U.S. patent application number 10/632396 was filed with the patent office on 2004-02-12 for novel aminophosphonium compounds.
This patent application is currently assigned to Clariant GmbH. Invention is credited to Pfirmann, Ralf, Schiemenz, Berthold, Wessel, Thomas.
Application Number | 20040029723 10/632396 |
Document ID | / |
Family ID | 7915816 |
Filed Date | 2004-02-12 |
United States Patent
Application |
20040029723 |
Kind Code |
A1 |
Schiemenz, Berthold ; et
al. |
February 12, 2004 |
Novel aminophosphonium compounds
Abstract
The present invention relates to compounds of the formula 1 in
which one, two or three of the radicals R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are 2 --N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2,
3 or --N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2 where
m and n are an integer from 1 to 10, R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are, independently of one another, identical or different
and are a straight-chain or branched alkyl radical having 1 to 10
carbon atoms, and the remaining radical(s) R.sup.1 to R.sup.4 are 4
or --NR.sup.9R.sup.10, where R.sup.9 and R.sup.10 are identical or
different and are a straight-chain or branched alkyl radical having
1 to 10 carbon atoms, and X.sup.- is an inorganic or organic anion
or an equivalent of a multiply charged inorganic or organic anion.
The invention further relates to mixtures of substances comprising
compounds of the formula (1), to a process for preparing the
compounds of the formula (1) and to the use thereof.
Inventors: |
Schiemenz, Berthold;
(Frankfurt am Main, DE) ; Wessel, Thomas;
(Frankfurt am Main, DE) ; Pfirmann, Ralf;
(Griesheim, DE) |
Correspondence
Address: |
CLARIANT CORPORATION
INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Assignee: |
Clariant GmbH
|
Family ID: |
7915816 |
Appl. No.: |
10/632396 |
Filed: |
August 1, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10632396 |
Aug 1, 2003 |
|
|
|
10135252 |
Apr 30, 2002 |
|
|
|
6645904 |
|
|
|
|
10135252 |
Apr 30, 2002 |
|
|
|
09617471 |
Jul 17, 2000 |
|
|
|
6465643 |
|
|
|
|
Current U.S.
Class: |
502/162 ;
502/164; 544/157; 544/337; 546/22; 548/413; 564/12 |
Current CPC
Class: |
C07C 45/63 20130101;
B01J 31/0237 20130101; C07C 45/63 20130101; C07B 39/00 20130101;
B01J 31/0268 20130101; C07F 9/572 20130101; C07C 47/55 20130101;
C07F 9/6533 20130101; C07F 9/06 20130101; C07F 9/650952 20130101;
B01J 2531/985 20130101; C07F 9/59 20130101 |
Class at
Publication: |
502/162 ;
502/164; 544/157; 544/337; 546/22; 548/413; 564/12 |
International
Class: |
B01J 031/00; C07F
009/28 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 23, 1999 |
DE |
19934595.3 |
Claims
1. A compound of the formula 22in which one, two or three of the
radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
23--N{(CH.sub.2--CH.sub.2--O).- sub.mR.sup.5}.sub.2, 24or
--N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup- .8}.sub.2 where m
and n are an integer from 1 to 10, R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are, independently of one another, identical or different
and are a straight-chain or branched alkyl radical having 1 to 10
carbon atoms, and the remaining radical(s) R.sup.1 to R.sup.4 are
25or --NR.sup.9R.sup.10, where R.sup.9 and R.sup.10 are identical
or different and are a straight-chain or branched alkyl radical
having 1 to 10 carbon atoms, and X.sup.- is an inorganic or organic
anion or an equivalent of a multiply charged inorganic or organic
anion.
2. A compound as claimed in claim 1, wherein one or two of the
radicals R.sup.1, R.sup.2,
26--N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2, 27or
--N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2 and the
remaining radicals R.sup.1 to R.sup.4 are 28or
--NR.sup.9R.sup.10.
3. A compound as claimed in claim 1, wherein m and n are an integer
from 1 to 6, and R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and
R.sup.10 are identical or different and are a straight-chain or
branched alkyl radical having 1 to 4 carbon atoms.
4. A compound as claimed in claim 1, wherein X.sup.- is F.sup.-,
Cl.sup.-, Br.sup.-, I.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, NO.sub.3.sup.-, HSO.sub.4.sup.-, 1/2
SO.sub.4.sup.2-, H.sub.2PO.sub.4.sup.-, 1/2 HPO.sub.4.sup.2-, 1/3
PO.sub.4.sup.3-, R'--COO.sup.-, where R' is an alkyl radical having
1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl
radical, R"--SO.sub.3.sup.-, where R" is an alkyl radical having 1
to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl
radical, HCO.sub.3.sup.-, 1/2 CO.sub.3.sup.2- or 1/2
C.sub.6H.sub.4(COO.sup.-).sub.2.
5. A mixture of substances comprising at least one compound of the
formula 29in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X have
the above meaning, and at least one compound selected from the
group of quaternary ammonium compounds of the formula 30quaternary
ammonium salts or phosphonium salts of the formula 31polyethers of
the formula R.sup.20--(O--C.sub.xH.sub.2x).sub.s--OR.sup.21 (4) and
crown ethers, in which in formula (2) R.sup.11, R.sup.12 and
R.sup.13 are identical or different and are a linear or branched
radical of the formula --(C.sub.pH.sub.2pO).sub.rR.sup.15 in which
R.sup.15 is hydrogen or a linear or branched alkyl radical having 1
to 16 carbon atoms, p is an integer from 1 to 10 and r is an
integer from 1 to 15; or a linear or branched alkyl radical having
1 to 30 carbon atoms; or an unsubstituted phenyl or naphthyl
radical, or a substituted phenyl or naphthyl radical, where the
substituents have the meaning of halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, nitro or cyano; R.sup.14 is a linear or
branched radical of the formula --(C.sub.pH .sub.2pO).sub.rR.sup.15
and Y.sup.- is an inorganic anion; and in formula (3) R.sup.16,
R.sup.17, R.sup.18 and R.sup.19 are identical or different and are
a linear or branched alkyl radical having 1 to 22 carbon atoms; or
an unsubstituted or substituted aryl radical or a
C.sub.1-C.sub.4-alkylaryl radical, where aryl has the meaning of
phenyl or naphthyl, and said substituents are halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, nitro or cyano; Z
has the meaning of N or P, and Y.sup.- is an inorganic anion; and
in formula (4) R.sup.20 and R.sup.21 are identical or different and
are a linear or branched alkyl radical having 1 to 16 carbon atoms;
x is an integer from 2 to 6 and s is an integer from 1 to 60; or
one of the radicals R.sup.20 and R.sup.21 is hydrogen and the other
one of the radicals is a linear or branched alkyl radical having 1
to 16 carbon atoms, x is an integer from 2 to 6 and s is an integer
from 2 to 50, or the radicals R.sup.20 and R.sup.21 are hydrogen, x
is an integer from 2 to 6 and s is an integer from 3 to 5.
6. A mixture of substances as claimed in claim 5, which comprise at
least one compound of the formula (1) and at least one compound
selected from the group of quaternary ammonium compounds of the
formula (2), quaternary ammonium salts and phosphonium salts of the
formula (3), polyethers of the formula (4) and crown ethers, in
which in formula (2) R.sup.11, R.sup.12 and R.sup.13 are identical
or different and are a linear or branched radical of the formula
--(C.sub.pH.sub.2pO).sub.rR.sup.5 in which R.sup.15 is hydrogen or
a linear or branched alkyl radical having 1 to 8 carbon atoms, p is
an integer from 1 to 5 and r is an integer from 2 to 10; or a
linear or branched alkyl radical having 1 to 18 carbon atoms; or an
unsubstituted phenyl or naphthyl radical; R.sup.14 is a linear or
branched radical of the formula --(C.sub.pH
.sub.2pO).sub.rR.sup.15, in which R.sup.15 is hydrogen or a linear
or branched alkyl radical having 1 to 8 carbon atoms, p is an
integer from 1 to 5 and r is an integer from 2 to 10; and X.sup.-
is fluoride, chloride, bromide, SO.sub.4.sup.2-/2 or hydrogen
sulfate.
7. A mixture of substances as claimed in claim 5, which comprises
at least one compound of the formula (1) and at least one compound
from the group of quaternary ammonium compounds of the formula
(2).
8. A process for preparing compounds of the formula 32which
comprises reacting a phosphorus pentahalide in the presence of an
inert solvent at from -70 to 140.degree. C. with from 1 to 6 mol of
33HN{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}2, 34or
HN{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}, per halogen
equivalent to be exchanged, and subsequently reacting the reaction
product with from 1 to 10 mol of 35or HNR.sup.9R.sup.10 per halogen
equivalent still to be exchanged.
9. The process as claimed in claim 8, wherein PCl.sub.5 or
PBr.sub.5 is employed as phosphorus pentahalide.
10. The process as claimed in claim 8, wherein an aliphatic,
cycloaliphatic or aromatic hydrocarbon or a mono- or
polychlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon
is employed as inert solvent.
11. The use of a compound of the formula (1) as catalyst and
cocatalyst for phase-transfer reactions, nucleophilic substitutions
and halogen-fluorine exchange reactions.
12. The use of a mixture of substances comprising at least one
compound of the formula (1) and at least one compound selected from
the group of quaternary ammonium compounds of the formula (2),
quaternary ammonium salts or phosphonium salts of the formula (3),
polyethers of the formula (4) and crown ethers as catalyst for
phase-transfer reactions, nucleophilic substitutions and
halogen-fluorine exchange reactions.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to novel aminophosphonium
compounds, to substance mixtures containing them, and to the
preparation and use thereof.
[0002] Aminophosphonium compounds are used, as is evident from WO
98/32532 and WO 98/22413, as catalysts for preparing
fluorine-containing compounds by a halogen/fluorine exchange
reaction (halex reaction). Although the
tetrakis-(diethylamino)phosphonium bromide used in WO 98/32532 and
WO 98/22413 gives good results, it has a very high dermal toxicity
which stands in the way of industrial use, however.
SUMMARY OF THE INVENTION
[0003] The object is to provide novel compounds which are suitable
as catalyst or component of catalyst systems for phase-transfer
reactions, in particular for halogen-fluorine exchange reactions,
have a lower dermal toxicity and achieve or even exceed the results
obtainable on use of tetrakis(diethylamino)phosphonium bromide.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0004] This object is achieved by compounds of the formula 5
[0005] in which one, two or three of the radicals R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are 6
[0006] --N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2, 7
[0007] or
--N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2
[0008] where m and n are an integer from 1 to 10, R.sup.5, R.sup.6
R.sup.7 and R.sup.8 are, independently of one another, identical or
different and are a straight-chain or branched alkyl radical having
1 to 10 carbon atoms, and the remaining radical(s) R.sup.1 to
R.sup.4 are 8
[0009] or --NR.sup.9R.sup.10, where R.sup.9 and R.sup.10 are
identical or different and are a straight-chain or branched alkyl
radical having 1 to 10 carbon atoms, and X.sup.- is an inorganic or
organic anion or an equivalent of a multiply charged inorganic or
organic anion.
[0010] Compounds of interest are those of the formula (1) in which
one or two of the radicals R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are 9
[0011] --N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2, 10
[0012] or
--N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2
[0013] and the remaining radicals R.sup.1 to R.sup.4 are 11
[0014] or --NR.sup.9R.sup.10.
[0015] Importance further attaches to compounds of the formula (1)
in which m and n are an integer from 1 to 6, and R.sup.5, R.sup.6,
R.sup.7, R.sup.1, R.sup.9 and R.sup.10 are identical or different
and are a straight-chain or branched alkyl radical having 1 to 4
carbon atoms.
[0016] The aforementioned radicals R.sup.1, R.sup.2 R.sup.3 and
R.sup.4 are, in particular, 12
[0017] --N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2 or
--N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2
[0018] preferably --N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2
or --N{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}.sub.2,
particularly preferably
--N{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2.
[0019] The aforementioned remaining radical(s) R.sup.1 to R.sup.4
are, in particular, 13
[0020] In the compounds of the formula (1), X.sup.- is F.sup.-,
Cl.sup.-, Br.sup.-, I.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, NO.sub.3.sup.-, HSO.sub.4.sup.-, 1/2
SO.sub.4.sup.2-, H.sub.2PO.sub.4.sup.-, 1/2 HPO.sub.4.sup.2-, 1/3
PO.sub.4.sup.3-, R'--COO.sup.-, where R' is an alkyl radical having
1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl
radical, R"--SO.sub.3.sup.-, where R" is an alkyl radical having 1
to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl
radical, HCO.sub.3.sup.-, 1/2 CO.sub.3.sup.2- or 1/2
C.sub.6H.sub.4(COO.sup.-).sub.2.
[0021] X.sup.- is, in particular, F.sup.-, Cl.sup.-, Br.sup.-,
I.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.- or 1/2 SO.sub.4.sup.2-,
preferably F.sup.-, Cl.sup.-, or Br.sup.-, particularly preferably
Cl.sup.-.
[0022] The following aminophosphonium compounds (aminophosphonium
salts) may be mentioned as examples without claiming
completeness.
[0023] Bis(2-methoxyethyl)amino-tris(pyrrolidino)phosphonium
chloride
[0024] Di(bis(2-methoxyethyl)amino)-bis(pyrrolidino)phosphonium
chloride
[0025] Tri(bis(2-methoxyethyl)amino)-(pyrrolidino)phosphonium
chloride
[0026]
Bis(methyl-diethoxyethylene)amino-tris(pyrrolidino)phosphonium
chloride
[0027]
Di(bis(methyl-diethoxyethylene)amino)-bis(pyrrolidino)phosphonium
chloride
[0028]
Tri(bis(methyl-diethoxyethylene)amino)-(pyrrolidino)phosphonium
chloride
[0029]
Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium
chloride
[0030]
Di(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)phosphoniu-
m chloride
[0031]
Tri(bis(methyl-tetraethoxyethylene)amino)-(pyrrolidino)phosphonium
chloride
[0032] Morpholino-tris(pyrrolidino)phosphonium chloride
[0033] Dimorpholino-bis(pyrrolidino)phosphonium chloride
[0034] Trimorpholino-(pyrrolidino)phosphonium chloride
[0035] Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium
chloride
[0036] Di(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium
chloride
[0037] Tri(bis(2-methoxyethyl)amino)-(piperidino)phosphonium
chloride
[0038]
Bis(methyl-diethoxyethylene)amino-tris(piperidino)phosphonium
chloride
[0039]
Di(bis(methyl-diethoxyethylene)amino)-bis(piperidino)phosphonium
chloride
[0040]
Tri(bis(methyl-diethoxyethylene)amino)-(piperidino)phosphonium
chloride
[0041]
Bis(methyl-tetraethoxyethylene)amino-tris(piperidino)phosphonium
chloride
[0042]
Di(bis(methyl-tetraethoxyethylene)amino)-bis(piperidino)phosphonium
chloride
[0043]
Tri(bis(methyl-tetraethoxyethylene)amino)-(piperidino)phosphonium
chloride
[0044] Morpholino-tris(piperidino)phosphonium chloride
[0045] Dimorpholino-bis(piperidino)phosphonium chloride
[0046] Bis(2-methoxyethyl)amino-tris(diethylamino)phosphonium
chloride
[0047] Di(bis(2-methoxyethyl)amino)-bis(diethylamino)phosphonium
chloride
[0048] Tri(bis(2-methoxyethyl)amino)-(diethylamino)phosphonium
chloride
[0049]
Bis(methyl-tetraethoxyethylene)amino-tris(diethylamino)phosphonium
chloride
[0050]
Di(bis(methyl-tetraethoxyethylene)amino)-bis(diethylamino)phosphoni-
um chloride
[0051]
Tri(bis(methyl-tetraethoxyethylene)amino)-(diethylamino)phosphonium
chloride
[0052] Morpholino-tris(diethylamino)phosphonium chloride
[0053] Dimorpholino-bis(diethylamino)phosphonium chloride
[0054] Trimorpholino-(diethylamino)phosphonium chloride
[0055] Bis(2-methoxyethyl)amino-tris(dimethylamino)phosphonium
chloride
[0056] Di(bis(2-methoxyethyl)amino)-bis(dimethylamino)phosphonium
chloride
[0057] Tri(bis(2-methoxyethyl)amino)-(dimethylamino)phosphonium
chloride
[0058]
Bis(methyl-bisethoxyethylene)amino-tris(dimethylamino)phosphonium
chloride
[0059]
Di(bis(methyl-bisethoxyethylene)amino)-bis(dimethylamino)phosphoniu-
m chloride
[0060]
Tri(bis(methyl-bisethoxyethylene)amino)-(dimethylamino)phosphonium
chloride
[0061]
Bis(methyl-tetraethoxyethylene)amino-tris(dimethylamino)phosphonium
chloride
[0062]
Di(bis(methyl-tetraethoxyethylene)amino)-bis(dimethylamino)phosphon-
ium chloride
[0063]
Tri(bis(methyl-tetraethoxyethylene)amino)-(dimethylamino)phosphoniu-
m chloride
[0064] Tris(dimethylamino)-morpholino-phosphonium chloride
[0065] Bis(dimethylamino)-dimorpholino-phosphonium chloride
[0066] Dimethylamino-trimorpholino-phosphonium chloride
[0067] Bis(2-methoxyethyl)amino-tris(butyl-ethylamino)phosphonium
chloride
[0068]
Di(bis(2-methoxyethyl)amino)-bis(butyl-ethylamino)phosphonium
chloride
[0069] Tri(bis(2-methoxyethyl)amino)-(butyl-ethylamino)phosphonium
chloride
[0070]
Bis(methyl-tetraethoxyethylene)amino-tris(butyl-ethylamino)phosphon-
ium chloride
[0071] Di
(bis(methyl-tetraethoxyethylene)amino)-bis(butyl-ethylamino)phos-
phonium chloride
[0072]
Tri(bis(methyl-tetraethoxyethylene)amino)-(butyl-ethylamino)phospho-
nium chloride
[0073] Tris(butyl-ethylamino)-morpholino-phosphonium chloride
[0074] Bis(butyl-ethylamino)-dimorpholino-phosphonium chloride
[0075] (Butyl-ethylamino)-trimorpholino-phosphonium chloride
[0076] N-Methylpiperazino-tris(pyrrolidino)phosphonium chloride
[0077] Bis(N-methylpiperazino)-bis(pyrrolidino)phosphonium
chloride
[0078] Tris(N-methylpiperazino)-(pyrrolidino)phosphonium
chloride
[0079] N-Methylpiperazino-tris(diethylamino)phosphonium
chloride
[0080] Bis(N-methylpiperazino)-bis(diethylamino)phosphonium
chloride
[0081] Tris(N-methylpiperazino)-(diethylamino)phosphonium
chloride
[0082] N-Methylpiperazino-tris(dimethylamino)phosphonium
chloride
[0083] Bis(N-methylpiperazino)-bis(dimethylamino)phosphonium
chloride
[0084] Tris(N-methylpiperazino)-(dimethylamino)phosphonium
chloride
[0085] N-Methylpiperazino-tris(butyl-ethylamino)phosphonium
chloride
[0086] Bis(N-methylpiperazino)-bis(butyl-ethylamino)phosphonium
chloride
[0087] Tris(N-methylpiperazino)-(butyl-ethylamino)phosphonium
chloride
[0088] In place of the listed aminophosphonium chlorides it is also
possible to employ, for example, the corresponding bromides,
iodides, fluorides, sulfates, hydrogen sulfates, acetates or
phthalates.
[0089] The present invention also relates to mixtures of substances
comprising at least one compound of the formula 14
[0090] in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X.sup.- have
the above meaning, and at least one compound selected from the
group of quaternary ammonium compounds of the formula 15
[0091] quaternary ammonium salts or phosphonium salts of the
formula 16
[0092] polyethers of the formula
R.sup.20--(O--C.sub.xH.sub.2x).sub.s--OR.- sup.21 (4) and crown
ethers,
[0093] in which in formula (2) R.sup.11, R.sup.12 and R.sup.13 are
identical or different and are a linear or branched radical of the
formula --(C.sub.pH.sub.2pO).sub.rR.sup.15 in which R.sup.15 is
hydrogen or a linear or branched alkyl radical having 1 to 16
carbon atoms, p is an integer from 1 to 10 and r is an integer from
1 to 15;
[0094] or a linear or branched alkyl radical having 1 to 30 carbon
atoms;
[0095] or an unsubstituted phenyl or naphthyl radical, or a
substituted phenyl or naphthyl radical, where the substituents have
the meaning of halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy, nitro or cyano;
[0096] R.sup.14 is a linear or branched radical of the formula
--(C.sub.pH.sub.2pO).sub.rR.sup.15 and
[0097] Y.sup.- is an inorganic anion;
[0098] and in formula (3)
[0099] R.sup.16, R.sup.17, R.sup.18 and R.sup.19 are identical or
different and are a linear or branched alkyl radical having 1 to 22
carbon atoms; or an unsubstituted or substituted aryl radical or a
C.sub.1-C.sub.4-alkylaryl radical, where aryl has the meaning of
phenyl or naphthyl, and said substituents are halogen,
[0100] C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, nitro or
cyano; Z has the meaning of N or P, and Y.sup.- is an inorganic
anion;
[0101] and in formula (4)
[0102] R.sup.20 and R.sup.21 are identical or different and are a
linear or branched alkyl radical having 1 to 16 carbon atoms;
[0103] x is an integer from 2 to 6 and
[0104] s is an integer from 1 to 60;
[0105] or one of the radicals R.sup.20 and R.sup.21 is hydrogen and
the other one of the radicals is a linear or branched alkyl radical
having 1 to 16 carbon atoms,
[0106] x is an integer from 2 to 6 and s is an integer from 2 to
50, or the radicals R.sup.20 and R.sup.21 are hydrogen, x is an
integer from 2 to 6 and s is an integer from 3 to 5.
[0107] The present invention relates in particular to mixtures of
substances which comprise at least one compound of the formula (1)
and at least one compound selected from the group of quaternary
ammonium compounds of the formula (2), quaternary ammonium salts
and phosphonium salts of the formula (3), polyethers of the formula
(4) and crown ethers, in which in formula (2) R.sup.11, R.sup.12
and R.sup.13 are identical or different and are a linear or
branched radical of the formula --(C.sub.pH.sub.2pO).sub.rR.sup.15
in-which R.sup.15 is hydrogen or a linear or branched alkyl radical
having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an
integer from 2 to 10; or a linear or branched alkyl radical having
1 to 18 carbon atoms; or an unsubstituted phenyl or naphthyl
radical; R.sup.14 is a linear or branched radical of the formula
--(C.sub.pH.sub.2pO).sub.rR.sup.15, in which R.sup.15 is hydrogen
or a linear or branched alkyl radical having 1 to 8 carbon atoms, p
is an integer from 1 to 5 and r is an integer from 2 to 10; and
X.sup.- is fluoride, chloride, bromide, SO.sub.4.sup.2-/2 or
hydrogen sulfate.
[0108] Mixtures of substances of particular interest are those
comprising at least one compound of the formula (1) and at least
one compound from the group of quaternary ammonium compounds of the
formula (2).
[0109] Mention should also be made of mixtures of substances of the
above type comprising at least one ammonium salt or phosphonium
salt of the formula (3), in which in formula (3) R.sup.16,
R.sup.17, R.sup.18 and R.sup.19 are identical or different and are
a linear or branched alkyl radical having 1 to 16 carbon atoms; or
an unsubstituted or substituted aryl radical or a
C.sub.1-C.sub.4-alkylaryl radical, where aryl has the meaning of
phenyl or naphthyl, and said substituents are halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, nitro or cyano.
[0110] Mixtures of substances of the above type comprising at least
one polyether of the formula (4) or crown ether, in which in
formula (4) R.sup.20 and R.sup.21 are identical or different and
are hydrogen or a linear or branched alkyl radical having 1 to
8.1carbon atoms, x is an integer from 2 to 3 and s is an integer
from 4 to 50, are likewise of interest.
[0111] The mixtures of substances normally comprise from 5 to 95%
by weight, in particular 20 to 80% by weight, preferably 25 to 75%
by weight, of at least one compound of the formula (1). The
residual 95 to 5% by weight, in particular 80 to 20% by weight,
preferably 75 to 25% by weight, of the mixtures of substances
account for the remainder, namely at least one compound selected
from the group of quaternary ammonium compounds of the formula (2)
of quaternary ammonium or phosphonium salts of the formula (3),
polyethers of the formula (4) and crown ethers, in particular at
least one compound from the group of quaternary ammonium compounds
of the formula (2).
[0112] The present invention further relates to a process for
preparing compounds of the formula 17
[0113] It comprises reacting a phosphorus pentahalide in the
presence of an inert solvent at -70 to 140.degree. C., in
particular -30 to 120.degree. C., preferably -15 to 60.degree. C.,
with from 1 to 6 mol, in particular 1 to 2.5 mol, of 18
[0114] HN{(CH.sub.2--CH.sub.2--O).sub.mR.sup.5}.sub.2 19
[0115] or HN{(CH.sub.2--CH.sub.2--N(R.sup.7)).sub.nR.sup.8}, per
halogen equivalent to be exchanged, and subsequently reacting the
reaction product with from 1 to 10 mol, in particular 1 to 3 mol,
of 20
[0116] or HNR.sup.9R.sup.10 per halogen equivalent still to be
exchanged. This reaction of the reaction product takes place at -15
to 140.degree. C., in particular 0 to 130.degree. C., preferably 20
to 130.degree. C.
[0117] The phosphorus pentahalide employed is PCl.sub.5 or
PBr.sub.5, in particular PCl.sub.5.
[0118] The inert solvent employed is an aliphatic, cycloaliphatic
or aromatic hydrocarbon or a mono- or polychlorinated aliphatic,
cycloaliphatic or aromatic hydrocarbon.
[0119] Very suitable inert solvents are, for example, hexane,
cyclohexane, methylcyclohexane, toluene, ethylbenzene, mesitylene,
o-xylene, m-xylene, p-xylene, technical mixtures of isomeric
xylenes, methylene chloride, tetrachloroethane, chlorobenzene,
dichlorobenzene or chlorotoluene. It is also possible to use
mixtures of solvents.
[0120] The phosphorus pentahalide is suspended or dissolved in the
inert solvent and the reaction is carried out with the addition of
the aforementioned nitrogen-containing compounds.
[0121] This results in compounds of the formula (1) in which
X.sup.- is a halide. If required, the halide can be exchanged for
another one of the aforementioned anions by metathesis.
[0122] The invention further relates to the use of the compounds of
the formula (1) as catalyst and cocatalyst for phase-transfer
reactions, nucleophilic substitutions and halogen-fluorine exchange
reactions.
[0123] The invention further relates to the use of the mixtures of
substances comprising at least one compound of the formula (1) and
at least one compound selected from the group of quaternary
ammonium compounds of the formula (2), quaternary ammonium salts or
phosphonium salts of the formula (3), polyethers of the formula (4)
and crown ethers as catalyst for phase-transfer reactions,
nucleophilic substitutions and halogen-fluorine exchange
reactions.
EXAMPLES
[0124] The following examples describe the present invention
further without restricting it.
[0125] Experimental Section
[0126] Preparation of the aminophosphonium compounds
(aminophosphonium salts)
Example 1
Bis(2-methoxyethyl)amino-tris(pyrrolidino)phosphonium Chloride
[0127] 104.12 g (0.5 mol) of phosphorus pentachloride are
introduced into 400 g of chlorobenzene and cooled to -20 to
-10.degree. C. At this temperature, 66.89 g (0.5 mol) of
bis-(2-methoxyethyl)amine are added dropwise in such a way that the
internal temperature does not exceed 0.degree. C. After the
addition, the mixture is allowed to warm slowly to 30.degree. C.
and is then heated at 90-100.degree. C. for one hour.
[0128] It is then cooled again to 10.degree. C., and 214.5 g (3.0
mol) of pyrrolidine are added dropwise in such a way that the
internal temperature does not exceed 15.degree. C. After the
addition, the mixture is heated to reflux for two hours.
[0129] After cooling to 0.degree. C., 779.94 g (3.9 mol) of 20%
strength sodium hydroxide solution are cautiously used to make
alkaline. The aqueous phase is separated off and discarded. Excess
amine is then distilled out of the organic phase. After the end of
the distillation, HCl is used to acidify to pH=6-7 and, after
filtration, the chloro-benzene is stripped off in a rotary
evaporator.
[0130] Elemental analysis: C=55.2%, H=8.9%, N=12.9%, P=7.0%,
Cl=8.2%
Example 2
Bis(bis(2-methoxyethyl)amino)-bis(pyrrolidino)phosphonium
Bromide
[0131] 104, 12 g (0.5 mol) of phosphorus pentachloride are
introduced into 400 g of chlorobenzene and cooled to -20 tol
.degree. C. At this temperature, 133.78 g (1 mol) of
bis-(2-methoxyethyl)amine are added dropwise in such a way that the
internal temperature does not exceed 0.degree. C. After the
addition, the mixture is heated at 100.degree. C. for one hour.
[0132] It is then cooled again to 10.degree. C., and 214.55 g (3.0
mol) of pyrrolidine are added dropwise in such a way that the
internal temperature does not exceed 15.degree. C. After the
addition, the mixture is heated to reflux for two hours. After
cooling to 0.degree. C., 779.94 g (3.9 mol) of 20% strength sodium
hydroxide solution (equivalent to 155.99 g of NaOH) are cautiously
used to make alkaline. The aqueous phase is separated off and
discarded. After addition of 71.93 g (0.6 mol) of potassium
bromide, excess free amine is distilled out of the organic phase.
After the end of the distillation, HBr is used to acidify to pH=6-7
and, after filtration, the chlorobenzene is stripped off in a
rotary evaporator.
[0133] Elemental analysis: C=46.9%, H=8.8%, N=10.6%, P=5.9%,
Br=15.2%, Cl=0.14%
Example 3
(n-Butyl-ethylamino)-tris-(pyrrolidino)phosphonium Bromide
[0134] 42.7 g (0.6 mol) of pyrrolidine are added dropwise to 20.8 g
(0.1 mol) of PCl.sub.5 in 100 ml of chlorobenzene in 1 hour so that
the internal temperature does not exceed 15.degree. C. After the
addition, the mixture is stirred at 50.degree. C. for one hour and
then, at a reaction temperature of 25.degree. C., 16 g (0.22 mol)
of n-butylamine are added.
[0135] After 1 hour under reflux, the mixture is again cooled to
25.degree. C. and hydrolyzed with 200 ml of ice-water, and the
aqueous phase is separated off. After the excess amine has been
distilled off, 19.9 g (0.5 mol) of NaOH in 20 ml of water are
introduced. At 50.degree. C., 12.0 g (0.11 mol) of ethyl bromide
are added dropwise. After stirring at 70.degree. C. for 3 hours,
the mixture is cooled to 25.degree. C. and diluted with 200 ml of
water. The organic phase is separated off and acidified to pH=6-7
with 60% strength hydro-bromic acid. After all the volatile
constituents have been distilled off, 33.6 g
(n-butyl-ethylamino)-tris-(pyrrolidino)phosphonium bromide are
obtained as a pale brownish oil.
Example 4
Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium
Chloride
[0136]
Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium
chloride is prepared in analogy to Example 1 from 104.12 g (0.5
mol) of phosphorus penta-chloride, 198.75 g (0.5 mol) of
bis-(methyl-tetraethoxye- thylene)amine
(.dbd.HN{(CH.sub.2--CH.sub.2--O).sub.4CH.sub.3}.sub.2) and 214.55 g
(3.0 mol) of pyrrolidine.
[0137] Elemental analysis: C=53.6%, H=9.6%, N=8.1%, P=4.3%,
Cl=5.6%
Example 5
Bis(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)-phosphonium
Chloride
[0138]
Bis(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)phosphoni-
um chloride is prepared in analogy to Example 2 from 104.12 g (0.5
mol) of phosphorus penta-chloride, 397.51 g (1 mol) of
bis-(methyl-tetraethoxyeth- ylene)amine
(.dbd.HN{(CH.sub.2--CH.sub.2--O).sub.4CH.sub.3}.sub.2) and 214.55 g
(3.0 mol) of pyrrolidine.
[0139] Elemental analysis: C=44.7%, H=8.3%, N=6.5%, P=3.7%,
Cl=4.5%
Example 6
Tris(2-methoxyethyl)amino-(diethylamino)phosphonium Bromide
[0140] 104.12 g (0.5 mol) of phosphorus pentachloride are
introduced into 400 g of chlorobenzene and cooled to -20 to
-10.degree. C. At a reaction temperature of <5.degree. C.,
401.34 g (3 mol) of bis-(2-methoxyethyl)amine are added dropwise.
After the addition, the mixture is slowly allowed to warm to
30.degree. C. and is then heated at 100.degree. C. for one
hour.
[0141] At 20.degree. C., 36 g (2.1 mol) of ammonia are passed in.
After hydrolysis with 850 g of 20% strength aqueous sodium
hydroxide solution, the chlorobenzene and the excess
bis(2-methoxyethyl)amine are distilled out of the organic phase
(120.degree. C., 10 mbar). The oily residue is taken up in 300 ml
of chlorobenzene, and 340 g of 50% strength aqueous sodium
hydroxide solution are added. At 50.degree. C., 119 g (1.1 mol) of
ethyl bromide are added dropwise, and the mixture is then stirred
at 70.degree. C. for three hours to complete the reaction. Then, at
20.degree. C., 350 ml of water are added and, after phase
separation, the organic phase is neutralized with 24 g of 36%
strength hydrobromic acid. Removal of all volatile constituents by
distillation results in 33.6 g of
tris(2-methoxyethyl)amino-(diethylamino)phosphonium bromide as a
brownish oil:
[0142] Elemental analysis: C=36.1%, H=7.9%, N=7.5%, P=4.15%,
Br=9.8%, Cl=0.5%.
Example 7
N-Methylpiperazino-tris(pyrrolidino)phosphonium Chloride
[0143] 41.65 g (0.2 mol) of phosphorus pentachloride are introduced
into 200 g of toluene and cooled to -20.degree. C. Then 20.03 g
(0.2 mol) of N-methylpiperazine are added dropwise in such a way
that the internal temperature does not exceed 5.degree. C. After
the addition, the mixture is heated at 100.degree. C. for one
hour.
[0144] At 10.degree. C., 56.9 g (0.8 mol) of pyrrolidine are added
dropwise. After the addition, the mixture is allowed to warm slowly
to 20.degree. C. After a further 30 min, it is heated to reflux for
two hours.
[0145] After hydrolysis with 20% strength aqueous sodium hydroxide
solution, the toluene and the excess amine are distilled out of the
organic phase (120.degree. C., 10 mbar). 69.6 g of
N-methylpiperazino-tris(pyrrolidino)phosphonium chloride are
obtained as a brownish oil.
[0146] Elemental analysis: C=54.3%, H=9.6%, N=18.5%, P=8.15%,
Cl=9.7%
Example 8
Dioctylamino-tris(pyrrolidino)phosphonium Chloride
[0147] Dioctylamino-tris(pyrrolidino)phosphonium chloride is
prepared in analogy to Example 1 from 41.65 g (0.2 mol) of
phosphorus pentachloride, 48.3 g (0.2 mol) of dioctylamine and 99.6
g (1.4 mol) of pyrrolidine.
[0148] Elemental analysis: C=65.3%, H=11.6%, N=10.5%, P=5.9%,
Cl=7.0%
Example 9
Morpholino-tris(pyrrolidino)phosphonium Chloride
[0149] Morpholino-tris(pyrrolidino)phosphonium chloride is prepared
in analogy to Example 1 from 104.12 g (0.5 mol) of phosphorus
pentachloride, 43.6 g (0.5 mol) of morpholine and 214.6 g (3.0 mol)
of pyrrolidine.
[0150] Elemental analysis: C=52.8%, H=9.0%, N=15.3%, P=8.4%,
Cl=10.1%
[0151] The corresponding bromide is obtained by salts metathesis in
analogy to Example 2.
Example 10
Bis(morpholino)-bis(pyrrolidino)phosphonium Chloride
[0152] Bis(morpholino)-bis(pyrrolidino)phosphonium chloride is
prepared in analogy to Example 2 from 104.12 g (0.5 mol) of
phosphorus pentachloride, 87.12 g (1 mol) of morpholine and 214.55
g (3.0 mol) of pyrrolidine.
[0153] Elemental analysis: C=50.6%, H=8.7%, N=14.6%, P=8.0%,
Cl=9.5%
[0154] The corresponding bromide is obtained by salt metathesis in
analogy to Example 2.
Example 11
Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium Chloride
[0155] Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium
chloride is prepared in analogy to Example 2 from 104.12 g (0.5
mol) of phosphorus pentachloride, 66.9 g (0.5 mol) of
bis-(2-methoxyethyl)amine and 255.4 g (3.0 mol) of piperidine.
Example 12
Bis(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium
Chloride
[0156] Bis(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium
chloride is prepared in analogy to Example 1 from 104.12 g (0.5
mol) of phosphorus pentachloride, 133.2 g (1 mol) of
bis-(2-methoxyethyl)amine and 212.9 g (2.5 mol) of piperidine.
Comparative Example A: Tetrakis(diethylamino)phosphonium
Bromide
[0157] (Comparison Substance)
[0158] 109.7 g (1.5 mol) of diethylamine are added dropwise to a
52.1 g (0.25 mol) of PCl.sub.5 in 220 ml of chlorobenzene in 1 hour
so that the internal temperature does not exceed 5.degree. C. After
the addition, the mixture is stirred at 30.degree. C. for one hour
and then, at T=15.degree. C., 30 g of ammonia are passed in:
[0159] After 1 hour, 340 g of 20% strength sodium hydroxide
solution are added, and the aqueous phase is separated off. The
excess diethylamine is distilled out of the organic phase. Then 170
g of 50% strength sodium hydroxide solution and 60 g (0.55 mol) of
ethyl bromide are added, and the mixture is heated at 50.degree. C.
for 4 hours. After phase separation, the organic phase is acidified
to pH=6-7 with 60% strength hydrobromic acid. Removal of all the
volatile constituents by distillation results in 83.9 g of
tetrakis(diethylamino)phosphonium bromide as a pale brownish
oil.
Comparative Example B: Tris(dibutylamino)-(diethylamino)phosphonium
Bromide
[0160] (Comparison Substance)
[0161] Tris(dibutylamino)-(diethylamino)phosphonium bromide is
prepared in analogy to Comparative Example A from 41.65 g (0.2 mol)
of phosphorus pentachloride, 77.50 g (0.6 mol) of dibutylamine, an
excess of ammonia and 47.9 g (0.44 mol) of ethyl bromide.
[0162] Elemental analysis: C=53.2%, H=10.9%, N=12.3%, P=6.75%,
Br=16.3%, Cl=0.7%
[0163] Testing of the Catalytic Activity:
[0164] Preparation of 2,6-difluorobenzaldehyde (DFBAL) from
2-chloro-6-fluorobenzaldehyde (CFBAL) by chlorine-fluorine exchange
reaction
Comparative Example 1A and 1 B
[0165] At 60.degree. C., 4.4 g (0.01 mol) of
tetrakis(diethylamino)phospho- nium bromide (Comparative Example
1A) or 5.7 g (0.01 mol) of
tris(dibutylamino)-(diethylamino)-phosphonium bromide (Comparative
Example 1B) and, in each case, 17.6 g (0.03 mol) of
methyl-tris(methyltetraethoxy)ammonium chloride
[{CH.sub.3--(O--C.sub.2H.- sub.4).sub.4}.sub.3NCH.sub.3]Cl, 58.3 g
(1 mol) of potassium fluoride and 10 ml of chlorobenzene are
successively added to 158.6 g (1 mol) of
2-chloro-6-fluorobenzaldehyde (CFBAL). The reaction mixture is
dried by azeotropic distillation of the chlorobenzene under reduced
pressure. After 20 hours at 170.degree. C., the formation of
2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction
are determined by gas chromatography.
EXAMPLES
[0166] In the following examples identified by an * in Table 1, in
place of tetrakis(diethylamino)phosphonium bromide there is used an
equivalent molar quantity of the aminophosphonium salt indicated in
each case in Table 1 (0.01 mol in each case) and 0.03 mol of
methyl-tris(methyltetraet- hoxy)ammonium chloride. The procedure is
otherwise analogous to Comparative Example 1A.
[0167] The numerical data in Table 1 correspond to GC percentage
areas. The difference from 100% (remainder) which is likewise
indicated in Table 1 is a measure of side reactions and
decomposition.
1TABLE 1 Yields of 2,6-difluorobenzaldehyde (DFBAL) from the halex
reaction of 2-chloro-6- fluorobenzaldehyde (CFBAL) in GC % areas
Re- Aminophosphonium salt DFBAL CFBAL mainder No catalysts 16.2
72.1 11.7 [(Et.sub.2N).sub.4P]Br 56.1 24.7 19.2 [(Bu.sub.2N)
.sub.3(Et.sub.2N)P]Br 63.0 20.1 16.9 [(Me(OCH.sub.2CH.sub.2).sub.2-
N)(pyrrolidino).sub.3P]Br * 68.9 15.0 16.1
[(Me(OCH.sub.2CH.sub.2).- sub.2N)(pyrrolidino).sub.3P]Cl * 67.7
17.8 14.5
[(Me(OCH.sub.2CH.sub.2).sub.2N).sub.2(pyrrolidino).sub.2P]Br * 70.2
12.3 17.5 [{(Et)(Bu)N}(pyrrolidino).sub.3P]Br * 64.4 22.6 13.0
[{(Me(O--C.sub.2H.sub.4).sub.4).sub.2N}(pyrrolidino).sub.3P]Br *
71.5 18.4 10.1
[{(Me(O--C.sub.2H.sub.4).sub.4).sub.2N}.sub.2(pyrrolidin-
o).sub.2P]Br * 70.8 17.2 12.0
[(N-Me(piperazino)(pyrrolidino).sub.3- P]Cl * 68.2 18.2 13.6
[(Morpholino)(pyrrolidino).sub.3P]Br * 68.5 18.1 13.4
[(Morpholino)(pyrrolidino).sub.3P]Cl * 68.2 17.1 14.7
[(Morpholino).sub.2(pyrrolidino).sub.2P]Br * 66.3 19.7 14.0
[(Morpholino).sub.2(pyrrolidino).sub.2P]Cl * 65.8 20.1 14.1
[(Me(OCH.sub.2CH.sub.2).sub.2N)(piperidino).sub.3P]Cl * 71.2 16.8
12.0 [(Me(OCH.sub.2CH.sub.2).sub.2N).sub.2(piperidino).sub.2P]Cl *
70.4 18.2 11.4 * Examples
[0168] Testing of the Catalytic Activity:
[0169] Preparation of 2,6-difluorobenzaldehyde (DFBAL) and
2-chloro-6-fluorobenzaldehyde (CFBAL) from 2,6-dichlorobenzaldehyde
(DCBAL) by chlorine-fluorine exchange reaction.
Comparative Example 2A and 2 B
[0170] At 60.degree. C., 8.8 g (0.02 mol) of
tetrakis(diethylamino)phospho- nium bromide (Comparative Example
2A) or 11.35 g (0.02 mol) of
tris(dibutylamino)(diethylamino)phosphonium bromide (Comparison
Example 2B) and, in each case, 35.2 g (0.06 mol) of
methyl-tris(methyltetraethoxy- )ammonium chloride, 116.2 g (2 mol)
of potassium fluoride and 10 ml of chlorobenzene are successfully
added to 175.0 g (1 mol) of 2,6-dichlorobenzaldehyde (DCBAL). The
reaction mixture is dried by azeotropic distillation of the
chlorobenzene under reduced pressure. After 20 hours at 165.degree.
C., the formation of 2-chloro-6-fluorobenzaldehyde (CFBAL) and
2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction
are determined by gas chromatography.
EXAMPLES
[0171] In the following examples identified by an * in Table 2, in
place of tetrakis-(diethylamino)phosphonium bromide there is used
an equivalent molar quantity of the aminophosphonium salt indicated
in each case (0.02 mol in each case) and 0.06 mol of
methyl-tris(methyltetraethoxy)ammonium chloride. The procedure is
otherwise analogous to Comparative Example 2A.
[0172] The numerical data in Table 2 correspond to GC percentage
areas. The difference from 100% (remainder) which is likewise
indicated in Table 2 is a measure of side reactions and
decomposition.
2TABLE 2 Yields of 2,6-difluorobenzaldehyde (DFBAL) and
2-chloro-6-fluorobenzaldehyde (CFBAL) from the halex reaction of
2,6-dichlorobenzaldehyde (DCBAL) in GC % areas Aminophosphonium
salt DFBAL CFBAL DCBAL Remainder no catalyst 1.2 11.4 71.5 15.9
[(Et.sub.2N).sub.4P]Br 40.2 26.9 11.2 21.7
[(Bu.sub.2N).sub.3(Et.sub.2N)P]Br 41.1 27.5 10.4 21.0
[(Me(OCH.sub.2CH.sub.2).sub.2N)(pyrrolidino).sub.3P]Br * 51.1 36.1
1.8 11.0 [(Me(OCH.sub.2CH.sub.2).sub.2N)(pyrrolidino).sub.3P]Cl *
50.7 37.8 2.1 9.4
[(Me(OCH.sub.2CH.sub.2).sub.2N).sub.2(pyrrolidino).su- b.2P]Br *
50.6 37.3 1.4 10.7 [{(Et)(Bu)N}(pyrrolidino).sub.3P]Br * 43.6 31.2
8.6 16.6 [(Octyl.sub.2N)(pyrrolidino).sub.3P]Br * 41.6 33.5 8.1
16.8 [{(Me(O--C.sub.2H.sub.4).sub.4).sub.2N}(pyrrolidino)-
.sub.3P]Br * 53.8 31.4 3.9 10.9
[{(Me(O--C.sub.2H.sub.4).sub.4).sub-
.2N}.sub.2(pyrrolidino).sub.2P]Br * 50.4 36.8 2.1 10.7
[(N-Me(piperazino)(pyrrolidino).sub.3P]Cl * 46.9 38.2 4.4 10.5
[(Morpholino)(pyrrolidino).sub.3P]Br * 46.9 32.3 5.1 15.7
[(Morpholino)(pyrrolidino).sub.3P]Cl * 47.2 34.8 5.4 12.6
[(Morpholino).sub.2(pyrrolidino).sub.2P]Br * 47.8 35.6 5.2 11.4
[(Morpholino).sub.2(pyrrolidino).sub.2P]Cl * 49.6 31.9 4.8 13.7
[(Me(OCH.sub.2CH.sub.2).sub.2N)(piperidino).sub.3P]Cl * 54.2 34.4
1.7 9.7 [(Me(OCH.sub.2CH.sub.2).sub.2N).sub.2(piperidino).sub.2P]Cl
* 53.1 35.5 1.5 9.9 * Examples
[0173] In Tables 1 and 2, Me stands for methyl, Et for ethyl and Bu
for butyl, Me(O--C.sub.2H.sub.4).sub.4 for
methyl-tetraethoxyethylene 21
* * * * *