylene terephthalate, polyolefins or cellulose
acetate, in particular in the form of films, and also metals such
as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO.sub.2, on which
a protective coating or, for example by imagewise exposure, an
image is to be applied.
[0516] The substrates can be coated by applying a liquid
composition, a solution or suspension to the substrate. The choice
of solvent and the concentration depend primarily on the type of
composition and on the coating procedure. The solvent should be
inert, i.e. it should not undergo any chemical reaction with the
components and should be capable of being removed again after the
coating operation, in the drying process. Examples of suitable
solvents are ketones, ethers and esters, such as methyl ethyl
ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone,
N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol,
2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl
acetate, n-butyl acetate and ethyl 3-ethoxypropionate.
[0517] Using known coating processes, the formulation is applied to
a substrate, e.g. by spincoating, dip coating, knife coating,
curtain coating, brushing, spraying, especially, for example, by
electrostatic spraying and reverse-roll coating, and by
electrophoretic deposition. It is also possible to apply the
photosensitive layer to a temporary, flexible support and then to
coat the final substrate, e.g. a copper-laminated circuit board, by
means of layer transfer via lamination.
[0518] The amount applied (layer thickness) and the type of
substrate (layer support) are dependant on the desired field of
application. The suitable layer thicknesses for the respective
fields of application, e.g. in the photoresist field, printing ink
field or paint field are known to the person skilled in the art.
Depending on the field of application, the layer thickness range
generally includes values from about 0.1 .mu.m to more than 10
mm.
[0519] The radiation-sensitive compositions according to the
invention are used, for example, as negative resists which have
very high photosensitivity and can be developed in an
aqueous-alkaline medium without swelling. They are suitable as
photoresists for electronics, such as galvanoresists, etch resists,
both in liquid and also dry films, solder stopping resists, as
resists for the production of colour filters for any desired type
of screen, or for the formation of structures in the manufacturing
process of plasma displays and electroluminescence displays, for
the production of printing plates, for example offset printing
plates, for the production of printing formes for typographic
printing, planographic printing, intaglio printing, flexographic
printing or screen printing formes, the production of relief
copies, e.g. for the production of texts in Braille, for the
production of stamps, for use in moulding etching or use as
microresists in the production of integrated circuits. The
compositions may also be used as photostructurable dielectrics, for
the encapsulation of materials or as insulator coating for the
production of computer chips, printed circuits and other electrical
or electronic components. The possible layer supports and the
processing conditions of the coated substrates are varied
accordingly.
[0520] The compounds according to the invention are also used for
the production of single-layer or multilayer materials for image
recording or image duplication (copies, reprography), which may be
monotone or multicoloured. Furthermore, these materials can also be
used as colour testing systems. In this technology, it is also
possible to use formulations which contain microcapsules and, to
generate the image, a thermal step can be connected downstream of
the exposure step. Such systems and technologies and their
applications are described, for example, in U.S. Pat. No.
5,376,459.
[0521] For photographic information recording, films made of
polyester, cellulose acetate or plastic-coated papers, for example,
are used, and for offset printing formes, specially treated
aluminium, for example, is used, for the production of printed
circuits, copper-faced laminates, for example, are used, and for
the production of integrated circuits, silicon wafers are used. The
usual layer thicknesses for photographic materials and offset
printing forms are generally about 0.5 .mu.m to 10 .mu.m, and for
printed circuits are from 1.0 .mu.m to about 100 .mu.m.
[0522] After the substrates have been coated, the solvent is
usually removed by drying, to leave a layer of the photoresist on
the support.
[0523] The term "imagewise" exposure encompasses both exposure via
a photomask containing a predetermined pattern, for example a
diapositive, exposure by a laser beam which is moved, for example
under control by a computer, over the surface of the coated
substrate, thereby generating an image, and irradiation with
computer-controlled electron beams. It is also possible to use
masks of liquid crystals which can be controlled pixel by pixel in
order to generate digital images, as described, for example, by A.
Bertsch, J. Y. Jezequel, J. C. Andre in Journal of Photochemistry
and Photobiology A: Chemistry 1997, 107, p. 275-281 and by K.-P.
Nicolay in Offset Printing 1997, 6, p. 34-37.
[0524] Conjugated polymers, for example polyanilines, can be
converted from a semiconducting state to a conducting state by
doping with protons. The photoinitiators according to the invention
can also be used for the imagewise exposure of polymerizable
compositions which contain such polymers in order to form
conducting structures (in the irradiated zones) which are embedded
in the insulating material (unexposed zones). Such materials can,
for example, be used as wiring or connecting components for the
production of electrical or electronic components.
[0525] Following the imagewise exposure of the material and prior
to the developing, it may be advantageous to carry out a thermal
treatment for a relatively short period. Here, only the exposed
parts are thermally cured. The temperatures used are generally
50-150.degree. C., preferably 80-130.degree. C.; the thermal
treatment time is usually between 0.25 and 10 minutes.
[0526] Furthermore, the photocurable composition can be used in a
process for the production of printing formes or photoresists, as
described, for example, in DE 4013358. Herein, prior to,
simultaneously with or following the imagewise irradiation, the
composition is briefly exposed to visible light having a wavelength
of at least 400 nm without a mask. Following the exposure and the
optional thermal treatment, the unexposed areas of the photoresist
are removed using a developer in a manner known per se.
[0527] As already mentioned, the compositions according to the
invention can be developed by aqueous-alkaline media. Suitable
aqueous-alkaline developer solutions are, in particular, aqueous
solutions of tetraalkylammonium hydroxides or of alkali metal
silicates, phosphates, hydroxides and carbonates. Relatively small
amounts of wetting agents and/or organic solvents can also be added
to these solutions. Typical organic solvents which may be added to
the developer liquids in small amounts are, for example,
cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of
such solutions.
[0528] Photocuring is of great importance for printing inks since
the drying time of the binder is a crucial factor for the
production rate of graphic products and should be in the order of
magnitude of fractions of seconds. UV-curable inks are of
importance particularly for screen, flexographic and offset
printing.
[0529] As already mentioned, the mixtures according to the
invention are also highly suitable for the production of printing
plates. Here, mixtures of soluble linear polyamides or
styrene/butadiene or styrene/isoprene rubber, polyacrylates or
polymethyl methacrylates containing carboxyl groups, polyvinyl
alcohols or urethane acrylates with photopolymerizable monomers,
for example acryl- or methacrylamides or acrylic or methacrylic
esters, and a photoinitiator, for example, are used. Films and
plates made from these systems (wet or dry) are exposed via the
negative (or positive) of the print original, and the uncured parts
are subsequently washed out using a suitable solvent.
[0530] A further field of use for photocuring is the coating of
metals, for example the coating of metal sheets and tubes, cans or
bottlecaps, and the photocuring of plastic coatings, for example
PVC-based floor or wall coverings. Examples of the photocuring of
paper coatings are the colourless coating of labels, record sleeves
or book covers.
[0531] Likewise of interest is the use of the compounds according
to the invention for the curing of mouldings made from composite
materials. The composite material consists of a self-supporting
matrix material, e.g. a glass-fibre fabric, or else, for example,
plant fibres [cf. K.-P. Mieck, T. Reussmann in Kunststoffe 85
(1995), 366-370], which is impregnated with the photocuring
formulation. Mouldings made of composite materials produced using
the compounds according to the invention have high mechanical
stability and resistance. The compounds according to the invention
can also be used as photocuring agents in moulding, impregnation or
coating materials, as described, for example, in EP 7086. Such
materials are, for example, fine coating resins, which are subject
to strict requirements with regard to their curing activity and
yellowing resistance, fibre-reinforced mouldings, for example
planar or longitudinally or transversely corrugated light-diffusing
panels. Processes for the production of such mouldings, for example
hand lay-up techniques, fibre lay-up spraying, centrifugal or
winding techniques, are described, for example, by P. H. Selden in
"Glasfaserverstarkte Kunststoffe" [Glass-fibre-reinforced
plastics], page 610, Springer Verlag Berlin-Heidelberg-New York
1967. Examples of articles which may be produced by this method are
boats, chipboard or plywood panels coated on both sides with
glass-fibre-reinforced plastic, pipes, sport articles, roof
coverings, and containers etc. Further examples of moulding,
impregnation and coating materials are UP resin fine coatings for
mouldings containing glass fibres (GFP), e.g. corrugated sheets and
paper laminates. Paper laminates may be based on urea or melamine
resins. The fine coating is produced on a support (e.g. a film)
prior to the production of the laminate. The photocurable
compositions according to the invention can also be used for
casting resins or for embedding articles, e.g. electronic
components etc. Moreover, they can also be used for the lining of
cavities and pipes. For curing, medium-pressure mercury lamps are
used, as are customary in UV curing. However, less intensive lamps
are also of particular interest, e.g. those of the type TL 40W/03
or TL40W/05. The intensity of these lamps corresponds approximately
to that of sunlight. It is also possible to use direct sunlight for
the curing. It is a further advantage that the composite material
can be removed from the light source in a partially cured, plastic
state and can be deformed. Curing is then carried out to
completion.
[0532] The compositions and compounds according to the invention
can also be used for the preparation of optical waveguides and
optical switches, use being made of the generation of a difference
in the refractive index between exposed and unexposed areas.
[0533] Also important is the use of photocurable compositions for
imaging processes and for the optical production of information
carriers. Here, as already described above, the coat (wet or dry)
applied to the support is irradiated with UV or visible light via a
photomask and the unexposed areas of the coat are removed by
treatment with a solvent (=developer). The photocurable layer can
also be applied to the metal by an electrodeposition technique. The
exposed areas are crosslinked/polymeric and thus insoluble and
remain on the support. Appropriate coloration produces visible
images. If the support is a metallicized layer, then the metal can
be removed from the unexposed areas by etching after exposure and
developing, or can be strengthened by electroplating. Printed
electronic circuits and photoresists can be produced in this
way.
[0534] The photosensitivity of the compositions according to the
invention generally ranges from about 200 nm to about 600 nm (UV
range). Suitable radiation comprises, for example, sunlight or
light from artificial light sources. Therefore, a large number of
very different types of light sources can be used. Point sources
and flat radiators (lamp carpets) are suitable. Examples are:
carbon arc lamps, xenon arc lamps, medium-pressure, high-pressure
and low-pressure mercury lamps, optionally doped with metal halides
(metal halogen lamps), microwave-stimulated metal vapour lamps,
excimer lamps, superactinic fluorescent tubes, fluorescent lamps,
incandescent argon lamps, flashlights, photographic floodlight
lamps, light-emitting diodes (LED), electron beams and X-rays. The
distance between the lamp and the substrate to be exposed according
to the invention can vary depending on the intended use and lamp
type and intensity, e.g. between 2 cm and 150 cm. Of particular
suitability are laser light sources, e.g. excimer lasers, such as
krypton F lasers for exposure at 248 nm. It is also possible to use
lasers in the visible region. Using this method it is possible to
produce printed circuits in the electronics industry, lithographic
offset printing plates or relief printing plates, and also
photographic image recording materials.
[0535] The invention therefore also provides a process for the
photopolymerization of nonvolatile monomeric, oligomeric or
polymeric compounds having at least one ethylenically unsaturated
double bond, which comprises irradiating a composition as described
above with light in the range from 200 to 600 nm. The invention
also provides for the use of the compounds of the formula II or III
as photoinitiators for the photopolymerization of nonvolatile
monomeric, oligomeric or polymeric compounds having at least one
ethylenically unsaturated double bond by irradiation with light in
the range from 200 to 600 nm .
[0536] The invention also provides for the use of the
above-described composition or a process for the preparation of
pigmented and unpigmented surface coatings, printing inks, for
example screen printing inks, offset printing inks, flexographic
printing inks, powder coatings, printing plates, adhesives, dental
compositions, optical waveguides, optical switches, colour testing
systems, composite materials, glass fibre cable coatings, screen
printing stencils, resist materials, colour filters, use for the
encapsulation of electrical and electronic components, for the
production of magnetic recording materials, for the production of
three-dimensional objects using stereolithography, for photographic
reproductions, and for use as image recording material, in
particular for holographic recordings, for decolouring materials,
for decolouring materials for image recording materials, for image
recording materials using microcapsules.
[0537] The invention likewise provides a coated substrate which has
been coated on at least one surface with a composition as described
above, and also a process for the photographic production of relief
images in which a coated substrate is subjected to imagewise
exposure and then the unexposed portions are removed with a
solvent. The imagewise exposure can be carried out via a mask or by
means of a laser beam. Of particular interest here is exposure by
means of a laser beam.
[0538] The examples below illustrate the invention in more detail,
although it is not intended that the invention be limited to the
examples. Unless stated otherwise, parts and percentages are based,
as elsewhere in the description and in the claims, on the weight.
Wherever reference is made to alkyl or alkoxy radicals having more
than three carbon atoms without stating the isomer, then the
n-isomers are always intended.
EXAMPLE 1
[0539] 2,4,6-Trimethylbenzoylisobutylphenylphosphine oxide
[0540] At -20.degree. C., 40 ml (0.064 mol) of butyllithium 1.6 M
are slowly added dropwise to 9.5 g (0.058 mol) of
isobutylphenylphosphine in 100 ml of tetrahydrofuran (THF). At the
same temperature, 11.7 g (0.064 mol) of 2,4,6-trimethylbenzoyl
chloride are then added dropwise. After the mixture has been
allowed to warm to room temperature, the orange reaction suspension
is concentrated using a rotary evaporator (Rotavap). The residue is
taken up in 150 ml of toluene, and is treated with 13.1 g (0.116
mol) of hydrogen peroxide 30%. After the mixture has been stirred
for 2 hours between 20-30.degree. C., the reaction is complete. The
reaction emulsion is poured onto water and washed with aqueous
saturated sodium hydrogencarbonate solution, then dried over
magnesium sulfate and filtered. The filtrate is concentrated using
the Rotavap. The residue is purified over silica gel and dried
under a high vacuum. 11.8 g of the title compound are obtained as a
yellow viscous oil.
[0541] .sup.31P-NMR: .delta. 28.94 ppm
[0542] .sup.1H-NMR, measured in CDCl.sub.3, .delta. [ppm]:
7.37-7.79 (m), 6.70 (s), 1.98-2.23 (m), 1.93 (s) and 0.87-1.02
(q)
EXAMPLE 2
[0543]
2,4,6-Trimethylbenzoyl-(2,4,4-trimethylpentyl)phenylphosphine
oxide
[0544] The compound is prepared analogously to the method described
in Example 1, but using 2,4,4-trimethylpentylphenylphosphine
instead of isobutylphenylphosphine. .sup.31P-NMR: .delta. 28.86
ppm
[0545] .sup.1H-NMR, measured in CDCl.sub.3, .delta. [ppm]:
7.37-7.80 (m), 6.69 (s), 2.01-2.45 (m), 1.93-1.94 (d), 0.91-1.43
(m) and 0.71-0.80 (d)
EXAMPLE 3
[0546] Lithium (2,4,6-trimethylbenzoyl)phenylphosphine
[0547] Under argon and with the exclusion of moisture, 14.0 g of
lithium (2.0 mol) are introduced into 250 ml of tetrahydrofuran at
room temperature. Following the addition of 1.25 g of naphthalene,
44.8 g (0.25 mol) of dichlorophenylphosphine are added dropwise
with stirring at 20-25.degree. C. and, after stirring for 4 h, the
black solution is filtered into a three-necked round flask through
a frit (G2 porosity) with the exclusion of moisture and under argon
as a protective gas. 47.2 g (0.258 mol) of 2,4,6-trimethylbenzoyl
chloride are added dropwise at room temperature over the course of
30 minutes with stirring and cooling. Stirring for 2 hours gives
the title compound as a red solution in tetrahydrofuran.
[0548] .sup.31P-NMR 8 98.4 ppm.
EXAMPLES 4-5
[0549] The compounds of Examples 4 and 5 are obtained analogously
to the method described in Example 3 using the corresponding
starting materials. The compounds and their spectroscopic data are
given in Table 1 below.
1TABLE 1 Exam- .delta. .sup.31P-NMR ple Compound Starting material
4 117 -45.232 ppm 2,6-Dimethoxybenzoyl chloride 5 118 52.876 ppm
2,6-Dichlorobenzoyl chloride
EXAMPLE 6
[0550] 2,4,6-Trimethylbenzoylphenylphosphine
[0551] 35 ml (0.022 mol) of the solution described in Example 3 are
added dropwise to a mixture of toluene/water and acetic acid. The
organic phase is separated off, dried over magnesium sulfate and
concentrated using the Rotavap under argon. A sample is distilled
at 200.degree. C. and 0.02 mbar by means of Kugelrohr oven
distillation. The title compound is obtained as a yellow viscous
oil.
[0552] .sup.31P-NMR .delta.: -1.0 ppm
[0553] .sup.1H-NMR, measured in C.sub.6D.sub.6, [ppm]: 2.05(s),
2.14(s), 4.82(s) +5.61 (s) (1H on the P), 6.55 (s), 7.04 (m), 7.40
(m).
EXAMPLE 7
[0554] 2,4,6-Trimethylbenzoyl-(2,6-dimethoxybenzoyl)phenylphosphine
oxide
[0555] 4.4 g (0.022 mol) of 2,6-dimethoxybenzoyl chloride,
dissolved in 20 ml of tetrahydrofuran, are added dropwise over the
course of 20 min to 35 ml (0.022 mol) of the solution obtained
according to Example 3 at 20-30.degree. C. After the mixture has
been afterstirred for 2 hours, the orange reaction suspension is
concentrated using the Rotavap. The residue is taken up in 50 ml of
toluene, and is treated with 5.7 g (0.05 mol) of hydrogen peroxide
30%. After the mixture has been stirred for 2 hours between
20-30.degree. C., the reaction is complete. The reaction emulsion
is poured onto water and washed with aqueous saturated sodium
hydrogencarbonate solution, then dried over magnesium sulfate and
filtered. The filtrate is concentrated using the Rotavap. The
residue is purified over silica gel and dried under a high vacuum.
1.5 g of the title compound are obtained as a yellow solid with a
melting point of 126-127.degree. C.
[0556] .sup.31P-NMR .delta. 6.89 ppm
[0557] .sup.1H-NMR, measured in CDCl.sub.3, [ppm]: 7.33-8.05 (m),
6.82 (s), 6.50-6.53 (d), 3.60 (s), 2.27 (s) 18 (s)
EXAMPLES 8-49
[0558] The compounds of Examples 8 to 49 are obtained analogously
to the method described in Example 7 using the corresponding
starting materials. The compounds and physical data are given Table
2.
2TABLE 2 Exam- .delta. NMR [ppm]* ple Compound Starting materials
Melting point 8 119 Lithium (2,6-di- methoxybenzoyl)
phenylphosphine; 2,6-dichloro- benzoyl chloride .sup.31P-NMR 32.08;
.sup.1H-NMR 7.2 (s), 7.23-8.05 (m), 6.46-6.49 (d) and 3.60 (s);
m.p. 168-169.degree. C. 9 120 Lithium (2,6- dichlorobenzoyl)-
phenylphosphine; 2,4,6-trimethyl- benzoyl chloride .sup.31P-NMR
5.78; .sup.1H-NMR 7.33-7.94 (m), 7.13-7.16 (d), 6.68 (s), 2.11 (s)
and 2.06 (s); m.p. 146-148.degree. C. 10 121 Lithium (2,4,6-
trimethylbenzoyl) phenylphosphine; pivaloyl chloride .sup.31P-NMR
32.552; .sup.1H-NMR 7.43-7.92 (m), 6.78 (s), 2.236 (s), 2.18 (s)
and 1.3 (s); - 11 122 Lithium (2,4,6- trimethylbenzoyl)
phenylphosphine; anthracene-9- carbonyl chloride .sup.31P-NMR 9.85
.sup.1H-NMR 8.76 (s), 7.46-8.30 (m), 7.06 (s), 2.52 (s) and 2.37
(s) m.p. 181-182.degree. C. 12 123 Lithium (2,4,6-
trimethylbenzoyl) phenylphosphine; diphenylacetyl chloride
.sup.31P-NMR 12.17 .sup.1H-NMR 6.98-7.65 (m), 6.74 (s), 4.92 (s),
2.25 (s), and 1.94 (s) m.p. 148-149.degree. C. 13 124 Lithium
(2,4,6- trimethylbenzoyl) phenylphosphine; 1-naphthoyl chloride
.sup.31P-NMR 13.04 .sup.1H NMR 9.11-9.09 (d); 8.88-8.86 (d);
8.16-8.11 (m); 7.91-7.89 (m); 7.68-7.53 (m); 6.86 (s); 2.28 (s);
2.14 (s) - 14 125 Lithium (2,4,6- trimethylbenzoyl)
phenylphosphine; benzyl chloroformate .sup.31P NMR 8.66 .sup.1H NMR
7.96-7.91 (m); 7.57-7.53 (m); 7.46-7.42 (m); 7.27 (s); 6.72 (s);
5.34-5.20 (q); 2.17 (s); 1.98 (s) - 15 126 Lithium (2,4,6-
trimethylbenzoyl) phenylphosphine; methyl chloroformate .sup.31P
NMR 8.45 .sup.1H NMR 7.97-7.93 (m); 7.59-7.55 (m); 7.49-7.44 (m);
6.76 (s); 3.84 (s); 2.20 (s); 2.07 (s) 16 127 Lithium (2,4,6-
trimethylbenzoyl) phenylphosphine; ethyl chloroformate .sup.31P NMR
8.5 .sup.1H NMR 1.35 (t), 2.15 (s), 2.27 (s) 4.41 (m), 6.84 (s),
7.53 (m), 7.64 (t), 8.03 (dd) 17 128 Lithium (2,4,6-
trimethylphosphine; phenylphosphine; 2,4,6-trimethyl- 1,5-dibenzoyl
chloride .sup.31P NMR 8.30 .sup.1H NMR 7.18-7.80 (m), 7.31-7.47
(m), 6.71 (s), 2.11 (s), 2.05 (s) 18 129 Lithium (2,4,6-
trimethylbenzoyl) phenylphosphine; phthaloyl dichloride
.sup.31P-NMR 13.12; .sup.1H-NMR 7.0-8.3 (m), 6.5 (s), 2.1 (s) and
1.6 (s); m.p. 202-203.degree. C. 19 130 Lithium (2,4,6-tri-
methyl-benzoyl) phenylphosphine; 3-(2-chlorphenyl)-
5-methylisoxazol- 4-carbonyl chloride .sup.31P-NMR 9.16;
.sup.1H-NMR 7.19-7.71 (m), 6.71 (s), 2.73 (s), 2.18 (s), 2.05 (s);
- 20 131 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2,4,6-triisopropyl- benzoyl chloride .sup.31P-NMR 8.62; .sup.1H-NMR
7.34-7.86 (m), 6.86 (s), 6.75 (s), 2.70-2.96 (m), 2.21 (s), 2.13
(s), 1.12-1.14 (d), 0.96-0.98 (d), 0.83-0.85 (d); 21 132 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; 2-ethoxy-1-
naphthoyl chloride .sup.31P-NMR 9.65; .sup.1H-NMR 7.71-7.90 (m),
7.28-7.48 (m), 6.99-7.03 (d), 6.72 (s), 3.94-4.06 (m), 3.62-3.72
(m), 2.19 (s), 2.06 (s), 1.07-1.12 (t); m.p. 138-139.degree. C. 22
133 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2-acetoxy-isobut- yryl chloride .sup.31P-NMR 8.88; .sup.1H-NMR
7.24-7.86 (m), 6.70 (s), 2.17 (s), 2.09 (s), 1.96 (s), 1.51 (s),
1.38 (s); 23 134 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos-
phine; 2-(trifluoromethyl)- benzoyl chloride .sup.31P-NMR 11.63;
.sup.1H-NMR 7.04-8.27 (m), 6.74 (s), 2.19 (s), 2.04 (s); - 24 135
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2-iodbenzoyl chloride .sup.31P-NMR 11.53; .sup.1H-NMR 7.10-8.27
(m), 6.71 (s), 2.19 (s), 2.03 (s); 25 136 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; 1-adamantan- carbonyl chloride
.sup.31P-NMR 10.66; .sup.1H-NMR 7.85-7.91 (m), 7.42-7.58 (m), 6.79
(s), 2.26 (s), 2.19 (s), 1.72-2.06 (m); 26 137 Lithium (2,4,6-tri-
methyl-benzoyl) phenylphosphine; 3-chlorpivaloyl- chloride -;
.sup.1H-NMR 7.97-8.03 (m), 7.52-7.70 (m), 6.90 (s), 4.22-4.26 (d),
3.89-3.93 (d), 2.36 (s), 2.29 (s), 1.50 (s), 1.43 (s); - 27 138
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
diethylcarbamyl- chloride .sup.31P-NMR 8.46; .sup.1H-NMR 7.94-8.00
(m), 7.40-7.58 (m), 6.78 (s), 3.74-4.03 (m), 3.25-3.49 (m), 2.24
(s), 1.08-1.18 (m); m.p. 109-110.degree. C. 28 139 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; diphenylcarbamyl
chloride .sup.31P-NMR 10.53; .sup.1H-NMR 7.69-7.75 (m), 7.10-7.49
(m), 6.78 (s), 2.24 (s), 2.20 (s); m.p. 153-154.degree. C. 29 140
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2-(benzoyl-oxy- methyl)-benzoyl chloride .sup.31P-NMR 13.48;
.sup.1H-NMR 8.73-8.75 (d), 7.91-8.04 (m), 7.34-7.57 (m), 6.73 (s),
5.59 (s), 2.18 (s), 2.02 (s); - 30 141 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; 2-methylbenzoyl chloride
.sup.31P-NMR 13.57; .sup.1H-NMR 8.59-8.62 (d), 8.02-8.08 (m),
7.27-7.65 (m), 6.83 (s), 2.54 (s), 2.28 (s), 2.10 (s); - 31 142
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2-fluor-6-(trifluor- methyl)-benzoyl chloride .sup.31P-NMR 5.96;
.sup.1H-NMR 7.97-8.31 (m), 7.09-7.88 (m), 6.83 (s), 2.27 (s), 2.18
(s); m.p. 109-110.degree. C. 32 143 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; 2-(difluormethyl- thio)-benzoyl
chloride .sup.31P-NMR 10.89; .sup.1H-NMR 8.20-8.23 (d), 7.35-8.17
(m), 6.74 (s), 2.19 (s), 2.08 (s), 2.04 (s); - 33 144 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; 9-fluorenylmethyl
chlorformiate .sup.31P-NMR 8.37; .sup.1H-NMR 7.11-7.94 (m), 6.76
(s), 4.55-4.57 (d), 4.16-4.21 (t), 2.20 (s), 2.05 (s); - 34 145
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine; phenyl
chloro- formiate .sup.31P-NMR 9.52; .sup.1H-NMR 8.00-8.04 (m),
7.07-7.81 (m), 6.75 (s) 2.20 (s), 2.12 (s); - 35 146 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; isobutylchloro
formiate .sup.31P-NMR 8.99; .sup.1H-NMR 7.92-7.97 (m), 7.44-7.56
(m), 6.75 (s), 4.02-4.10 (m), 2.19 (s), 2.07 (s), 1.94-1.99 (m),
0.84-0.93 (m); - 36 147 Lithium (2,4,6-tri- methyl-benzo-
yl)phenylphos- phine; 2-ethylhexyl chloroformiate .sup.31P-NMR
8.94; .sup.1H-NMR 7.91-7.96 (m), 7.42-7.56 (m), 6.75 (s), 4.14-4.24
(m), 2.18 (s), 2.09 (s), 1.56-1.60 (m), 1.18-1.30 (m), 0.77-0.82
(m); - 37 148 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos-
phine; 2-bromoethyl chloroformiate .sup.31P-NMR 8.99; .sup.1H-NMR
7.93-7.98 (m), 7.46-7.59 (m), 6.77 (s), 4.50-4.61 (m), 3.43-3.52
(m), 2.20 (s), 2.09 (s); m.p. 73-75.degree. C. 38 149 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; allyl
chloroformiate .sup.31P-NMR 8.56; .sup.1H-NMR 7.93-7.98 (m),
7.44-7.59 (m), 6.76 (s), 5.82-5.90 (m), 5.28 (d), 5.25 (d),
4.69-4.79 (m), 2.19 (s), 2.07 (s); 39 150 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; butyl chloroformiate
.sup.31P-NMR 8.81; .sup.1H-NMR 7.92-7.97 (m), 7.44-7.56 (m), 6.76
(s), 4.21-4.33 (m), 2.19 (s), 2.07 (s), 1.62 (quint.), 1.31
(sext.), 0.85 (t); - 40 151 Lithium (2,4,6-tri- methyl-benzo-
yl)phenylphos- phine; octyl chloroformiate .sup.31P-NMR 8.75;
.sup.1H-NMR 7.92-7.97 (m), 7.43-7.57 (m), 6.76 (s), 4.22-4.32 (m),
2.19 (s), 2.07 (s), 1.63 (quint.), 1.18-1.28 (m), 0.80 (t); - 41
152 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
2,2,2-trichloro- 1,1-dimethyl chloroformiate .sup.31P-NMR 9.95;
.sup.1H-NMR 7.93-7.98 (m), 7.43-7.58 (m), 6.75 (s), 2.19 (s), 2.07
(s), 1.96 (s), 1.93 (s); m.p. 88-92.degree. C. 42 153 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; 2,2,2-trichloro-
ethyl chloroformiate .sup.31P-NMR 9.51; .sup.1H-NMR 7.95-8.00 (m),
7.46-7.61 (m), 6.77 (s), 4.88 (d), 4.83 (d), 2.20 (s), 2.09 (s); -
43 154 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine;
cholesterole chloroformiate .sup.31P-NMR 7.48; .sup.1H-NMR
7.92-7.98 (m), 7.43-7.58 (m), 6.76 (s), 5.32-5.34 (m), 4.77-4.84
(m), 2.32-2.51 (m), 2.20 (s), 2.08 (s), 0.96-1.96 (m), 0.94 (s),
0.84 (d), 0.79 (d), 0.60 (s); m.p. 58-62.degree. C. 44 155 Lithium
(2,4,6-tri- methyl-benzo- yl)phenylphos- phine; 1-chloro-2-
methyl-propyl chloroformiate .sup.31P-NMR 8.82; .sup.1H-NMR
7.91-7.99 (m), 7.45-7.61 (m), 6.77 (s), 6.36 (d), 2.07-2.25 (m),
2.18 (s), 2.10 (s), 0.91-1.00 (m); - 45 156 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; p-tolyl chloroformiate
.sup.31P-NMR 9.68; .sup.1H-NMR 7.99-8.04 (m), 7.47-7.58 (m), 7.10
(d), 6.95 (d), 6.74 (s), 2.26 (s), 2.21 (s), 2.12 (s); - 46 157
Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos- phine; isopropyl
chloro- formiate .sup.31P-NMR 8.49; .sup.1H-NMR 7.92-7.97 (m),
7.43-7.57 (m), 6.76 (s), 5.22 (sept.), 2.22 (s), 2.07 (s), 1.26
(d); - 47 158 Lithium (2,4,6-tri- methyl-benzo- yl)phenylphos-
phine; propargyl chlor- roformiate .sup.31P-NMR 8.53; .sup.1H-NMR
7.93-7.98 (m), 7.42-7.59 (m), 6.76 (s), 4.75-4.87 (m), 2.47 (t),
2.19 (s), 2.09 (s); - 48 159 Lithium (2,4,6-tri- methyl-benzo-
yl)phenylphos- phine; neopentyl chloroformiate .sup.31P-NMR 9.08;
.sup.1H-NMR 7.92-7.97 (m), 7.43-7.58 (m), 6.76 (s), 3.97 (s), 2.19
(s), 2.19 (s), 2.09 (s), 0.88 (s); - 49 160 Lithium (2,4,6-tri-
methyl-benzo- yl)phenylphos- phine; (-)-menthyl chlo- roformiate
.sup.31P-NMR 8.45; .sup.1H-NMR 7.91-7.96 (m), 7.44-7.56 (m), 6.76
(s), 4.87-4.96 (m), 2.19 (s), 2.08 (s), 0.98-1.97 (m), 0.77-0.86
(m), 0.64-0.68 (m); - *.sup.1H-NMR measured in CDCl.sub.3
EXAMPLE 50
[0559] 2,4,6-Trimethylbenzoylbenzylphenylphosphine oxide
[0560] At 20-30.degree. C., 8.5 g (0.05 mol) of benzyl bromide are
added dropwise over the course of 20 min to 35 ml (0.022 mol) of
the solution obtained according to Example 3. After the mixture has
been afterstirred for 2 hours, the orange reaction suspension is
concentrated using the Rotavap. The residue is taken up in 50 ml of
toluene and, is treated with 5.7 g (0.05 mol) of hydrogen peroxide
30%. After the mixture has been stirred for 2 hours between
20-30.degree. C., the reaction is complete. The reaction emulsion
is poured onto water and washed with aqueous saturated sodium
hydrogencarbonate solution, then dried over magnesium sulfate and
filtered. The filtrate is concentrated using the Rotavap. The
residue is purified over silica gel and dried under a high vacuum.
1.4 g of the title compound are obtained as a yellow solid with a
melting point of 113-114.degree. C.
[0561] .sup.31P-NMR .delta. 26.26 ppm
[0562] .sup.1H-NMR, measured in CDCl.sub.3, [ppm]: 7.16-7.83 (m),
6.63(s), 3.43-3.88 (m), 2.13 (s) and 1.66 (s)
EXAMPLES 51-60
[0563] The compounds of Examples 51-60 are prepared analogously to
the method described in Example 50 using the corresponding starting
materials. The compounds and their physical data are given in Table
3.
3TABLE 3 Exam- ple Compound Starting materials .delta. NMR [ppm]*
51 161 Lithium (2,4,6- trimethylbenzoyl)- phenylphosphine; ally
bromide .sup.31P-NMR 26.60; .sup.1H-NMR 7.36-7.78 (m), 6.69 (s),
5.74-5.78 (m), 5.12-5.23 (m) 3.0-3.30 (m), 2.18 (s) and 1.97 (s) 52
162 Lithium (2,4,6- trimethylbenzoyl)- phenylphosphine;
2-ethylhexyl bromide .sup.31P-NMR 29.17; .sup.1H-NMR 7.36-7.79 (m),
6.70 (s), 2.15-2.25 (m), 2.15 (s), 1.94 (s), 1.36-1.38 (m),
1.06-1.19 (m) and 0.68-0.80 (m) 53 163 Lithium (2,4,6-
trimethylbenzoyl)- phenylphosphine; n-propyl bromide .sup.31P-NMR
30.35; .sup.1H-NMR 7.35-7.77 (m), 6.69 (s), 2.15-2.31 (m), 2.13
(s), 1.92 (s) 1.59-1.63 (m) and 0.94-0.97 (t) 54 164 Lithium
(2,4,6- trimethylbenzoyl)- phenylphosphine; n-butyl bromide
.sup.31P-NMR 30.35; .sup.1H-NMR 7.38-7.77 (m), 6.69 (s), 2.15-2.34
(m), 2.13 (s), 1.92 (s) 1.32-1.57 (m) and 0.80-0.84 (t) 55 165
Lithium (2,4,6- trimethylbenzoyl)- phenylphosphine;
tetrabromopenta- erythritol .sup.31P-NMR 22.60; .sup.1H-NMR
7.40-7.83 (m), 6.72 (s), 3.52-3.77 (q), 2.61-2.92 (m), 2.16 (s) and
1.94 (s) 56 166 Lithium (2,4,6- trimethylbenzoyl)- phenylphosphine;
methyl 3- bromopropionate .sup.31P-NMR 27.96; .sup.1H-NMR 7.42-7.78
(m), 6.72 (s), 3.60 (s), 2.50-2.65 (m), 2.19 (s) and 1.95 (s) 57
167 Lithium (2,4,6- trimethylbenzoyl)- phenylphosphine; octyl
2-bromo- propionate .sup.31P-NMR 18.63; .sup.1H-NMR 7.20-7.78 (m),
6.72 (s), 3.96-4.03 (m), 3.48-3.54 (m), 2.17 (s), 2.06 (s),
1.02-1.58 (m) and 0.54-0.77 (m) 58 168 Lithium (2,4,6-
trimethylbenzoyl)- phenylphosphine; methyl bromoacetate
.sup.31P-NMR 22.29; .sup.1H-NMR 7.32-7.74 (m), 6.65 (s), 3.18-3.74
(m), 2.09 (s) and 1.93 (s) 59 169 Lithium (2,4,6-
trimethylbenzoyl)- phenylphosphine; 1,3-bis(chloro-
propyl)tetramethyl- disiloxane .sup.31P-NMR 29.36; .sup.1H-NMR
7.45-7.84 (m), 6.77 (s), 3.44-3.49 (t), 2.24-2.44 (m), 2.24 (s),
2.0 (s), 1.69-1.77 (m), 0.53-0.69 (m) and 0.0 (s) 60 170 Lithium
(2,4,6- trimethylbenzoyl)- phenylphosphine; chloromethyl-
pentamethyl- disiloxane .sup.31P-NMR 28.32; .sup.1H-NMR 7.47-7.86
(m), 6.78 (s), 2.25 (s), 2.01 (s), 1.69-1.98 (m), 0.22 (s), 0.05
(s) and 0.0 (s)
EXAMPLE 61
[0564]
2,4,6-Trimethylbenzoyl-(5-trifluoromethyl)pyrid-2-ylphenylphosphine
oxide
[0565] At 20-30.degree. C., 4.0 g (0.022 mol) of
2-chloro-5-trifluoromethy- lpyridine, dissolved in 20 ml of
tetrahydrofuran, are added dropwise over the course of 20 min to 35
ml (0.022 mol) of the solution obtained according to Example 3.
After the mixture has been afterstirred for 2 hours, the orange
reaction suspension is concentrated using the Rotavap. The residue
is taken up in 50 ml of toluene, and is treated with 5.7 g (0.05
mol) of hydrogen peroxide 30%. After the mixture has been stirred
for 2 hours between 20-30.degree. C., the reaction is complete. The
reaction emulsion is poured onto water and washed with aqueous
saturated sodium hydrogencarbonate solution, then dried over
magnesium sulfate and filtered. The filtrate is concentrated using
the Rotavap. The residue is purified over silica gel and dried
under a high vacuum. 1.5 g of the title compound are obtained as a
yellow resin.
[0566] .sup.31P-NMR: .delta. 10.42 ppm
[0567] .sup.1H-NMR, measured in CDCl.sub.3, .delta. [ppm]: 8.98
(s), 7.37-8.14 (m), 6.69 (s), 2.15 (s) and 2.01 (s)
EXAMPLES 62-63
[0568] The compounds of Examples 62 and 63 are obtained analogously
to the method described in Example 61 using the corresponding
starting materials. The compounds and their physical data are given
in Table 4.
4TABLE 4 Exam- .delta. NMR [ppm]* ple Compound Starting materials
Melting point 62 171 Lithium (2,4,6- trimethylbenzoyl)-
phenylphosphine; 2,3,5-trichloro- thioxanthone .sup.31P-NMR 29.03;
.sup.1H-NMR 7.33-8.39 (m), 6.69 (s), 2.20 (s) and 2.15 (s); m.p.
172-173.degree. C. 63 172 Lithium (2,4,6- trimethylbenzoyl)-
phenylphosphine; 2-chloro-4,6-bis- (2,4-dimethyl- phenyl)-[1,3,5]-
triazine .sup.31P NMR 14.65 .sup.1H NMR 8.11-8.17 (m), 7.51-7.66
(m), 7.10-7.14 (m), 6.84 (s), 2.56 (s), 2.38 (s), 2.28 (s), 2.15
(s) m.p. 153-154.degree. C.
EXAMPLE 64
[0569] Phenyl-(2,4,6-trimethylbenzoyl)thiophosphinic
S-(4-methylphenyl) ester
[0570] At 20-30.degree. C., 4.8 g (0.025 mol) of 4-toluenesulfonyl
chloride, dissolved in 20 ml of toluene, are added dropwise over
the course of 20 min to 35 ml (0.025 mol) of the solution described
in Example 3. The yellow-brown reaction suspension is heated to
40.degree. C. and, after the mixture has been afterstirred for 2
hours, it is concentrated using the Rotavap. The residue is taken
up in 50 ml of toluene and washed with water and aqueous saturated
sodium hydrogencarbonate solution, then dried over magnesium
sulfate and filtered. The filtrate is concentrated using the
Rotavap. The residue is purified over silica gel and dried under a
high vacuum. The title compound is obtained as a yellow resin.
[0571] .sup.31P NMR: 34.79
[0572] .sup.1H NMR: 7.80-7.86 (m), 7.31-7.48 (m), 6.96-6.99(d),
6.67(s), 2.21 (s), 2.13(s), 1.84 (s)
EXAMPLE 65
[0573] A UV-curable white coat is prepared by mixing
[0574] 67.5 parts of polyester acrylate oligomer (.sup.RTMEBECRYL
830, UCB, Belgium)
[0575] 5.0 parts of hexanediol diacrylate
[0576] 2.5 parts of trimethylolpropane triacrylate
[0577] 25.0 parts of rutile titanium dioxide (.sup.RTMR-TC2,
Tioxide, France)
[0578] 2.0 parts of the photoinitiator from Example 7.
[0579] The coating is applied to a coil-coated aluminium sheet
using a 100 Am slotted doctor knife and then cured. Curing is
carried out by conveying the sample twice, on a conveyor belt which
is moving at a speed of 10 m/min, beneath an 80 W/cm
medium-pressure mercury lamp (Hanovia, USA). The pendulum hardness
is then determined in accordance with Konig (DIN53157) in [s]. The
pendulum hardness is a measure of the through-curing of the
composition. The higher the values, the more effective the curing
which has been carried out. A value of 161 s is achieved. After the
first pendulum hardness determination, the sample is after-exposed
under low-pressure mercury lamps of the type TL 40W/03 (Philips;
Emission maximum of 430 nm), and after 15 minutes the pendulum
hardness is determined again. Following after-exposure, a value of
181 s is obtained.
EXAMPLE 66
[0580] Two parts of the compound according to Example 65 are
incorporated instead of the photoinitiator compound from Example 7
into a photocurable formulation described as in Example 58, and the
formulation is applied to a coil-coated aluminium sheet as
described in Example 65. Curing is carried out by conveying the
sample four times, on a conveyor belt which is moving at a speed of
10 m/min, beneath an 80 W/cm medium-pressure mercury lamp (Hanovia,
USA). The yellowness index of the sample cured in this way is
determined in accordance with ASTMD 1925-88. A value of 2.0 is
obtained.
* * * * *