U.S. patent application number 09/891304 was filed with the patent office on 2002-05-16 for 2,2 (diarlyl) vinylphosphine compound,palladium catalyst thereof, and process forproducing arylamine, diaryl, or arylalkyne with the catalyst.
Invention is credited to Hagiwara, Toshimitsu, Hori, Yoji, Kobayashi, Tohru, Nishikawa, Takenobu, Suzuki, Ken.
Application Number | 20020058837 09/891304 |
Document ID | / |
Family ID | 18693474 |
Filed Date | 2002-05-16 |
United States Patent
Application |
20020058837 |
Kind Code |
A1 |
Suzuki, Ken ; et
al. |
May 16, 2002 |
2,2 (Diarlyl) Vinylphosphine compound,palladium catalyst thereof,
and process forproducing arylamine, diaryl, or arylalkyne with the
catalyst
Abstract
A novel 2,2-(diaryl)vinylphosphine compound represented by the
following general formula (1): 1 (wherein R.sup.1 is a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group
having 5 to 7 carbon atoms, etc.; R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, and R.sup.7 may be the same or different and each
is an alkyl group having 1 to 6 carbon atoms, an alicyclic group
having 5 to 7 carbon atoms, etc., provided that R.sup.4 and R.sup.5
taken together and/or R.sup.6 and R.sup.7 taken together may
represent a fused benzene ring, a substituted fused benzene ring, a
trimethylene group, etc.; and p, q, r, and s each is 0 to 5,
provided that p+q and r+s each is in the range of from 0 to 5); a
palladium-phosphine catalyst obtained by causing a palladium
compound to act on the novel 2,2-(diaryl)vinylphosphine compound;
and a process for obtaining an arylamine, a diaryl and an
arylalkyne in the presence of the palladium-phosphine catalyst.
Inventors: |
Suzuki, Ken; (Hiratsuka-shi,
JP) ; Kobayashi, Tohru; (Hiratsuka-shi, JP) ;
Nishikawa, Takenobu; (Hiratsuka-shi, JP) ; Hori,
Yoji; (Hiratsuka-shi, JP) ; Hagiwara, Toshimitsu;
(Hiratsuka-shi, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Family ID: |
18693474 |
Appl. No.: |
09/891304 |
Filed: |
June 27, 2001 |
Current U.S.
Class: |
564/15 ; 568/13;
568/17 |
Current CPC
Class: |
C07F 15/006 20130101;
C07F 15/0066 20130101; C07C 1/321 20130101; C07F 9/5013 20130101;
C07C 2531/24 20130101; C07B 37/04 20130101 |
Class at
Publication: |
564/15 ; 568/17;
568/13 |
International
Class: |
C07F 009/28 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 28, 2000 |
JP |
2000-194690 |
Claims
What is claimed is:
1. A 2,2-(diaryl)vinylphosphine compound represented by the
following general formula (1): 28wherein R.sup.1 is a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group
having 5 to 7 carbon atoms, or a phenyl group which may have one or
more substituents; R.sup.2 and R.sup.3 may be the same or different
and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic
group having 5 to 7 carbon atoms, or a phenyl group which may have
one or more substituents; R.sup.4, R.sup.5, R.sup.6, and R.sup.7
may be the same or different and each is an alkyl group having 1 to
6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, a
phenyl group which may have one or more substituents, an alkoxy
group having 1 to 6 carbon atoms, a dialkylamino group in which
each alkyl has 1 to 3 carbon atoms, a halogen atom, a benzyl group,
a naphthyl group, or a halogen-substituted lower alkyl group having
1 or 2 carbon atoms, provided that R.sup.4 and R.sup.5 taken
together and/or and R.sup.6 and R.sup.7 taken together may
represent a fused benzene ring, a substituted fused benzene ring, a
trimethylene group, a tetramethylene group, or a methylenedioxy
group; and p, q, r, and s each is 0 to 5, provided that p+q and r+s
each is in the range of from 0 to 5.
2. A palladium-phosphine catalyst obtained by causing a palladium
compound to act on the 2,2-(diaryl)vinylphosphine compound of claim
1.
3. The palladium-phosphine catalyst of claim 2, wherein the
palladium compound is a salt or complex of palladium having a
valence of 4, 2, or 0.
4. A process for producing an arylamine which comprises using the
palladium-phosphine catalyst of claim 2 or 3 in the amination
reaction of an aryl compound represented by the following general
formula (2): ArX.sup.1 (2) wherein Ar is an aryl group which may
have one or more substituents, or a heteroaryl group which may have
one or more substituents; and X.sup.1 is a halogen atom, a
trifluoromethanesulfonylox- y group, a methanesulfonyloxy group, or
a toluenesulfonyloxy group with an amine compound in the presence
of a base.
5. A process for producing a diaryl which comprises using the
palladium-phosphine catalyst of claim 2 or 3 in the carbon-carbon
bond formation reaction of an aryl compound represented by the
following general formula (2) ArX.sup.1 (2) wherein Ar and X.sup.1
have the same meanings as defined above with an arylboric acid
compound or an arylborate ester compound in the presence of a
base.
6. A process for producing an arylalkyne which comprises using the
palladium-phosphine catalyst of claim 2 or 3 in the carbon-carbon
bond formation reaction of an aryl compound represented by the
following general formula (2) ArX.sup.1 (2). wherein Ar and X.sup.1
have the same meanings as defined above with an alkyne compound in
the presence of a base.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a novel
2,2-(diaryl)vinylphosphine compound and a palladium-phosphine
catalyst obtained by causing a palladium compound to act on the
2,2-(diaryl)vinylphosphine compound. The invention further relates
to a process for obtaining an arylamine, a diaryl and an arylalkyne
in the presence of the palladium-phosphine catalyst.
BACKGROUND ART
[0002] Many transition metal complexes have conventionally been
used as catalysts for organic synthesis reactions. Phosphine
compounds play an extremely important role as ligands required of
these catalysts. For example, in Tsuji-Trost reaction, in which an
allyl compound reacts with a nucleating agent with the aid of a
palladium catalyst, phosphine compounds including
triphenylphosphine function to stabilize the catalyst and
accelerate the reaction (see Jiro Tsuji, Palladium Reagents and
Catalysts, JOHN WILEY & SONS, 1995, pp. 125-188, pp.
290-340).
[0003] In recent years, S. L. Buchwald et al. disclosed a method
for synthesizing an arylamine by the amination reaction of an aryl
compound having a leaving group (see U.S. Pat. No. 5,576,460,
International Publication 2000/02887, and S. L. Buchwald et al., J.
Org. Chem., 2000, 65, pp. 1158-1174). Also disclosed is a process
for arylamine production which is characterized by using a catalyst
comprising a trialkylphosphine and a palladium compound (see
JP-A-10-139742). (The term "JP-A" as used herein means an
"unexamined published Japanese patent application".)
[0004] Also disclosed is a method for synthesizing a diaryl
compound by the carbon-carbon bond formation reaction of an aryl
compound having a leaving group with an arylboric acid compound or
an arylborate ester compound (see A. F. Littke et al., J. Am. Chem.
Soc., 2000, 122, pp. 4020-4028, D. Z. Adriano et al., Tetrahedron
Letters, 2000, 41, pp. 8199-8202, and N. Miyaura and A. Suzuki,
Chem. Rev., 1995, 95, pp. 2457-2483).
[0005] Furthermore disclosed is a method for synthesizing an
arylalkyne by the carbon-carbon bond formation reaction of an aryl
compound having a leaving group with an alkyne compound (see H-F.
Chow et al., J. Org. Chem., 2001, 66, pp. 1910-1913, Y. Nishihara
et al., J. Org. Chem., 2000, 65, pp. 1780-1787, J-F. Nguefack et
al., Tetrahedron Letters, 1996, 37, pp. 5527-5530, and N. A.
Bumagin et al., Tetrahedron Letters, 1996, 37, pp. 897-900).
[0006] Although it is important to constitute an optimal catalyst
according to the intended reaction or the substrate to be reacted,
there can be a variety of complicated combinations of catalyst
components, i.e., a metal and a phosphine ligand. Consequently,
there are cases where even when phosphine ligands which have been
developed so far are used, the catalysts are insufficient in
catalytic activity, etc. and hence pose a problem when subjected to
practical use in industrial reactions. It is therefore important to
develop a novel phosphine ligand.
[0007] An object of the invention is to provide a novel ligand
useful in various catalytic reactions. Another object of the
invention is to provide a process for producing an arylamine, a
diaryl and an arylalkyne important as an intermediate for medicines
and agricultural chemicals and as an organic electronic material
using a catalyst containing the ligand.
SUMMARY OF THE INVENTION
[0008] In order to achieve the above objects, the present inventors
made extensive studies. As a result, it has been found that a novel
2,2-(diaryl)vinylphosphine compound. Furthermore, it has been found
that a catalyst prepared from this 2,2-(diaryl)vinylphosphine
compound and a palladium compound is effective in the amination
reaction of an aryl compound having a leaving group, the
carbon-carbon bond formation reaction of an aryl compound having a
leaving group with an arylboric acid compound or an arylborate
ester compound, and the carbon-carbon bond formation reaction of an
aryl compound having a leaving group with an alkyne compound, and
enables an arylamine, a diaryl and an arylalkyne to be produced
efficiently in a short time period. The invention has been
completed based on this finding.
[0009] The invention includes the following.
[0010] 1. A 2,2-(diaryl)vinylphosphine compound represented by the
following general formula (1): 2
[0011] (wherein R.sup.1 is a hydrogen atom, an alkyl group having 1
to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms,
or a phenyl group which may have one or more substituents; R.sup.2
and R.sup.3 may be the same or different and each is an alkyl group
having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon
atoms, or a phenyl group which may have one or more substituents;
R.sup.4, R.sup.5, R.sup.6, and R.sup.7 may be the same or different
and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic
group having 5 to 7 carbon atoms, a phenyl group which may have one
or more substituents, an alkoxy group having 1 to 6 carbon atoms, a
dialkylamino group having 1 to 3 carbon atoms, a halogen atom, a
benzyl group, a naphthyl group, or a halogen-substituted lower
alkyl group having 1 or 2 carbon atoms, provided that R.sup.4 and
R.sup.5 taken together and/or R.sup.6 and R.sup.7 taken together
may represent a fused benzene ring, a substituted fused benzene
ring, a trimethylene group, a tetramethylene group, or a
methylenedioxy group; and p, q, r, and s each is 0 to 5, provided
that p+q and r+s each is in the range of from 0 to 5).
[0012] 2. A palladium-phosphine catalyst obtained by causing a
palladium compound to act on the 2,2-(diaryl)vinylphosphine
compound described in 1 above.
[0013] 3. The palladium-phosphine catalyst described in 2 above
wherein the palladium compound is a salt or complex of palladium
having a valence of 4, 2, or 0.
[0014] 4. A process for producing an arylamine which comprises
using the palladium-phosphine catalyst described in 2 or 3 above in
the amination reaction of an aryl compound represented by the
following general formula (2):
ArX.sup.1 (2)
[0015] (wherein Ar is an aryl group which may have one or more
substituents, or a heteroaryl group which may have one or more
substituents; and X.sup.1 is a halogen atom, a
trifluoromethanesulfonylox- y group, a methanesulfonyloxy group, or
a toluenesulfonyloxy group) with an amine compound in the presence
of a base.
[0016] 5. A process for producing a diaryl which comprises using
the palladium-phosphine catalyst described in 2 or 3 above in the
carbon-carbon bond formation reaction of an aryl compound
represented by the following general formula (2)
ArX.sup.1 (2)
[0017] (wherein Ar and X.sup.1 have the same meanings as defined
above with an arylboric acid compound or an arylborate ester
compound in the presence of a base).
[0018] 6. A process for producing an arylalkyne which comprises
using the palladium-phosphine catalyst described in 2 or 3 above in
the carbon-carbon bond formation reaction of an aryl compound
represented by the following general formula (2)
ArX.sup.1 (2)
[0019] (wherein Ar and X.sup.1 have the same meanings as defined
above with an alkyne compound in the presence of a base).
DETAILED DESCRIPTION OF THE INVENTION
[0020] The invention will be explained below in detail.
[0021] In the compound (1) of the invention, R.sup.1 is a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group
having 5 to 7 carbon atoms, or a phenyl group which may have one or
more substituents. R.sup.1 is preferably a hydrogen atom, a lower
alkyl group having 1 to 3 carbon atoms, an alicyclic group having 6
carbon atoms, or a phenyl group.
[0022] Specific examples of R.sup.1 include a hydrogen atom; an
alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl,
propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl,
pentyl, or hexyl; an alicyclic group having 5 to 7 carbon atoms,
such as cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group
which may have one or more substitutents, for example, a lower
alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl,
propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a
lower alkoxy group having 1 to 4 carbon atoms, such as methoxy,
ethoxy, propoxy or butoxy, a di(lower alkyl)amino group in which
each alkyl has 1 to 3 carbon atoms, such as dimethylamino,
diethylamino or dipropylamino, or a halogen atom such as fluorine,
chlorine, bromine or iodine.
[0023] R.sup.2 and R.sup.3 may be the same or different and each is
an alkyl group having 1 to 6 carbon atoms, an alicyclic group
having 5 to 7 carbon atoms, or a phenyl group which may have one or
more substituents. Preferably, R.sup.2 and R.sup.3 may be the same
and different and each is a lower alkyl group having 1 to 4 carbon
atoms, an alicyclic group having 6 carbon atoms, or a phenyl
group.
[0024] Specific examples of R.sup.2 and R.sup.3 include an alkyl
group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl,
isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, pentyl or
hexyl; an alicyclic group having 5 to 7 carbon atoms, such as
cyclopentyl, cyclohexyl or cycloheptyl; a phenyl group which may
have one or more substitutents, for example, a lower alkyl group
having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,
isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl, a lower
alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy,
propoxy or butoxy, a di(lower alkyl)amino group in which each alkyl
has 1 to 3 carbon atoms, such as dimethylamino, diethylamino or
dipropylamino, or a halogen atom such as fluorine, chlorine,
bromine or iodine.
[0025] R.sup.4, R.sup.5, R.sup.6, and R.sup.7 may be the same or
different and each is an alkyl group having 1 to 6 carbon atoms, an
alicyclic group having 5 to 7 carbon atoms, a phenyl group which
may have one or more substituents, an alkoxy group having 1 to 6
carbon atoms, a dialkylamino group in which each alkyl has 1 to 3
carbon atoms, a halogen atom, a benzyl group, a naphthyl group, or
a halogen-substituted lower alkyl group having 1 or 2 carbon atoms,
provided that R.sup.4 and R.sup.5 taken together and/or R.sup.6 and
R.sup.7 taken together represent a fused benzene ring, a
substituted fused benzene ring, a trimethylene group, a
tetramethylene group, or a methylenedioxy group; and p, q, r, and s
each is 0 to 5, provided that p+q and r+s each is in the range of
from 0 to 5. Preferably, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 may
be the same or different and each is a lower alkyl group having 1
to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms,
a di(lower alkyl)amino group in which each alkyl has 1 or 2 carbon
atoms, or a halogen atom, provided that R.sup.4 and R.sup.5 may and
R.sup.6 and R.sup.7 may together represent a fused benzene ring or
a methylenedioxy group. Furthermore, p, q, r, and s each preferably
is 0 to 2.
[0026] Specific examples of R.sup.4, R.sup.5, R.sup.6, and R.sup.7
include a hydrogen atom; a lower alkyl group having 1 to 4 carbon
atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl,
tert-butyl, isobutyl or sec-butyl; an alicyclic group having 5 to 7
carbon atoms, such as cyclopentyl, cyclohexyl or cycloheptyl; a
phenyl group which may have one or more substitutents, for example,
a lower alkyl group having 1 to 4 carbon atoms, such as methyl,
ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl or
sec-butyl, a lower alkoxy group having 1 to 4 carbon atoms, such as
methoxy, ethoxy, propoxy or butoxy, a di(lower alkyl)amino group in
which each alkyl has 1 to 3 carbon atoms, such as dimethylamino,
diethylamino or dipropylamino, or a halogen atom such as fluorine,
chlorine, bromine or iodine; a lower alkoxy group having 1 to 4
carbon atoms, such as methoxy, ethoxy, propoxy, or butoxy; a
di(lower alkyl)amino group in which each alkyl has 1 to 3 carbon
atoms, such as dimethylamino, diethylamino or dipropylamino; a
halogen atom such as fluorine, chlorine, bromine or iodine; a
benzyl group; a naphthyl group; or a halogen-substituted lower
alkyl group having 1 or 2 carbon atoms, such as trifluoromethyl,
trichloromethyl, or tribromomethyl.
[0027] Furthermore, R.sup.4 and R.sup.5 taken together and/or
R.sup.6 and R.sup.7 taken together represent a fused benzene ring,
a substituted fused benzene ring, a trimethylene group, a
tetramethylene group, or a methylenedioxy group.
[0028] Preferred examples of the 2,2-(diaryl)vinylphosphine
compound of the invention, which is represented by general formula
(1) described above, include the compounds shown in Tables 1 to 17
given below. However, the compound of the invention should not be
construed as being limited to these examples.
[0029] The abbreviations used in Tables 1 to 17 have the following
meanings, respectively. The abbreviations used in compound names
appearing hereinafter have the same meanings. The numeral preceding
the abbreviation or symbol for a substituent indicates the position
of the substituent on the phenyl group (for example, 4-Me means a
methyl substituent bonded to the 4-position carbon atom of the
phenyl group).
[0030] Me methyl
[0031] Et ethyl
[0032] nPr n-propyl
[0033] iPr isopropyl
[0034] nBu n-butyl
[0035] iBu isobutyl
[0036] tBu tert-butyl
[0037] MeO methoxy
[0038] EtO ethoxy
[0039] F fluorine atom
[0040] Cl chlorine atom
[0041] Br bromine atom
[0042] Me.sub.2N dimethylamino
[0043] Et.sub.2N diethylamino
[0044] CyPe cyclopentyl
[0045] CyHx cyclohexyl
[0046] Ph phenyl
[0047] p-Tol p-tolyl
[0048] Xy 2,4-xylyl
[0049] 2,3-benzene means that the substituents fuse with the
benzene ring to form an .alpha.-naphthyl group.
[0050] 3,4-benzene means that the substituents fuse with the
benzene ring to form a .beta.-naphthyl group.
1TABLE 1 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 1 H Me Me 0 -- 0 --
0 -- 0 -- 2 H Et Et 0 -- 0 -- 0 -- 0 -- 3 H nPr nPr 0 -- 0 -- 0 --
0 -- 4 H iPr iPr 0 -- 0 -- 0 -- 0 -- 5 H nBu nBu 0 -- 0 -- 0 -- 0
-- 6 H iBu iBu 0 -- 0 -- 0 -- 0 -- 7 H tBu tBu 0 -- 0 -- 0 -- 0 --
8 H CyPe CyPe 0 -- 0 -- 0 -- 0 -- 9 H CyHx CyHx 0 -- 0 -- 0 -- 0 --
10 H Ph Ph 0 -- 0 -- 0 -- 0 -- 11 Me Me Me 0 -- 0 -- 0 -- 0 -- 12
Me Et Et 0 -- 0 -- 0 -- 0 -- 13 Me nPr nPr 0 -- 0 -- 0 -- 0 -- 14
Me iPr iPr 0 -- 0 -- 0 -- 0 -- 15 Me nBu nBu 0 -- 0 -- 0 -- 0 -- 16
Me iBu iBu 0 -- 0 -- 0 -- 0 -- 17 Me tBu tBu 0 -- 0 -- 0 -- 0 -- 18
Me CyPe CyPe 0 -- 0 -- 0 -- 0 -- 19 Me CyHx CyHx 0 -- 0 -- 0 -- 0
-- 20 Me Ph Ph 0 -- 0 -- 0 -- 0 --
[0051]
2TABLE 2 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 21 Et Me Me 0 -- 0
-- 0 -- 0 -- 22 Et Et Et 0 -- 0 -- 0 -- 0 -- 23 Et nPr nPr 0 -- 0
-- 0 -- 0 -- 24 Et iPr iPr 0 -- 0 -- 0 -- 0 -- 25 Et nBu nBu 0 -- 0
-- 0 -- 0 -- 26 Et iBu iBu 0 -- 0 -- 0 -- 0 -- 27 Et tBu tBu 0 -- 0
-- 0 -- 0 -- 28 Et CyPe CyPe 0 -- 0 -- 0 -- 0 -- 29 Et CyHx CyHx 0
-- 0 -- 0 -- 0 -- 30 Et Ph Ph 0 -- 0 -- 0 -- 0 -- 31 nPr Me Me 0 --
0 -- 0 -- 0 -- 32 nPr Et Et 0 -- 0 -- 0 -- 0 -- 33 nPr nPr nPr 0 --
0 -- 0 -- 0 -- 34 nPr iPr iPr 0 -- 0 -- 0 -- 0 -- 35 nPr nBu nBu 0
-- 0 -- 0 -- 0 -- 36 nPr iBu iBu 0 -- 0 -- 0 -- 0 -- 37 nPr tBu tBu
0 -- 0 -- 0 -- 0 -- 38 nPr CyPe CyPe 0 -- 0 -- 0 -- 0 -- 39 nPr
CyHx CyHx 0 -- 0 -- 0 -- 0 -- 40 nPr Ph Ph 0 -- 0 -- 0 -- 0 --
[0052]
3TABLE 3 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 41 iPr Me Me 0 -- 0
-- 0 -- 0 -- 42 iPr Et Et 0 -- 0 -- 0 -- 0 -- 43 iPr nPr nPr 0 -- 0
-- 0 -- 0 -- 44 iPr iPr iPr 0 -- 0 -- 0 -- 0 -- 45 iPr nBu nBu 0 --
0 -- 0 -- 0 -- 46 iPr iBu iBu 0 -- 0 -- 0 -- 0 -- 47 iPr tBu tBu 0
-- 0 -- 0 -- 0 -- 48 iPr CyPe CyPe 0 -- 0 -- 0 -- 0 -- 49 iPr CyHx
CyHx 0 -- 0 -- 0 -- 0 -- 50 iPr Ph Ph 0 -- 0 -- 0 -- 0 -- 51 nBu Me
Me 0 -- 0 -- 0 -- 0 -- 52 nBu Et Et 0 -- 0 -- 0 -- 0 -- 53 nBu nPr
nPr 0 -- 0 -- 0 -- 0 -- 54 nBu iPr iPr 0 -- 0 -- 0 -- 0 -- 55 nBu
nBu nBu 0 -- 0 -- 0 -- 0 -- 56 nBu iBu iBu 0 -- 0 -- 0 -- 0 -- 57
nBu tBu tBu 0 -- 0 -- 0 -- 0 -- 58 nBu CyPe CyPe 0 -- 0 -- 0 -- 0
-- 59 nBu CyHx CyHx 0 -- 0 -- 0 -- 0 -- 60 nBu Ph Ph 0 -- 0 -- 0 --
0 --
[0053]
4TABLE 4 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 61 iBu Me Me 0 -- 0
-- 0 -- 0 -- 62 iBu Et Et 0 -- 0 -- 0 -- 0 -- 63 iBu nPr nPr 0 -- 0
-- 0 -- 0 -- 64 iBu iPr iPr 0 -- 0 -- 0 -- 0 -- 65 iBu nBu nBu 0 --
0 -- 0 -- 0 -- 66 iBu iBu iBu 0 -- 0 -- 0 -- 0 -- 67 iBu tBu tBu 0
-- 0 -- 0 -- 0 -- 68 iBu CyPe CyPe 0 -- 0 -- 0 -- 0 -- 69 iBu CyHx
CyHx 0 -- 0 -- 0 -- 0 -- 70 iBu Ph Ph 0 -- 0 -- 0 -- 0 -- 71 tBu Me
Me 0 -- 0 -- 0 -- 0 -- 72 tBu Et Et 0 -- 0 -- 0 -- 0 -- 73 tBu nPr
nPr 0 -- 0 -- 0 -- 0 -- 74 tBu iPr iPr 0 -- 0 -- 0 -- 0 -- 75 tBu
nBu nBu 0 -- 0 -- 0 -- 0 -- 76 tBu iBu iBu 0 -- 0 -- 0 -- 0 -- 77
tBu tBu tBu 0 -- 0 -- 0 -- 0 -- 78 tBu CyPe CyPe 0 -- 0 -- 0 -- 0
-- 79 tBu CyHx CyHx 0 -- 0 -- 0 -- 0 -- 80 tBu Ph Ph 0 -- 0 -- 0 --
0 --
[0054]
5TABLE 5 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 81 CyEx Me Me 0 --
0 -- 0 -- 0 -- 82 CyHx Et Et 0 -- 0 -- 0 -- 0 -- 83 CyHx nPr nPr 0
-- 0 -- 0 -- 0 -- 84 CyHx iPr iPr 0 -- 0 -- 0 -- 0 -- 85 CyHx nBu
nBu 0 -- 0 -- 0 -- 0 -- 86 CyHx iBu iBu 0 -- 0 -- 0 -- 0 -- 87 CyHx
tBu tBu 0 -- 0 -- 0 -- 0 -- 88 CyHx CyPe CyPe 0 -- 0 -- 0 -- 0 --
89 CyHx CyHx CyHx 0 -- 0 -- 0 -- 0 -- 90 CyHx Ph Ph 0 -- 0 -- 0 --
0 -- 91 Ph Me Me 0 -- 0 -- 0 -- 0 -- 92 Ph Et Et 0 -- 0 -- 0 -- 0
-- 93 Ph nPr nPr 0 -- 0 -- 0 -- 0 -- 94 Ph iPr iPr 0 -- 0 -- 0 -- 0
-- 95 Ph nBu nBu 0 -- 0 -- 0 -- 0 -- 96 Ph iBu iBu 0 -- 0 -- 0 -- 0
-- 97 Ph tBu tBu 0 -- 0 -- 0 -- 0 -- 98 Ph CyPe CyPe 0 -- 0 -- 0 --
0 -- 99 Ph CyHx CyHx 0 -- 0 -- 0 -- 0 -- 100 Ph Ph Ph 0 -- 0 -- 0
-- 0 --
[0055]
6TABLE 6 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 101 Me Ph Ph 1 4-Me
0 -- 1 4-Me 0 -- 102 Me Ph Ph 1 4-Et 0 -- 1 4-Et 0 -- 103 Me Ph Ph
1 4-MeO 0 -- 1 4-MeO 0 -- 104 Me Ph Ph 1 4-EtO 0 -- 1 4-EtO 0 --
105 Me Ph Ph 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 106 Me Ph Ph 1
4-Et.sub.2N 0 -- 1 4-Et.sub.2N 0 -- 107 Me Ph Ph 1 4-F 0 -- 1 4-F 0
-- 108 Me Ph Ph 1 4-Cl 0 -- 1 4-Cl 0 -- 109 Me Ph Ph 1 4-Br 0 -- 1
4-Br 0 -- 110 Me Ph Ph 1 3-Me 1 5-Me 1 3-Me 1 5-Me 111 Me Ph Ph
3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 112 Me Ph Ph 5 Me 0 -- 5 Me 0 --
113 Me Ph Ph 1 3-MeO 1 4-MeO 1 3-MeO 1 4-MeO 114 Me nPr nPr 1
4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 115 Me iPr iPr 1 4-Me.sub.2N 0
-- 1 4-Me.sub.2N 0 -- 116 Me nBu nBu 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 -- 117 Me iBu iBu 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0
-- 118 Me tBu tBu 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 119 Me CyPe
CyPe 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 120 Me CyHx CyHx 1
4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 --
[0056]
7TABLE 7 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 121 Ph Ph Ph 1 4-Me
0 -- 1 4-Me 0 -- 122 Ph Ph Ph 1 4-Et 0 -- 1 4-Et 0 -- 123 Ph Ph Ph
1 4-MeO 0 -- 1 4-MeO 0 -- 124 Ph Ph Ph 1 4-EtO 0 -- 1 4-EtO 0 --
125 Ph Ph Ph 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 126 Ph Ph Ph 1
4-Et.sub.2N 0 -- 1 4-Et.sub.2N 0 -- 127 Ph Ph Ph 1 4-F 0 -- 1 4-F 0
-- 128 Ph Ph Ph 1 4-Cl 0 -- 1 4-Cl 0 -- 129 Ph Ph Ph 1 4-Br 0 -- 1
4-Br 0 -- 130 Ph Ph Ph 1 3-Me 1 5-Me 1 3-Me 1 5-Me 131 Ph Ph Ph
3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 132 Ph Ph Ph 5 Me 0 -- 5 Me 0 --
133 Ph Ph Ph 1 3-MeO 1 4-MeO 1 3-MeO 1 4-MeO 134 Ph nPr nPr 1
4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 135 Ph iPr iPr 1 4-Me.sub.2N 0
-- 1 4-Me.sub.2N 0 -- 136 Ph nBu nBu 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 -- 137 Ph iBu iBu 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0
-- 138 Ph tBu tBu 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 139 Ph CyPe
CyPe 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 140 Ph CyHx CyHx 1
4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 --
[0057]
8TABLE 8 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 141 Me Ph Ph 1 4-Ph
0 -- 1 4-Ph 0 -- 142 Me Ph Ph 0 -- 0 -- 1 4-Me 1 2-Me 143 Me iPr
iPr 1 4-Me 0 -- 0 -- 0 -- 144 Me iPr iPr 1 4-Me 0 -- 1 4-Me 0 --
145 Me iPr iPr 1 4-tBu 0 -- 1 4-tBu 0 -- 146 Me iPr iPr 1 4-MeO 0
-- 1 4-MeO 0 -- 147 Me iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 148 Me
ipr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 149 Me iPr iPr 1 4-Ph 0 --
1 4-Ph 0 -- 150 Me CyHx CyHx 1 4-Me 0 -- 1 4-Me 0 -- 151 Me CyHx
CyEx 1 4-MeO 0 -- 1 4-MeO 0 -- 152 Me CyHx CyHx 1 2-Me 1 4-Me 1
2-Me 1 4-Me 153 Me CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-Me0 154 Me
CyHx CyHx 1 4-F 0 -- 1 4-F 0 -- 155 Me CyHx CyHx 1 4-tBu 0 -- 1
4-tBu 0 -- 156 Me CyHx CyHx 1 4-Cl 0 -- 1 4-Cl 0 -- 157 Me CyHx
CyHx 2,3-benzene 2,3-benzene 158 Me CyHx CyHx 3,4-benzene
3,4-benzene 159 Me CyHx CyHx 3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 160
Me CyHx CyHx 2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4--
[0058]
9TABLE 9 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 161 Me CyHx CyHx
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 162 Me tBu tBu 1 4-Me
0 -- 0 -- 0 -- 163 Me tBu tBu 1 4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1
2-Me 164 Me tBu tBu 1 4-MeO 0 -- 1 4-MeO 0 -- 165 Me tBu tBu 1 2-Me
1 4-Me 1 2-Me 1 4-Me 166 Me tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO
167 Me tBu tBu 1 4-F 0 -- 1 4-F 0 -- 168 Me tBu tBu 1 4-tBu 0 -- 1
4-tBu 0 -- 169 Me tBu tBu 1 4-Cl 0 -- 1 4-Cl 0 -- 170 Me tBu tBu 1
4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1 2-Me 171 Me tBu tBu 2,3-benzene
3,4-benzene 172 Me tBu tBu 3,4-benzene 3,4-benzene 173 Me tBu tBu
3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 174 Me tBu tBu
2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4-- 175 Me tBn tBu
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 176 Me p-Tol p-Tol 0
-- 0 -- 0 -- 0 -- 177 Me p-Tol p-Tol 1 4-Me 0 -- 1 4-Me 0 -- 178 Me
p-Tol p-Tol 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 179 Me Xy Xy 0 --
0 -- 1 -- 0 -- 180 Me Xy Xy 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0
--
[0059]
10TABLE 10 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 181 iPr Ph Ph 1
4-Ph 0 -- 1 4-Ph 0 -- 182 iPr Ph Ph 0 -- 0 -- 1 4-Me 1 2-Me 183 iPr
iPr iPr 1 4-Me 0 -- 0 -- 0 -- 184 iPr iPr iPr 1 4-Me 0 -- 1 4-Me 0
-- 185 iPr iPr iPr 1 4-tBu 0 -- 1 4-tBu 0 -- 186 iPr iPr iPr 1
4-MeO 0 -- 1 4-MeO 0 -- 187 iPr iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me
188 iPr iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 189 iPr iPr iPr 1
4-Ph 0 -- 1 4-Ph 0 -- 190 iPr CyHx CyHx 1 4-Me 0 -- 1 4-Me 0 -- 191
iPr CyHx CyHx 1 4-MeO 0 -- 1 4-MeO 0 -- 192 iPr CyHx CyHx 1 2-Me 1
4-Me 1 2-Me 1 4-Me 193 iPr CyEx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1
4-MeO 194 iPr CyHx CyHx 1 4-F 0 -- 1 4-F 0 -- 195 iPr CyHx CyHx 1
4-tBu 0 -- 1 4-tBu 0 -- 196 iPr CyHx CyHx 1 4-Cl 0 -- 1 4-Cl 0 --
197 iPr CyHx CyHx 2,3-benzene 2,3-benzene 198 iPr CyHx CyHx
3,4-benzene 3,4-benzene 199 iPr CyHx CyHx 3,4-OCH.sub.2O--
3,4-OCH.sub.2O-- 200 iPr CyHx CyHx 2,3-(CH.sub.2).sub.4--
2,3-(CH.sub.2).sub.4--
[0060]
11TABLE 11 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 P R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 201 iPr CyHx CyHx
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 202 iPr tBu tBu 1
4-Me 0 -- 0 -- 0 -- 203 iPr tBu tBu 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 -- 204 iPr tBu tBu 1 4-MeO 0 -- 1 4-MeO 0 -- 205 iPr
tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 206 iPr tBu tBu 1 2-MeO 1 4-MeO
1 2-MeO 1 4-MeO 207 iPr tBu tBu 1 4-F 0 -- 1 4-F 0 -- 208 iPr tBu
tBu 1 4-tBu 0 -- 1 4-tBu 0 -- 209 iPr tBu tBu 1 4-Cl 0 -- 1 4-Cl 0
210 iPr tBu tBu 1 4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1 2-Me 211 iPr
tBu tBu 2,3-benzene 2,3-benzene 212 iPr tBu tBu 3,4-benzene
3,4-benzene 213 iPr tBu tBu 3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 214
iPr tBu tBu 2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4-- 215 iPr
tBu tBu 2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 216 iPr p-Tol
p-Tol 0 -- 0 -- 0 -- 0 -- 217 iPr p-Tol p-Tol 1 4-Me 0 -- 1 4-Me 0
-- 218 iPr p-Tol p-Tol 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 219
iPr Xy Xy 0 -- 0 -- 1 -- 0 -- 220 iPr Xy Xy 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 --
[0061]
12TABLE 12 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 221 CyHx Ph Ph 1
4-Ph 0 -- 1 4-Ph 0 -- 222 CyHx Ph Ph 0 -- 0 -- 1 4-Me 1 2-Me 223
CyHx iPr iPr 1 4-Me 0 -- 0 -- 0 -- 224 CyHx iPr iPr 1 4-Me 0 -- 1
4-Me 0 -- 225 CyHx iPr iPr 1 4-tBu 0 -- 1 4-tBu 0 -- 226 CyHx iPr
iPr 1 4-MeO 0 -- 1 4-MeO 0 -- 227 CyHx iPr iPr 1 2-Me 1 4-Me 1 2-Me
1 4-Me 228 CyHx iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 229 CyHx
iPr iPr 1 4-Ph 0 -- 1 4-Ph 0 -- 230 CyHx CyHx CyHx 1 4-Me 0 -- 1
4-Me 0 -- 231 CyHx CyHx CyHx 1 4-MeO 0 -- 1 4-MeO 0 -- 232 CyHx
CyHx CyHx 1 2-Me 1 4-Me 1 2-Me 1 4-Me 233 CyHx CyHx CyHx 1 2-MeO 1
4-MeO 1 2-MeO 1 4-MeO 234 CyHx CyHx CyHx 1 4-F 0 -- 1 4-F 0 -- 235
CyHx CyHx CyHx 1 4-tBu 0 -- 1 4-tBu 0 -- 236 CyHx CyHx CyHx 1 4-Cl
0 -- 1 4-Cl 0 -- 237 CyHx CyHx CyHx 2,3-benzene 2,3-benzene 238
CyHx CyHx CyHx 3,4-benzene 3,4-benzene 239 CyHx CyHx CyHx
3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 240 CyHx CyHx CyHx
2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4--
[0062]
13TABLE 13 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 241 CyHx CyHx CyHx
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 242 CyHx tBu tBu 1
4-Me 0 -- 0 -- 0 -- 243 CyHx tBu tBu 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 -- 244 CyHx tBu tBu 1 4-MeO 0 -- 1 4-MeO 0 -- 245
CyHx tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 246 CyHx tBu tBu 1 2-MeO 1
4-MeO 1 2-MeO 1 4-MeO 247 CyHx tBu tBu 1 4-F 0 -- 1 4-F 0 -- 248
CyHx tBu tBu 1 4-tBu 0 -- 1 4-tBu 0 -- 249 CyHx tBu tBu 1 4-Cl 0 --
1 4-Cl 0 -- 250 CyHx tBu tBu 1 4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1
2-Me 251 CyHx tBu tBu 2,3-benzene 2,3-benzene 252 CyHx tBu tBu
3,4-benzene 3,4-benzene 253 CyHx tBu tBu 3,4-OCH.sub.2O--
3,4-OCH.sub.2O-- 254 CyHx tBu tBu 2,3-(CH.sub.2).sub.4--
2,3-(CH.sub.2).sub.4-- 255 CyHx tBu tBu 2,3-(CH.sub.2).sub.3--
2,3-(CH.sub.2).sub.3-- 256 CyHx p-Tol p-Tol 0 -- 0 -- 0 -- 0 -- 257
CyHx p-Tol p-Tol 1 4-Me 0 -- 1 4-Me 0 -- 258 CyHx p-Tol p-Tol 1
4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 259 CyHx Xy Xy 0 -- 0 -- 1 -- 0
-- 260 CyHx Xy Xy 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2H 0 --
[0063]
14TABLE 14 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 261 tBu Ph Ph 1
4-Ph 0 -- 1 4-Ph 0 -- 262 tBu Ph Ph 0 -- 0 -- 1 4-Me 1 2-Me 263 tBu
iPr iPr 1 4-Me 0 -- 0 -- 0 -- 264 tBu iPr iPr 1 4-Me 0 -- 1 4-Me 0
-- 265 tBu iPr iPr 1 4-tBu 0 -- 1 4-tBu 0 -- 266 tBu iPr iPr I
4-MeO 0 -- 1 4-MeO 0 -- 267 tBu iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me
268 tBu iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 269 tBu iPr iPr 1
4-Ph 0 -- 1 4-Ph 0 -- 270 tBu CyHx CyHx 1 4-Me 0 -- 1 4-Me 0 -- 271
tBu CyHx CyHx 1 4-MeO 0 -- 1 4-MeO 0 -- 272 tBu CyHx CyHx 1 2-Me 1
4-Me 1 2-Me 1 4-Me 273 tBu CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1
4-MeO 274 tBu CyHx CyHx 1 4-F 0 -- 1 4-F 0 -- 275 tBu CyHx CyHx 1
4-tBu 0 -- 1 4-tBu 0 -- 276 tBu CyHx CyHx 1 4-Cl 0 -- 1 4-Cl 0 --
277 tBu CyHx CyHx 2,3-benzene 2,3-benzene 278 tBu CyHx CyHx
3,4-benzene 3,4-benzene 279 tBu CyHx CyHx 3,4-OCH.sub.2O--
3,4-OCH.sub.2O-- 280 tBu CyHx CyHx 2,3-(CH.sub.2).sub.4--
2,3-(CH.sub.2).sub.4--
[0064]
15TABLE 15 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 281 tBu CyHx CyHx
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 282 tBu tBu tBu 1
4-Me 0 -- 0 -- 0 -- 283 tBu tBu tBu 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 -- 284 tBu tBu tBu 1 4-MeO 0 -- 1 4-MeO 0 -- 285 tBu
tBu tBu 1 2-Me 1 4-Me 1 2-Me 1 4-Me 286 tBu tBu tBu 1 2-MeO 1 4-MeO
1 2-MeO 1 4-MeO 287 tBu tBu tBu 1 4-F 0 -- 1 4-F 0 -- 288 tBu tBu
tBu 1 4-tBu 0 -- 1 4-tBu 0 -- 289 tBu tBu tBu 1 4-Cl 0 -- 1 4-Cl 0
-- 290 tBu tBu tBu 1 4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1 2-Me 291
tBu tBu tBu 2,3-benzene 2,3-benzene 292 tBu tBu tBu 3,4-benzene
3,4-benzene 293 tBu tBu tBu 3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 294
tBu tBu tBu 2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4-- 295 tBu
tBu tBu 2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 296 tBu p-Tol
p-Tol 0 -- 0 -- 0 -- 0 -- 297 tBu p-Tol p-Tol 1 4-Me 0 -- 1 4-Me 0
-- 298 tBu p-Tol p-Tol 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 299
tBu Xy Xy 0 -- 0 -- 1 -- 0 -- 300 tBu Xy Xy 1 4-Me.sub.2N 0 -- 1
4-Me.sub.2N 0 --
[0065]
16TABLE 16 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 301 Ph Ph Ph 1 4-Ph
0 -- 1 4-Ph 0 -- 302 Ph Ph Ph 0 -- 0 -- 1 4-Me 1 2-Me 303 Ph iPr
iPr 1 4-Me 0 -- 0 -- 0 -- 304 Ph iPr iPr 1 4-Me 0 -- 1 4-Me 0 --
305 Ph iPr iPr 1 4-tBu 0 -- 1 4-tBu 0 -- 306 Ph iPr iPr 1 4-MeO 0
-- 1 4-MeO 0 -- 307 Ph iPr iPr 1 2-Me 1 4-Me 1 2-Me 1 4-Me 308 Ph
iPr iPr 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 309 Ph iPr iPr 1 4-Ph 0 --
1 4-Ph 0 -- 310 Ph CyHx CyHx 1 4-Me 0 -- 1 4-Me 0 -- 311 Ph CyHx
CyHx 1 4-MeO 0 -- 1 4-MeO 0 -- 312 Ph CyHx CyHx 1 2-Me 1 4-Me 1
2-Me 1 4-Me 313 Ph CyHx CyHx 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO 314 Ph
CyHx CyHx 1 4-F 0 -- 1 4-F 0 -- 315 Ph CyHx CyHx 1 4-tBu 0 -- 1
4-tBu 0 -- 316 Ph CyHx CyHx 1 4-Cl 0 -- 1 4-Cl 0 -- 317 Ph CyHx
CyHx 2,3-benzene 2,3-benzene 318 Ph CyHx CyHx 3,4-benzene
3,4-benzene 319 Ph CyHx CyHx 3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 320
Ph CyHx CyHx 2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4--
[0066]
17TABLE 17 General Formula (1) Exemplified Compound R.sup.1 R.sup.2
R.sup.3 p R.sup.4 q R.sup.5 r R.sup.6 s R.sup.7 321 Ph CyHx CyHx
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 322 Ph tBu tBu 1 4-Me
0 -- 0 -- 0 -- 323 Ph tBu tBu 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 --
324 Ph tBu tBu 1 4-MeO 0 -- 1 4-MeO 0 -- 325 Ph tBu tBu 1 2-Me 1
4-Me 1 2-Me 1 4-Me 326 Ph tBu tBu 1 2-MeO 1 4-MeO 1 2-MeO 1 4-MeO
327 Ph tBu tBu 1 4-F 0 -- 1 4-F 0 -- 328 Ph tBu tBu 1 4-tBu 0 -- 1
4-tBu 0 -- 329 Ph tBu tBu 1 4-Cl 0 -- 1 4-Cl 0 -- 330 Ph tBu tBu 1
4-Me.sub.2N 1 2-Me 1 4-Me.sub.2N 1 2-Me 331 Ph tBu tBu 2,3-benzene
2,3-benzene 332 Ph tBu tBu 3,4-benzene 3,4-benzene 333 Ph tBu tBu
3,4-OCH.sub.2O-- 3,4-OCH.sub.2O-- 334 Ph tBu tBu
2,3-(CH.sub.2).sub.4-- 2,3-(CH.sub.2).sub.4-- 335 Ph tBu tBu
2,3-(CH.sub.2).sub.3-- 2,3-(CH.sub.2).sub.3-- 336 Ph p-Tol p-Tol 0
-- 0 -- 0 -- 0 -- 337 Ph p-Tol p-Tol 1 4-Me 0 -- 1 4-Me 0 338 Ph
p-Tol p-Tol 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0 -- 339 Ph Xy Xy 0 --
0 -- 1 -- 0 -- 340 Ph Xy Xy 1 4-Me.sub.2N 0 -- 1 4-Me.sub.2N 0
--
[0067] The compound (1) of the invention is produced, for example,
by the process shown by the following reaction formula. 3
[0068] (In the formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, p, q, r, and s have the same meanings as
defined above; X is a halogen atom; and R is a lower alkyl group
having 1 to 4 carbon atoms.)
[0069] Specifically, the process comprises the following five steps
as shown above.
[0070] First Step: A step in which an alcohol compound (8) is
obtained by a) a method comprising the reaction of a diaryl ketone
(3) with a Grignard reagent (5), or by b) a method comprising the
reaction of an ester (4) with a Grignard reagent (6) and/or another
Grignard reagent.
[0071] Second Step: A step in which the alcohol compound (8) is
dehydrated with an acid catalyst (e.g., p-toluenesulfonic acid) to
obtain a vinyl compound (9).
[0072] Third Step: A step in which the vinyl compound (9) is caused
to addition reaction of a halogen to thereby obtain a dihalide
compound (10).
[0073] Fourth Step: A step in which the dihalide compound (10) is
subjected to dehydrohalogenation optionally in the presence of a
base (e.g., pyridine) to obtain a vinyl halide compound (11).
[0074] Fifth Step: A step in which lithium metal, an alkyllithium,
or magnesium metal is caused to act on the vinyl halide compound
(11) to prepare a vinyllithium compound or vinyl Grignard reagent
and this reaction product is subjected to coupling reaction with a
phosphorus halide compound (12) to obtain a
2,2-(diaryl)vinylphosphine compound (1) of the invention.
[0075] In the compound (3) to compound (10) in the formula shown
above, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, p, q, r, and s have the same meanings as defined above; X
is a halogen atom; and R in the compound (4) is a lower alkyl group
having 1 to 4 carbon atoms.
[0076] Examples of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, and R.sup.7 include the same groups and atoms as
enumerated above.
[0077] Examples of X include a halogen atom such as fluorine,
chlorine, bromine or iodine.
[0078] Examples of R include a lower alkyl group having 1 to 4
carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl,
tert-butyl, isobutyl or sec-butyl.
[0079] As the diaryl ketone (3) and the ester (4) may be used a
commercial diaryl ketone compound and a commercial ester compound
(e.g., ones manufactured by Tokyo Kasei Kogyo Co., Ltd. and Nacalai
Tesque, Inc.) without any treatment. Alternatively, the ketone (3)
and ester (4) may be synthesized by known methods.
[0080] The Grignard reagents (5), (6), and (7) may be ones prepared
by a known method from corresponding halogen compounds on the
market or from halogen compounds synthesized by a known method.
[0081] For conducting the first step, in which an alcohol compound
(8) is obtained by a) a method comprising the reaction of a diaryl
ketone (3) with a Grignard reagent (5), or by b) a method
comprising the raction of an ester (4) with a Grignard reagent (6)
and/or another Grignard reagent, an ordinary Grignard reaction can
be used.
[0082] In the Grignard reaction by method a), an alcohol compound
(8) can be obtained by the reaction of a diaryl ketone (3) with a
Grignard reagent (5).
[0083] The amount of the Grignard reagent (5) to be used is
preferably about from 0.5 to 10 mol, more preferably about from 0.8
to 3.0 mol, per mol of the diaryl ketone (3).
[0084] Examples of reaction solvents include ether solvents such as
diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane,
dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether
and tetrahydrofuran. Such a solvent may be used in an amount of
preferably about from 1.0 to 80 times by volume, more preferably
about from 2.0 to 30 times by volume, the amount of the diaryl
ketone (3).
[0085] Appropriate additives may be added in conducting in this
reaction in order to accelerate the reaction. Examples of the
additives include cesium trichloride, zinc chloride, zinc bromide,
copper chloride, copper bromide, copper iodide, aluminum
trichloride, and titanium tetrachloride. Preferred of these are
cesium trichloride, copper chloride, copper bromide, and copper
iodide. The amount of such additives to be used is preferably about
from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol,
per mol of the diaryl ketone (3).
[0086] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 30 hours,
preferably about from 30 minutes to 12 hours, and the reaction
temperature is generally about from -20 to 100.degree. C.,
preferably about from 0 to 70.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the diaryl ketone (3) and
Grignard reagent (5) to be used, etc.
[0087] In the Grignard reaction by method b), an alcohol compound
(8) can be obtained by the reaction of an ester (4) with a Grignard
reagent (6) and/or another Grignard reagent.
[0088] The amount of the Grignard reagents (6) and (7) to be used
is preferably about from 1.0 to 10 mol, more preferably about from
1.6 to 4.8 mol, per mol of the ester (4).
[0089] Examples of reaction solvents include ether solvents such as
diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane,
dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether
and tetrahydrofuran. Such a solvent may be used in an amount of
preferably about from 1.0 to 50 times by volume, more preferably
about from 4.0 to 10 times by volume, the amount of the ester
(4).
[0090] Appropriate additives may be added in conducting the
reaction in order to accelerate the reaction. Examples of the
additives include cesium trichloride, zinc chloride, zinc bromide,
copper chloride, copper bromide, copper iodide, aluminum
trichloride, and titanium tetrachloride. Preferred of these are
cesium trichloride, copper chloride, copper bromide, and copper
iodide. The amount of such additives to be used is preferably about
from 0.01 to 10 mol, more preferably about from 0.05 to 3.0 mol,
per mol of the ester (4).
[0091] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 30 hours,
preferably about from 30 minutes to 8 hours, and the reaction
temperature is generally about from -20 to 100.degree. C.,
preferably about from 0 to 70.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the ester (4) and Grignard
reagents (6) and (7) to be used, etc.
[0092] In each of a) and b) described above, an ordinary
post-treatment is conducted after completion of the reaction,
whereby the target compound can be obtained.
[0093] For conducting the second step, in which the alcohol
compound (8) is dehydrated with an acid catalyst (e.g.,
p-toluenesulfonic acid) to obtain a vinyl compound (9), an ordinary
dehydration reaction can be used.
[0094] Examples of the acid catalyst include hydrochloric acid,
sulfuric acid, camphorsulfonic acid, benzenesulfonic acid, and
p-toluenesulfonic acid. Preferred of these is p-toluenesulfonic
acid. The amount of the acid catalyst to be used is preferably
about from 0.0001 to 0.2 mol, more preferably about from 0.005 to
0.05 mol, per mol of the alcohol compound (8).
[0095] Examples of reaction solvents include aromatic hydrocarbons
such as benzene, toluene, xylene, and chlorobenzene; and ether
solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran,
dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are
benzene, toluene, and xylene. Such a solvent may be used in an
amount of preferably about from 1.0 to 50 times by volume, more
preferably about from 2.0 to 20 times by volume, the amount of the
alcohol compound (8).
[0096] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 30 hours,
preferably about from 30 minutes to 8 hours, and the reaction
temperature is generally about from 20 to 180.degree. C.,
preferably about from 70 to 140.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the alcohol compound (8) and
acid catalyst to be used, etc.
[0097] After completion of the reaction, an ordinary post-treatment
is conducted, whereby the target compound can be obtained.
[0098] For conducting the third step, in which the vinyl compound
(9) is caused to add a halogen to thereby obtain a dihalide
compound (10), the ordinary halogen addition reaction to an olefin
can be used.
[0099] Examples of the halogen include chlorine, bromine, and
iodine, and bromine is preferred. The amount of the halogen to be
used is preferably about from 0.5 to 2.0 mol, more preferably about
from 0.8 to 1.2 mol, per mol of the vinyl compound (9).
[0100] Examples of reaction solvents include aromatic hydrocarbons
such as benzene, toluene, xylene, and chlorobenzene; ether solvents
such as diethyl ether, diisopropyl ether, tetrahydrofuran,
dimethoxyethane, dioxane, and 1,3-dioxolane; and halogenated
solvents such as dichloromethane, chloroform, carbon tetrachloride,
dichloroethane, dibromomethane, and dibromoethane. Preferred of
these are halogenated solvents such as dichloromethane,
dichloroethane, chloroform, and carbon tetrachloride. Such a
solvent may be used in an amount of preferably about from 0.2 to 50
times by volume, more preferably about from 0.5 to 20 times by
volume, the amount of the vinyl compound (9).
[0101] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 24 hours,
preferably about from 30 minutes to 8 hours, and the reaction
temperature is generally about from -60 to 100.degree. C.,
preferably about from -30 to 50.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the vinyl compound (9) and
halogen to be used, etc.
[0102] After completion of the reaction, an ordinary post-treatment
is conducted, whereby the target compound can be obtained.
[0103] For conducting the fourth step, in which the dihalide
compound (10) is subjected to dehydrohalogenation optionally in the
presence of a base to obtain a vinyl halide compound (11), an
ordinary dehydrohalogenation reaction can be used.
[0104] Examples of the base include triethylamine, dimethylaniline,
diethylaniline, pyridine, picoline, lutidine, ethylpyridine,
quinoline, and isoquinoline. Preferred of these is pyridine. Such a
base may be used in an amount of preferably about from 0.5 to 30
mol, more preferably about from 1.0 to 10 mol, per mol of the
dihalide compound (10).
[0105] Examples of reaction solvents include aromatic hydrocarbons
such as benzene, toluene, xylene, and chlorobenzene; and ether
solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran,
dimethoxyethane, dioxane, and 1,3-dioxolane. Preferred of these are
benzene, toluene, and xylene. Such a solvent may be used in an
amount of preferably about from 0.2 to 30 times by volume, more
preferably about from 0.5 to 10 times by volume, the amount of the
dihalide compound (10).
[0106] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 30 hours,
preferably about from 30 minutes to 16 hours, and the reaction
temperature is generally about from 20 to 140.degree. C.,
preferably about from 60 to 110.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the dihalide compound (10)
and base to be used, etc.
[0107] After completion of the reaction, an ordinary post-treatment
is conducted, whereby the target compound can be obtained.
[0108] For conducting the fifth step, in which lithium metal, an
alkyllithium, or magnesium metal is caused to act on the vinyl
halide compound (11) to prepare a vinyllithium compound or vinyl
Grignard reagent and this reaction product is subjected to coupling
reaction with a phosphorus halide compound (12) to obtain a
2,2-(diaryl)vinylphosphine compound (1) of the invention, use can
be made of the ordinary coupling reaction of a lithium reagent or
Grignard reagent with a phosphorus halide compound.
[0109] The amount of the lithium metal, alkyllithium, or magnesium
metal to be used is preferably about from 0.5 to 3.0 mol, more
preferably about from 0.8 to 1.5 mol, per mol of the vinyl halide
compound (11).
[0110] The amount of the halogenated phosphorus compound (12) to be
used is preferably about from 0.5 to 3.0 mol, more preferably about
from 0.7 to 1.5 mol, per mol of the vinyl halide compound (11).
[0111] Examples of reaction solvents include ether solvents such as
diethyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane,
dioxane, and 1,3-dioxolane. Preferred of these are diethyl ether
and tetrahydrofuran. Such a solvent may be used in an amount of
preferably about from 1.0 to 50 times by volume, more preferably
about from 4.0 to 30 times by volume, the amount of the vinyl
halide compound (11).
[0112] Appropriate additives may be added in conducting in this
reaction in order to accelerate the reaction. Examples of the
additives include copper chloride, copper bromide, copper iodide,
copper triflate, copper cyanide, a copper iodide-dimethyl sulfide
complex, a copper iodide-triphenylphosphine complex, and a copper
iodide-tributylphosphine complex. Preferred of these are copper
chloride, copper bromide, and copper iodide. The amount of such
additives to be used is preferably about from 0.01 to 10 mol, more
preferably about from 0.05 to 3.0 mol, per mol of the vinyl halide
compound (11).
[0113] This reaction is usually conducted under an inert gas
atmosphere such as nitrogen gas or argon gas. In this reaction, the
reaction time is generally about from 10 minutes to 40 hours,
preferably about from 30 minutes to 24 hours, and the reaction
temperature is generally about from -100 to 120.degree. C.,
preferably about from -80 to 80.degree. C. Although such conditions
can be used to carry out the reaction, they may be suitably varied
according to the kinds and amounts of the vinyl halide compound
(11) and phosphorus halide compound (12) to be used, etc.
[0114] After completion of the reaction, an ordinary post-treatment
is conducted, whereby the target compound can be obtained.
[0115] The compound (1) of the invention thus obtained serves as a
ligand to form a palladium-phosphine catalyst in cooperation with a
palladium compound.
[0116] The palladium compound to be used as a catalyst precursor
for forming the palladium-phosphine catalyst is not particularly
limited. However, salts or complexes of palladium having a valence
of 4, 2, or 0 are mainly used.
[0117] Specific examples of the palladium compound include
compounds of tetravalent palladium, such as sodium
hexachloropalladate(IV) tetrahydrate and potassium
hexachloropalladate(IV), compounds of bivalent palladium, such as
palladium(II) chloride, palladium(II) bromide, palladium(II)
acetate, palladium(II) acetylacetonate,
dichlorobis(benzonitrile)palladium(II),
dichlorobis(acetonitrile)palladiu- m(II),
dichlorobis(triphenylphosphine)palladium(II),
dichlorotetraamminepalladium(II),
dichloro(cycloocta-1,5-diene)palladium(- II), palladium(II)
trifluoroacetate, and .pi.-allylpalladium(II) chloride diner, and
compounds of zero-valent palladium, such as
tris(dibenzylideneacetone)dipalladium(0),
tris(dibenzylideneacetone)dipal- ladium(0)-chloroform complex, and
tetrakis(triphenylphosphine)palladium(0)- .
[0118] The palladium-phosphine catalyst obtained by causing a
palladium compound to act on the novel 2,2-(diaryl)vinylphosphine
compound (1) can be prepared, for example, by reacting the
2,2-(diaryl)vinylphosphine compound (1) with
.pi.-allylpalladium(II) chloride dimer according to the method
described in Y. Uozumi and T. Hayashi, J. Am. Chem. Soc., 1991,
Vol. 113, p.9887.
[0119] The palladium-phosphine catalyst thus obtained by causing a
palladium compound to act on the novel 2,2-(diaryl)vinylphosphine
compound (1) of the invention can be used as a catalyst in the
amination reaction or the carbon-carbon bond formation reaction in
which an aryl compound having a leaving group is reacted with this
reaction substance (an amine compound, an arylboric acid compound,
an arylborate ester compound, or an alkyne compound) in the
presence of a base.
[0120] The aryl compound having a leaving group in the invention is
represented by general formula (2):
ArX.sup.1 (2)
[0121] (wherein Ar is an aryl group which may have one or more
substituents or a heteroaryl group which may have one or more
substituents; and X.sup.1 is a halogen atom, a
trifluoromethanesulfonylox- y group, a methanesulfonyloxy group, or
a toluenesulfonyloxy group).
[0122] The aryl compound (2) to be used in the invention is not
particularly limited. Examples thereof include aryl bromides, aryl
chlorides, aryl iodides, aryl fluorides, aryl
trifluoromethanesulfonate, aryl methanesulfonate, aryl
p-toluenesulfonate, and aryl halides having two or more halogen
atoms.
[0123] Specific examples of the aryl compound (2) include: aryl
bromides such as bromobenzene, o-bromoanisole, m-bromoanisole,
p-bromoanisole, o-bromotoluene, m-bromotoluene, p-bromotoluene,
o-bromophenol, m-bromophenol, p-bromophenol,
2-bromobenzotrifluoride, 3-bromobenzotrifluoride,
4-bromobenzotrifluoride, 1-bromo-2,4-dimethoxybe- nzene,
1-bromo-2,5-dimethoxybenzene, 2-bromophenethyl alcohol,
3-bromophenethyl alcohol, 4-bromophenethyl alcohol,
5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene, 2-bromo-p-xylene,
3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene,
5-bromo-m-xylene, 1-bromo-3-(trifluoromethoxy)benzene,
1-bromo-4-(trifluoromethoxy)benzene, 2-bromobiphenyl,
3-bromobiphenyl, 4-bromobiphenyl,
4-bromo-1,2-(methylenedioxy)benzene, 1-bromonaphthalene,
2-bromonaphthalene, 1-bromo-2-methylnaphthalene,
1-bromo-4-methylnaphthal- ene, 1,4-dibromonaphthalene,
4,4'-dibromobiphenyl, 2-bromothiophene, 3-bromothiophene,
2-bromopyridine, 3-bromopyridine, 4-bromopyridine,
9-bromophenanthrene, 2-bromofuran, and 3-bromofuran;
[0124] aryl chlorides such as chlorobenzene, o-chloroanisole,
m-chloroanisole, p-chloroanisole, o-chlorotoluene, m-chlorotoluene,
p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol,
2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride,
4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene,
1-chloro-2,5-dimethoxybenzene, 2-chlorophenethyl alcohol,
3-chlorophenethyl alcohol, 4-chlorophenethyl alcohol,
5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene,
2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene,
4-chloro-m-xylene, 5-chloro-m-xylene,
1-chloro-3-(trifluoromethoxy)benzene,
1-chloro-4-(trifluoromethoxy)benzene, 2-chlorobiphenyl,
3-chlorobiphenyl, 4-chlorobiphenyl, 3-chloronaphthalene,
2-chloronaphthalene, 1-chloro-2-methylnaphthalene,
2-chloro-4-methylnaphthalene, 1,4-dichloronaphthalene,
4,4'-dichlorobiphenyl, 2-chlorothiophene, 3-chlorothiophene,
2-chloropyridine, 3-chloropyridine, 4-chloropyridine,
9-chlorophenanthrene, 2-chlorofuran, and 3-chlorofuran;
[0125] aryl iodides such as iodobenzene, o-iodoanisole,
m-iodoanisole, p-iodoanisole, o-iodotoluene, m-iodotoluene,
p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol,
2-iodobenzotrifluoride, 3-iodobenzotrifluoride,
4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxybenze- ne,
1-iodo-2,5-dimethoxybenzene, 2-iodophenethyl alcohol,
3-iodophenethyl alcohol, 4-iodophenethyl alcohol,
5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo-p-xylene,
3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m-xylene,
1-iodo-3-(trifluoromethoxy)benzene,
1-iodo-4-(trifluoromethoxy)benzene, 2-iodobiphenyl, 3-iodobiphenyl,
4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene,
1-iodo-2-methylnaphthalene, 1-iodo-4-methylnaphthalene,
1,4-diiodonaphthalene, 4,4'-diiodobiphenyl, 2-iodothiophene,
3-iodothiophene, 2-iodopyridine, 3-iodopyridine, 4-iodopyridine,
9-iodophenanthrene, 2-iodofuran, and 3-iodofuran;
[0126] aryl fluorides such as fluorobenzene, o-fluoroanisole,
m-fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene,
p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol,
2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride,
4-fluorobenzotrifluoride, 1-fluoro-2,4-dimethoxybenzene,
1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol,
3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol,
5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene,
2-fluoro-p-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene,
4-fluoro-m-xylene, 5-fluoro-m-xylene,
1-fluoro-3-(trifluoromethoxy)benzene,
1-fluoro-4-(trifluoromethoxy)benzene, 2-fluorobiphenyl,
3-fluorobiphenyl, 4-fluorobiphenyl,
4-fluoro-1,2-(methylenedioxy)benzene, 1-fluoronaphthalene,
2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene,
1-fluoro-4-methylnaphthalene, 1,4-difluoronaphthalene,
4,4'-difluorobiphenyl, 2-fluorothiophene, 3-fluorothiophene,
2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine,
9-fluorophenanthrene, 2-fluorofuran, and 3-fluorofuran;
[0127] aryl trifluoromethanesulfonate such as
trifluoromethanesulfonyloxyb- enzene,
o-trifluoromethanesulfonyloxyanisole, m-trifluoromethanesulfonylox-
yanisole, p-trifluoromethanesulfonyloxyanisole,
o-trifluoromethanesulfonyl- oxytoluene,
m-trifluoromethanesulfonyloxytoluene, p-trifluoromethanesulfon-
yloxytoluene, p-trifluoromethanesulfonyloxyphenol,
o-trifluoromethanesulfo- nyloxyphenol,
p-trifluoromethanesulfonyloxyphenol, 2-trifluoromethanesulfo-
nyloxybenzotrifluoride,
3-trifluoromethanesulfonyloxybenzotrifluoride,
4-trifluoromethanesulfonyloxybenzotrifluoride,
1-trifluoromethanesulfonyl- oxy-2,4-dimethoxybenzene,
1-trifluoromethanesulfonyloxy-2,5-dimethoxybenze- ne,
2-trifluoromethanesulfonyloxyphenethyl alcohol,
3-trifluoromethanesulfonyloxyphenethyl alcohol,
4-trifluoromethanesulfony- loxyphenethyl alcohol,
5-trifluoromethanesulfonyloxy-1,2,4-trimethylbenzen- e,
2-trifluoromethanesulfonyloxy-m-xylene,
2-trifluoromethanesulfonyloxy-p- -xylene,
3-trifluoromethanesulfonyloxy-o-xylene, 4-trifluoromethanesulfony-
loxy-o-xylene, 4-trifluoromethanesulfonyloxy-m-xylene,
5-trifluoromethanesulfonyloxy-m-xylene,
1-trifluoromethanesulfonyloxy-3-(- trifluoromethoxy)benzene,
1-trifluoromethanesulfonyloxy-4-(trifluoromethox- y)benzene,
2-trifluoromethanesulfonyloxybiphenyl, 3-trifluoromethanesulfon-
yloxybiphenyl, 4-trifluoromethanesulfonyloxybiphenyl,
4-trifluoromethanesulfonyloxy-1,2-(methylenedioxy)benzene,
1-trifluoromethanesulfonyloxynaphthalene,
2-trifluoromethanesulfonyloxyna- phthalene,
1-trifluoromethanesulfonyloxy-2-methylnaphthalene,
1-trifluoromethanesulfonyloxy-4-methylnaphthalene,
1,4-ditrifluoromethanesulfonyloxynaphthalene,
4,4'-ditrifluoromethanesulf- onyloxybiphenyl,
2-trifluoromethanesulfonyloxythiophene,
3-trifluoromethanesulfonyloxythiophene,
2-trifluoromethanesulfonyloxypyri- dine,
3-trifluoromethanesulfonyloxypyridine,
4-trifluoromethanesulfonyloxy- pyridine,
9-trifluoromethanesulfonyloxyphenanthrene,
2-trifluoromethanesulfonyloxyfuran, and
3-trifluoromethanesulfonyloxyfura- n;
[0128] aryl methanesulfonate such as methanesulfonyloxybenzene,
o-methanesulfonyloxyanisole, m-methanesulfonyloxyanisole,
p-methanesulfonyloxyanisole, o-methanesulfonyloxytoluene,
m-methanesulfonyloxytoluene, p-methanesulfonyloxytoluene,
o-methanesulfonyloxyphenol, m-methanesulfonyloxyphenol,
p-methanesulfonyloxyphenol, 2-methanesulfonyloxybenzotrifluoride,
3-methanesulfonyloxybenzotrifluoride,
4-methanesulfonyloxybenzotrifluorid- e,
1-methanesulfonyloxy-2,4-dimethoxybenzene,
1-methanesulfonyloxy-2,5-dim- ethoxybenzene,
2-methanesulfonyloxyphenethyl alcohol,
3-methanesulfonyloxyphenethyl alcohol,
4-methanesulfonyloxyphenethyl alcohol,
5-methanesulfonyloxy-1,2,4-trimethylbenzene,
2-methanesulfonyloxy-m-xylene, 2-methanesulfonyloxy-p-xylene,
3-methanesulfonyloxy-o-xylene, 4-methanesulfonyloxy-o-xylene,
4-methanesulfonyloxy-m-xylene, 5-methanesulfonyloxy-m-xylene,
1-methanesulfonyloxy-3-(trifluoromethoxy)benzene,
1-methanesulfonyloxy-4-- (trifluoromethoxy)benzene,
2-methanesulfonyloxybiphenyl, 3-methanesulfonyloxybiphenyl,
4-methanesulfonyloxybiphenyl,
4-methanesulfonyloxy-1,2-(methylenedioxy)benzene,
1-methanesulfonyloxynap- hthalene, 2-methanesulfonyloxynaphthalene,
1-methanesulfonyloxy-2-methylna- phthalene,
1-methanesulfonyloxy-4-methylnaphthalene,
1,4-dimethanesulfonyloxynaphthalene,
4,4'-dimethanesulfonyloxybiphenyl, 2-methanesulfonyloxythiophene,
3-methanesulfonyloxythiophene, 2-methanesulfonyloxypyridine,
3-methanesulfonyloxypyridine, 4-methanesulfonyloxypyridine,
9-methanesulfonyloxyphenanthrene, 2-methanesulfonyloxyfuran, and
3-methanesulfonyloxyfuran; and
[0129] aryl p-toluenesulfonate such as p-toluenesulfonyloxybenzene,
o-(p-toluenesulfonyloxy)anisole, m-(p-toluenesulfonyloxy)anisole,
p-(p-toluenesulfonyloxy)anisole, o-(p-toluenesulfonyloxy)toluene,
m-(p-toluenesulfonyloxy)toluene, p-(p-toluenesulfonyloxy)toluene,
o-(p-toluenesulfonyloxy)phenol, m-(p-toluenesulfonyloxy)phenol,
p-(p-toluenesulfonyloxy)phenol,
2-(p-toluenesulfonyloxy)benzotrifluoride,
3-(p-toluenesulfonyloxy)benzotrifluoride,
4-(p-toluenesulfonyloxy)benzotr- ifluoride,
1-(p-toluenesulfonyloxy)-2,4-dimethoxybenzene,
1-(p-toluenesulfonyloxy)-2,5-dimethoxybenzene,
2-(p-toluenesulfonyloxy)ph- enethyl alcohol,
3-(p-toluenesulfonyloxy)phenethyl alcohol,
4-(p-toluenesulfonyloxy)phenethyl alcohol,
5-(p-toluenesulfonyloxy)-1,2,4- -trimethylbenzene,
2-(p-toluenesulfonyloxy)-m-xylene,
2-(p-toluenesulfonyloxy)-p-xylene,
3-(p-toluenesulfonyloxy)-o-xylene,
4-(p-toluenesulfonyloxy)-o-xylene,
4-(p-toluenesulfonyloxy)-m-xylene,
5-(p-toluenesulfonyloxy)-m-xylene,
1-(p-toluenesulfonyloxy)-3-(trifluorom- ethoxy)benzene,
1-(p-toluenesulfonyloxy)-4-(trifluoromethoxy)benzene,
2-(p-toluenesulfonyloxy)biphenyl, 3-(p-toluenesulfonyloxy)biphenyl,
4-(p-toluenesulfonyloxy)biphenyl,
4-(p-toluenesulfonyloxy)-1,2-(methylene- dioxy)benzene,
1-(p-toluenesulfonyloxy)naphthalene,
2-(p-toluenesulfonyloxy)naphthalene,
1-(p-toluenesulfonyloxy)-2-methylnap- hthalene,
1-(p-toluenesulfonyloxy)-4-methylnaphthalene,
1,4-di(p-toluenesulfonyloxy)naphthalene,
4,4'-di(p-toluenesulfonyloxy)bip- henyl,
2-(p-toluenesulfonyloxy)thiophene,
3-(p-toluenesulfonyloxy)thiophen- e,
2-(p-toluenesulfonyloxy)pyridine, 3-(p-toluenesulfonyloxy)pyridine,
4-(p-toluenesulfonyloxy)pyridine,
9-(p-toluenesulfonyloxy)phenanthrene,
2-(p-toluenesulfonyloxy)furan, and
3-(p-toluenesulfonyloxy)furan.
[0130] Other examples of aryl halides which can be used in the
invention include aryl halides having two or more halogen atoms,
such as 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene,
9,10-dibromoanthracene, 9,10-dichloroanthracene,
1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene,
1-bromo-4-fluorobenzene, 2-bromochlorobenzene,
3-bromochlorobenzene, 4-bromochlorobenzene,
2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride,
5-bromo-2-chlorobenzotrifluoride, 1-bromo-2,3-dichlorobenzene,
1-bromo-2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene,
2-bromo-4-fluorotoluene, 2-bromo-5-fluorotoluene,
3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene- , and
4-bromo-3-fluorotoluene.
[0131] Examples of the amine compound to be used in the invention
include primary amines, secondary amines, imines, and amides.
[0132] The primary amines are not particularly limited. Examples
thereof include aliphatic primary amines such as ethylamine,
propylamine, butylamine, isobutylamine, tert-butylamine,
pentylamine, cyclopentylamine, hexylamine, cyclohexylamine,
heptylamine, and octylamine; and aromatic primary amines such as
aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline,
o-anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine,
p-toluidine, 2-naphthylamine, 2-aminobiphenyl, 4-aminobiphenyl,
3,4-methylenedioxyaniline, m-xylidine, and p-xylidine.
[0133] The secondary amines are not particularly limited. Examples
thereof include cyclic secondary amines such as piperazine,
2-methylpiperazine, homopiperazine, N-methylhomopiperazine,
2,6-dimethylpiperazine, N-methylpiperazine, N-ethylpiperazine,
N-ethoxycarbonylpiperazine, N-benzylpiperazine, morpholine,
2,6-dimethylmorpholine, piperidine, 2,6-dimethylpiperidine,
3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine,
4-piperidone, pyrrolidine, 2,5-dimethylpyrrolidine, carbazole,
indole, and indoline; and noncyclic secondary amines such as
dimethylamine, diethylamine, and other noncyclic secondary amines
which may have one or more substituents on the aromatic ring(s),
such as N-methylaniline, N-ethylaniline, N-methylbenzylamine,
N-methylphenethylamine, and diphenylamine derivatives.
[0134] The imines are not particularly limited. Examples thereof
include benzophenonimine and 4,4'-dimethoxybenzophenoneimine.
[0135] The amides are not particularly limited. Examples thereof
include 2-azetidinone (.beta.-propiolactam), .gamma.-butyrolactam,
.delta.-valerolactam, .epsilon.-caprolactam, acetamide,
propionamide, cyclohexanecarboxamide, benzamide, N-methylformamide,
N-methylacetamide, N-ethylacetamide,
N-methylcyclohexanecarboxamide, and N-methylbenzamide.
[0136] The arylboric acid compounds and the arylborate ester
compounds to be used in the invention are not particularly limited.
Examples thereof include phenylboric acid, 4-methylphenylboric
acid, 2-thienylboric acid, 2-furylboric acid,
2,3,4,5,6-pentafluorophenylboric acid, 2-fluorophenylboric acid,
3-fluorophnylboric acid, 4-fluorophenylboric acid,
2-chlorophenylboric acid, 3-chlorophenylboric acid,
4-chlorophenylboric acid, 2-bromophenylboric acid,
3-bromophenylboric acid, 4-bromophenylboric acid, 2-iodophenylboric
acid, 3-iodophenylboric acid, 4-iodophenylboric acid,
2,4-difluorophenylboric acid, 2,5-difluorophenylboric acid,
2,6-difluorophenylboric acid, 3,4-difluorophenylboric acid,
3,5-difluorophenylboric acid, 4-trifluoromethylphenylboric acid,
3,5-bis(trifluoromethyl)phenylboric acid, 3-cyanophenylboric acid,
4-formylphenylboric acid, 4-methoxyphenylboric acid,
1-naphthylboric acid, 2-naphthylboric acid, ferrocenylboric acid,
4-hydroxyphenylboric acid, and the aryl borate ester compound (such
as dimethyl, diethyl, dipropyl, diisoprpyl and pinacol ester) of
the arylboric acid compound as defined above.
[0137] The arylalkyne compounds to be used in the invention are not
particularly limited. Examples thereof include acetylene, propyne,
1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne,
phenylacetylene, 2-propyn-1-ol, 3-butyn-1-ol,
2-methyl-3-butyn-2-ol, 1-ethynyl-cyclohexanol, and
trimethylsilylacetylene.
[0138] In the invention, the amine compound may be used so as to be
present in the reaction system in an amount of from 0.1 to 50 mol
per mol of the aryl compound (2) or in an amount of from 0.1 to 50
mol per mol of the leaving group on the ring structure of the aryl
compound (2). However, from the standpoint of facilitating the
recovery of the amine compound remaining unreacted, the amine
compound is preferably used so as to be present in the reaction
system in an amount of from 0.2 to 30 mol per mol of the aryl
compound (2) or in an amount of from 0.2 to 60 mol per mol of the
leaving group on the ring structure of the aryl compound (2).
[0139] In the invention, the aryl boric acid compound or aryl
borate ester compound may be used so as to be present in the
reaction system in an amount of from 0.1 to 50 mol per mol of the
aryl compound (2) or in an amount of from 0.1 to 50 mol per of the
leaving group on the ring structure of the aryl compound (2).
However, from the standpoint of facilitating the recovery of the
aryl boric acid compound or aryl borate ester compound remaining
unreacted, the aryl boric acid compound or aryl borate ester
compound is preferably used so as to be present in the reaction
system in an amount of from 0.2 to 30 mol per mol of the aryl
compound (2) or in an amount of from 0.2 to 60 mol per mol of the
leaving group on the ring structure of the aryl compound (2).
[0140] In the invention, the alkyne compound may be used so as to
be present in the reaction system in an amount of from 0.1 to 50
mol per mol of the aryl compound (2) or in an amount of from 0.1 to
50 mol per of the leaving group on the ring structure of the aryl
compound (2). However, from the standpoint of facilitating the
recovery of the alkyne compound remaining unreacted, the aryl boric
acid compound or aryl borate ester compound is preferably used so
as to be present in the reaction system in an amount of from 0.2 to
30 mol per mol of the aryl compound (2) or in an amount of from 0.2
to 60 mol per mol of the leaving group on the ring structure of the
aryl compound (2).
[0141] The base to be used in the invention is not particularly
limited, and may be selected from inorganic bases and/or organic
bases. Preferred examples thereof include alkali metal fluorides
such as lithium fluoride, sodium fluoride, potassium fluoride,
rubidium fluoride, and cesium fluoride; alkali metal or alkaline
earth metal carbonates such as lithium carbonate, sodium carbonate,
potassium carbonate, rubidium carbonate, cesium carbonate,
magnesium carbonate, calcium carbonate, and barium carbonate;
alkali metal alkoxides such as sodium methoxide, sodium ethoxide,
sodium phenoxide, potassium methoxide, potassium ethoxide,
potassium phenoxide, lithium phenoxide, lithium tert-butoxide,
sodium tert-butoxide, and potassium tert-butoxide; alkali metal
phosphates such as lithium phosphate, potassium phosphate, and
sodium phosphate; and tertiary amines such as triethylamine,
tripropylamine, triisopropylamine, tributylamine,
tricyclohexylamine; and secondary amines such as diethylamine,
dipropylamine, diisopropylamine, dibutylamine, and
dicyclohexylamine. Besides being added as it is to the reaction
system, such as a base may be supplied to the reaction system by in
situ preparing it from an alkali metal, alkali metal hydride,
alkali metal hydroxide, or alkali metal phosphate and an
alcohol.
[0142] The amount of the base to be used is preferably at least 0.5
mol per mol of the leaving group of the aryl compound (2). If the
amount of the base is smaller than 0.5 mol, there are cases where
the yield of an arylamine, a diaryl and an arylalkyne is reduced.
Even when the base is added in large excess, the yield of an
arylamine, a diaryl and an arylalkyne remains unchanged, resulting
only in a complicated post-treatment after completion of the
reaction. Consequently, the amount of the base to be added is more
preferably in the range of from 1 to 5 mol.
[0143] The reaction according to the invention is usually conducted
in the presence of an inert solvent. The solvent to be used is not
particularly limited as long as it does not considerably inhibit
the reaction. Examples thereof include aliphatic organic solvents
such as pentane, hexane, heptane, and octane; alicyclic organic
solvents such as cyclohexane and methylcyclohexane; aromatic
organic solvents such as benzene, toluene, and xylene; ether type
organic solvents such as diethyl ether, diisopropyl ether,
dimethoxyethane, tetrahydrofuran, dioxane, and dioxolane; and
acetonitrile, dimethylformamide, dimethyl sulfoxide, and
hexamethylphosphoric triamide. Preferred of these are aromatic
organic solvents such as benzene, toluene, and xylene and ether
type organic solvents such as diethyl ether, dimethoxyethane,
tetrahydrofuran, and dioxane.
[0144] In this reaction, the catalyst produces the same results
when used by any of the following methods: a) a method in which a
palladium compound; a base; an amine compound, an arylboric acid
compound, an arylborate ester compound, or an alkyne compound; an
aryl compound havng a leaving group; and the
2,2-(diaryl)vinylphosphine compound (1), which each has been
described above, are charged into a reactor simultaneously; b) a
method in which a palladium compound, the reaction substrate, and
the 2,2-(diaryl)vinylphosphine compound (1) are separately charged
into a reactor in the presence of a base; c) a method in which a
palladium compound is mixed beforehand with the
2,2-(diaryl)vinylphosphine compound (1) in a reaction system to
prepare a catalyst, and an aryl compound having a leaving group is
then added to the reaction system in the presence of a base; and d)
a method in which a palladium compound is mixed beforehand with the
2,2-(diaryl)vinylphosphine compound (1) to prepare a catalyst, and
this catalyst and an aryl compound having a leaving group and this
reaction substance are separately charged into a reactor.
[0145] The amount of the palladium compound to be used for the
amination reaction or the carbon-carbon bond formation reaction is
generally from 0.001 to 20 mol %, preferably from 0.01 to 5 mol %,
based on this reaction substance (the amine compound, the arylboric
acid compound, the arylborate ester compound, or the alkyne
compound). The amount of the 2,2-(diaryl)vinylphosphine compound to
be used for this reaction is generally from 0.1 to 10 times by mol,
preferably from 1 to 5 times by mol, the amount of the palladium
compound.
[0146] In the invention, a palladium compound and the
2,2-(diaryl)vinylphosphine compound (1) are indispensable.
[0147] The amination reaction or the carbon-carbon bond formation
reaction according to the invention may be conducted at ordinary
pressure under an inert gas atmosphere such as nitrogen or argon,
or may be conducted at an elevated pressure.
[0148] The reaction according to the invention may be conducted at
a temperature of generally from 10 to 300.degree. C, preferably
from 20 to 200.degree. C.
[0149] Although the reaction time in the invention varies depending
on the amounts of the aryl compound (2), this reaction substance
(the amine compound, the arylboric acid compound, the arylborate
ester compound, or the alkyne compound), base, palladium compound,
and 2,2-(diaryl)vinylphosphine compound (1) and on the reaction
temperature, it may be selected in the range of from several
minutes to 72 hours.
[0150] After completion of the reaction, the reaction mixture is
treated in an ordinary way, whereby the target compound can be
obtained.
[0151] The novel 2,2-(diaryl)vinylphosphine compound of the
invention, when used together with a palladium compound, serves as
the catalyst of an amination reaction or a carbon-carbon bond
formation reaction to show excellent performances. When this
catalyst is used in the amination reaction or the carbon-carbon
formation reaction of an aryl compound having a leaving group, an
arylamine, a diaryl or an arylalkyne can be efficiently produced in
a shorter time period than in the amination reaction or the
carbon-carbon bond formation reaction with any conventional
amination catalyst or any conventional carbon-carbon bond formation
reaction catalyst. It is hence an excellent catalyst for industrial
use.
[0152] The invention will be explained below in more detail by
reference to Examples. However, the invention should not be
construed as being limited by these Examples in any way.
[0153] In the Examples, properties were determined using the
following apparatus.
[0154] 1) .sup.1H-NMR Spectrometry: Apparatus Type GEMINI 2000
(manufactured by Varian) or apparatus Type DRX-500 (manufactured by
Varian).
[0155] Internal standard substance: tetramethylsilane
[0156] 2) .sup.31P-NMR Spectrometry: Apparatus Type DRX-500
(manufactured by Bruker)
[0157] External standard substance: 85% phosphoric acid
[0158] 3) .sup.19F-NMR Spectrometry: Apparatus Type DRX-500
(manufactured by Bruker)
[0159] Internal standard substance: trifluoroacetic acid
[0160] 4) Melting Point: Yanaco MP-500D (manufactured by Yanagimoto
Shoji K. K.)
[0161] 5) Gas Chromatograph: GC 353 (manufactured by GL
Science)
[0162] Column: NB-1 (30 m.times.0.25 mm) (manufactured by GL
Science)
[0163] Internal standard substance: o-terphenyl or tridecane
[0164] 6) Mass Spectrometry (MS):
[0165] Mass spectrometer M-80: Ionization voltage, 20 eV
(manufactured by Hitachi Ltd.)
EXAMPLE 1
Synthesis of 1,1-Diphenyl-2-(diphenylphosphino)propene (Exemplified
Compound 20)
[0166] (1) Synthesis of 1-Diphenylpropene
[0167] Into a reactor were introduced 96.0 g (3.95 mol) of
magnesium and 500 mL of tetrahydrofuran (hereinafter abbreviated as
THF) under a nitrogen atmosphere. Iodine and bromobenzene were
added to the mixture in a slight amount to ascertain initiation of
a reaction. Thereafter, a mixture of 677 g (4.31 mol) of
bromobenzene and 1,500 mL of THF was gradually added dropwise
thereto while keeping the temperature of the system at about
40.degree. C., and this mixture was refluxed for 1 hour. Thereto
was gradually added dropwise 140 g (1.59 mol) of methyl propionate
while keeping the temperature of the system at about 40.degree. C.
This mixture was stirred at 60.degree. C. for 3 hours. The
resultant reaction mixture was washed with 0.1 M hydrochloric acid,
saturated aqueous sodium hydrogen carbonate solution, and saturated
aqueous sodium chloride solution and then dried with anhydrous
magnesium sulfate. Thereafter, the solvent was removed under
reduced pressure. The concentrate was dissolved in 800 mL of
toluene, and 3.8 g of p-toluenesulfonic acid monohydrate was added
thereto. Azeotropic dehydration was conducted for 1.5 hours with
toluene refluxing. After being cooled, the reaction mixture was
washed with saturated aqueous sodium hydrogen carbonate solution
and saturated aqueous sodium chloride solution and then dried with
anhydrous magnesium sulfate. Thereafter, the solvent was removed
under reduced pressure. The resultant concentrate was
recrystallized from methanol to obtain 230 g (75%) of the target
compound as white crystals.
[0168] Melting point: 48-49.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.76 (d, J=7.1 Hz, 3H), 6.17 (q, J=7.1 Hz, 1H), 7.08-7.44
(m, 10H)
[0169] (2) Synthesis of 2-Bromo-1,1-diphenylpropene
[0170] Into a reactor were introduced 19.4 g (100 mmol) of the
1,1-diphenylpropene and 78 mL of 1,2-dichloroethane under a
nitrogen atmosphere. The contents were cooled to 0.degree. C., and
15.9 g (100 mmol) of bromine was gradually added dropwise thereto.
The resultant mixture was stirred at room temperature for 1 hour.
Thereafter, 32.4 mL (400 mmol) of pyridine and 156 mL of toluene
were added thereto and this mixture was stirred at 80.degree. C.
for 3 hours. After being cooled, the reaction mixture was washed
with saturated aqueous sodium hydrogen carbonate solution and
saturated aqueous sodium chloride solution and then dried with
anhydrous magnesium sulfate. Thereafter, the solvent was removed
under reduced pressure. The concentrate was purified by column
chromatography and then recrystallized from methanol to obtain 14.5
g (53%) of the target compound as white crystals.
[0171] Melting point: 46-47.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 2.43 (s, 3H), 7.14-7.38 (m, 10H)
[0172] (3) Synthesis of 1,1-Diphenyl-2-(diphenylphosphino)propene
(Exemplified Compound 20)
[0173] Into a reactor were introduced 1.37 g (5.00 mmol) of the
2-bromo-1,1-diphenylpropene and 14 mL of THF under a nitrogen
atmosphere. The contents were cooled to -70.degree. C,. and 3.4 mL
(5.5 mmol; 1.6 M hexane solution) of butyllithium was gradually
added dropwise thereto. The resultant mixture was stirred for 30
minutes. Thereafter, 1.1 mL (6.0 mmol) of chlorodiphenylphosphine
was added, and this mixture was heated to room temperature and then
stirred for 13 hours. Water was added to the reaction mixture. The
organic layer was extracted with ethyl acetate, and the extract was
dried with anhydrous magnesium sulfate. Thereafter, the solvent was
removed under reduced pressure. The concentrate was recrystallized
from ethanol to obtain 1.08 g (60%) of the target compound as white
crystals.
[0174] Melting point: 128-130.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.70 (d, J=2.8 Hz, 3H), 7.12-7.47 (m, 20H) .sup.31P-NMR
(CDCl.sub.3) .delta. -4.68
EXAMPLE 2
Synthesis of 1,1-Diphenyl-2-(dicyclohexylphosphino)propene
(Exemplified Compound 19)
[0175] Into a reactor were introduced 8.50 g (31.1 mmol) of the
2-bromo-1,1-diphenylpropene obtained in Example 1 (2) and 85 mL of
THF under a nitrogen atmosphere. The contents were cooled to
-70.degree. C. Thereto was gradually added dropwise 21.4 mL (34.2
mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture
was stirred for 30 minutes. Thereafter, 8.25 ml (37.3 mmol) of
chlorodicyclohexylphosphine was added, and this mixture was stirred
for 75 minutes, subsequently heated to room temperature, and then
further stirred for 15.5 hours. Water was added to the reaction
mixture. The organic layer was extracted with ethyl acetate, and
the extract was dried with anhydrous magnesium sulfate. Thereafter,
the solvent was removed under reduced pressure. The concentrate was
recrystallized from ethanol to obtain 8.80 g (72%) of the target
compound as white crystals.
[0176] Melting point: 128-130.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.06-1.94 (m, 25H), 7.04-7.36 (m, 10H) .sup.31P-NMR
(CDCl.sub.3) .delta. -3.68
EXAMPLE 3
Synthesis of 1,1-Diphenyl-2-(di-tert-butylphosphino)propene
(Exemplified Compound 17)
[0177] Into a reactor were introduced 1.37 g (5.0 mmol) of the
2-bromo-1,1-diphenylpropene obtained in Example 1 (2), 0.134 g (5.5
mmol) of magnesium, and 11 mL of THF under a nitrogen atmosphere.
Iodine and bromobenzene were added to the mixture in a slight
amount to ascertain initiation of a reaction. Thereafter, the
reaction mixture was refluxed for 2 hours and then cooled. Thereto
were added 0.520 g (5.3 mmol) of copper chloride and 1.1 mL (5.5
mmol) of chlorodi-t-butylphosphine. This reaction mixture was
refluxed for 18 hours and then cooled to room temperature. Thereto
was added 14 mL of heptane. The crystals yielded were taken out by
filtration and dissolved in 40 mL of ethyl acetate. The resultant
solution was washed with 28% ammonia water and an aqueous sodium
chloride solution and then dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was recrystallized from ethanol to obtain 0.736 g (43%)
of the target compound as white crystals.
[0178] Melting point: 130-133.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.21 (s, 9H), 1.26 (s, 9H), 2.06 (d, J=1.4 Hz, 3H),
7.08-7.36 (m, 10H) .sup.31 P-NMR (CDCl.sub.3) .delta. 30.13
EXAMPLE 4
Synthesis of
1,1-Bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene
(Exemplified Compound 105)
[0179] (1) Synthesis of 1,1-Bis(4-dimethylaminophenyl)propene
[0180] Into a reactor was introduced 102 ml (82.0 mmol; 0.80 M THF
solution) of ethylmagnesium bromide under a nitrogen atmosphere.
The contents were cooled to 0.degree. C. Thereto was gradually
added dropwise a solution prepared by mixing 20.0 g (74.5 mmol) of
4,4'-bis(dimethylamino)benzophenone and 40 mL of THF. This mixture
was stirred at room temperature for 5 hours. Saturated aqueous
ammonium chloride solution was added to the resultant reaction
mixture, and the metal salt yielded was removed by Celite
filtration. The organic layer was separated from the filtrate and
then extracted with toluene. Thereafter, the solvent was removed
under reduced pressure. The concentrate was dissolved in 150 mL of
toluene, and 0.1 g of p-toluenesulfonic acid monohydrate was added
thereto. Azeotropic dehydration was conducted with toluene
refluxing. After being cooled, the reaction mixture was washed with
saturated aqueous sodium hydrogen carbonate solution and saturated
aqueous sodium chloride solution, subsequently dried with anhydrous
magnesium sulfate, and then concentrated under reduced pressure.
This concentrate was purified by column chromatography to obtain
13.6 g (65%) of light-yellow crystals.
[0181] .sup.1H-NMR (CDCl.sub.3) .delta. 1.77 (d, J=7.0 Hz, 3H),
2.92 (s, 6H), 2.98 (s, 6H), 5.94 (q, J=7.0 Hz, 1H), 6.58-6.79 (m,
4H), 7.02-7.18 (m, 4H)
[0182] (2) Synthesis of
1,1-Bis(4-dimethylaminophenyl)-2-bromopropene
[0183] Into a reactor were introduced 13.6 g (48.5 mmol) of the
1,1-bis(4-dimethylaminophenyl)propene and 54 mL of
1,2-dichloroethane under a nitrogen atmosphere. The contents were
cooled to 0.degree. C. Thereto was gradually added dropwise 7.76 g
(48.5 mmol) of bromine. The resultant mixture was stirred at room
temperature for 2.5 hours. Thereafter, 15.7 mL (194 mmol) of
pyridine and 109 mL of toluene were added thereto and this mixture
was stirred at 80.degree. C. for 3 hours. After being cooled, the
reaction mixture was washed with saturated aqueous sodium hydrogen
carbonate solution and saturated aqueous sodium chloride solution,
subsequently dried with anhydrous magnesium sulfate, and then
concentrated under reduced pressure. The concentrate was purified
by column chromatography and then crystallized from methanol to
obtain 12.0 g (69%) of the target compound as green-yellow
crystals.
[0184] Melting point: 119-122.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 2.46 (s, 3H) , 2.94 (s, 12H) , 6.58-6.70 (m, 4H), 6.96-7.20
(m, 4H)
[0185] (3) Synthesis of
1,1-Bis(4-dimethylaminophenyl)-2-(diphenylphosphin- o)propene
(Exemplified Compound 105)
[0186] Into a reactor were introduced 3.0 g (8.3 mmol) of the
1,1-bis(4-dimethylaminophenyl)-2-bromopropene and 10 mL of THF
under a nitrogen atmosphere. The contents were cooled to
-60.degree. C. Thereto was gradually added dropwise 5.2 mL (8.3
mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture
was stirred for 30 minutes. Thereafter, 1.1 mL (6.0 mmol) of
chlorodiphenylphosphine was added thereto and this mixture was
heated to room temperature and stirred for 16 hours. Water was
added to the reaction mixture. The resultant mixture was extracted
with ethyl acetate, and the extract was dried with anhydrous
magnesium sulfate. Thereafter, the solvent was removed under
reduced pressure. The concentrate was recrystallized twice from
hexane/ethanol to obtain 1.9 g (60%) of the target compound as
white crystals.
[0187] Melting point: 95-97.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.73 (d, J=2.8 Hz, 3H) 2.91 (s, 6H), 2.95 (s, 6H),
6.52-6.69 (m, 4H), 6.97-7.10 (m, 4H), 7.18-7.49 (m, 10H)
.sup.31P-NMR (CDCl.sub.3) .delta. -2.79
EXAMPLE 5
Synthesis of
1,1-Bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)prope- ne
(Exemplified Compound 120)
[0188] Into a reactor were introduced 1.44 g (4.00 mmol) of the
1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4
(2) and 14 mL of THF under a nitrogen atmosphere. The contents were
cooled to -60.degree. C. Thereto was gradually added dropwise 2.8
mL (4.4 mmol; 1.6 M hexane solution) of butyllithium. The resultant
mixture was stirred at that temperature for 1 hour. Thereafter,
0.97 mL (4.4 mmol) of chlorodicyclohexylphosphine was added
thereto, and this mixture was stirred for 30 minutes, subsequently
heated to room temperature, and then further stirred for 17 hours.
Water was added to the reaction mixture. The organic layer was
extracted with ethyl acetate, and the extract was dried with
anhydrous magnesium sulfate. Thereafter, the solvent was removed
under reduced pressure. The concentrate was recrystallized from
ethanol and hexane to obtain 0.44 g (23%) of the target compound as
white crystals.
[0189] Melting point: 159-164.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.04-2.15 (m, 25H), 2.91 (s, 6H), 2.92 (s, 6H), 6.50-6.75
(m, 4H), 6.85-7.08 (m, 4H) .sup.31P-NMR (CDCl.sub.3) .delta.
-2.19
EXAMPLE 6
Synthesis of
1,1-Bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propene
(Exemplified Compound 118)
[0190] Into a reactor were introduced 1.44 g (4.00 mmol) of the
1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4
(2), 0.107 g (4.4 mmol) of magnesium, and 11.5 mL of THF under a
nitrogen atmosphere. A slight amount of iodine was added to the
mixture to ascertain initiation of a reaction. Thereafter, the
reaction mixture was refluxed for 2 hours and then cooled. Thereto
were added 0.416 g (4.2 mmol) of copper chloride and 0.91 mL (4.4
mmol) of chlorodi-tert-butylphosphine. The reaction mixture was
refluxed for 18 hours and then cooled to room temperature. Thereto
were added 22.5 mL of heptane and 7.5 ml of diethyl ether. The
crystals yielded were taken out by filtration and dissolved in 30
mL of ethyl acetate. The resultant solution was washed with 28%
ammonia water and an aqueous sodium chloride solution and then
dried with anhydrous magnesium sulfate. Thereafter, the solvent was
removed under reduced pressure. The concentrate was recrystallized
from ethanol to obtain 0.34 g (20%) of the target compound as white
crystals.
[0191] Melting point: 133-135.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.21 (s, 9H), 1.26 (s, 9H), 2.21 (d, J=1.6 Hz, 3H), 2.91
(s, 6H), 2.92 (s, 6H), 6.50-6.69 (m, 4H), 6.91-7.04 (m, 4H)
.sup.31P-NMR (CDCl.sub.3) .delta. 31.68
EXAMPLE 7
Synthesis of 2,2-Diphenyl-1-(diphenylphosphino)ethylene
(Exemplified Compound 10)
[0192] (1) Synthesis of 1,1-Diphenylethylene
[0193] Into a reactor were introduced 31.6 g (1.30 mol) of
magnesium and 50 mL of THF under a nitrogen atmosphere. Iodine and
ethyl bromide were added to the mixture in a slight amount to
ascertain initiation of a reaction. Thereafter, 600 mL of THF was
added thereto, and methyl chloride gas having a regulated
temperature was bubbled into the resultant mixture at a regulated
rate so as to keep the mixture at 30 to 40.degree. C. After heat
generation ended and the magnesium metal was ascertained to have
disappeared, the reaction mixture was stirred at that temperature
for 1 hour. Subsequently, a mixture of 182 g (1.10 mol) of
benzophenone and 364 mL of THF was gradually added dropwise thereto
at 35 to 40.degree. C. and this mixture was stirred for 15 hours.
This reaction mixture was cooled and then poured into 10% aqueous
ammonium chloride solution. The resultant mixture was stirred for
30 minutes. After liquid separation, the organic layer was washed
with an aqueous sodium chloride solution and water, subsequently
dried with anhydrous magnesium sulfate, and then concentrated under
reduced pressure. To the concentrate were added 400 mL of toluene
and 1 g of p-toluenesulfonic acid monohydrate. The resultant
solution was subjected to azeotropic dehydration for 2 hours with
toluene refluxing. After being cooled, the reaction mixture was
washed with 2% aqueous sodium carbonate solution and water and then
dried with anhydrous magnesium sulfate. Thereafter, the solvent was
removed under reduced pressure. The concentrate was purified by
distillation to obtain 174 g (97%) of the target compound.
[0194] Melting point: 103.degree. C./134 Pa (1 mmHg)
[0195] (2) Synthesis of 1-Bromo-2,2-diphenylethylene
[0196] Into a reactor were introduced 110 g (0.60 mol) of the
1,1-diphenylethylene and 1,098 g of carbon tetrachloride under a
nitrogen atmosphere. A solution prepared by mixing 95.9 g (0.60
mol) of bromine with 288 g of carbon tetrachloride was added
dropwise thereto over 1 hour with cooling with ice. After
completion of the addition, the reaction mixture was stirred at
that temperature for 7 hours and then concentrated. To the residue
were added 119 g of pyridine and 500 mL of toluene. This mixture
was refluxed for 3 hours. After being cooled, the reaction mixture
was washed with 5% hydrochloric acid and water, subsequently dried
with anhydrous sodium sulfate, and then concentrated under reduced
pressure. The resultant concentrate was distilled and then
recrystallized from methanol to obtain 126 g (81%) of the target
compound as white crystals.
[0197] Melting point: 45.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 6.77 (s, 1H), 7.15-7.47 (m, 10H)
[0198] (3) Synthesis of 2,2-Diphenyl-1-(diphenylphosphino)ethylene
(Exemplified Compound 10)
[0199] The same procedure as in Example 1 (3) was conducted, except
that 1.30 g (5.00 mmol) of 2-bromo-1,1-diphenylethylene was used in
place of 2-bromo-1,1-diphenylpropene. Thus, 1.03 g (57%) of the
target compound was obtained as white crystals.
[0200] Melting point: 116-118.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 6.85 (d, J=3.4 Hz, 1H), 7.16-7.50 (m, 20H) .sup.31P-NMR
(CDCl.sub.3) .delta. -23.01
EXAMPLE 8
Synthesis of 1,1-Diphenyl-2-(dicyclohexylphosphino)-3-methylbutene
(Exemplified Compound 49)
[0201] (1) Synthesis of 1,1-Diphenyl-3-methylbutene
[0202] Into a reactor were introduced 2.92 g (120 mmol) of
magnesium and 100 mL of THF under a nitrogen atmosphere. Iodine and
bromobenzene were added to the mixture in a slight amount to
ascertain initiation of a reaction. Thereafter, 17.3 g (110 mmol)
of bromobenzene was gradually added dropwise thereto and the
resultant mixture was refluxed for 10 minutes. Subsequently, 6.51 g
(50.0 mmol) of ethyl isovalerate was gradually added dropwise to
the reaction mixture while keeping the temperature of the system at
about 40.degree. C., and this mixture was refluxed for 3 hours. The
resultant reaction mixture was washed with 0.1 M hydrochloric acid,
saturated aqueous sodium hydrogen carbonate solution, and saturated
aqueous sodium chloride solution and then dried with anhydrous
magnesium sulfate. Thereafter, the solvent was removed under
reduced pressure. The concentrate was dissolved in 50 mL of
toluene, and 0.05 g of p-toluenesulfonic acid monohydrate was added
thereto. Azeotropic dehydration was conducted for 2 hours with
toluene refluxing. After being cooled, the reaction mixture was
washed with saturated aqueous sodium hydrogen carbonate solution
and saturated aqueous sodium chloride solution, subsequently dried
with anhydrous magnesium sulfate, and then concentrated under
reduced pressure to obtain 8.81 g (79%) of a transparent oily
substance.
[0203] .sup.1H-NMR (CDCl.sub.3) .delta. 1.01 (d, J=6.6 Hz, 6H),
2.29-2.58 (m, 1H) 5.89 (d, J=10.2 Hz, 1H), 7.13-7.43 (m, 10H)
[0204] (2) Synthesis of 2-Bromo-1,1-diphenyl-3-methylbutene
[0205] Into a reactor were introduced 8.81 g (39.6 mmol) of the
1,1-diphenyl-3-methylbutene and 35 mL of 1,2-dichloroethane under a
nitrogen atmosphere. The contents were cooled to 0.degree. C., and
6.33 g (39.6 mmol) of bromine was gradually added dropwise thereto.
This mixture was stirred at room temperature for 1 hour. The
resultant reaction mixture was washed with saturated aqueous sodium
hydrogen carbonate solution and saturated aqueous sodium chloride
solution and then dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was recrystallized from ethanol and ethyl acetate to
obtain 8.64 g (72%) of the target compound as white crystals.
[0206] Melting point: 112-114.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.11 (d, J=6.6 Hz, 6H), 2.87 (septet, J=6.6 Hz, 1H),
7.13-7.38 (m, 10H)
[0207] (3) Synthesis of
1,1-Diphenyl-2-(dicyclohexylphosphino)-3-methylbut- ene
(Exemplified Compound 49)
[0208] Into a reactor were introduced 1.20 g (4.00 mmol) of the
2-bromo-1,1-diphenyl-3-methylbutene and 12 mL of THF under a
nitrogen atmosphere. The contents were cooled to -70.degree. C.,
and 2.8 mL (4.4 mmol; 1.6 M hexane solution) of butyllithium was
gradually added dropwise thereto. The resultant mixture was stirred
at that temperature for 30 minutes. Thereafter, 1.1 mL (4.8 mmol)
of chlorodicyclohexylphosphine was added thereto, and this mixture
was stirred at that temperature for 3 hours and then heated to room
temperature over 13 hours. Water was added to the reaction mixture.
The organic layer was extracted with ethyl acetate, and the extract
was dried with anhydrous magnesium sulfate. Thereafter, the solvent
was removed under reduced pressure. The concentrate was
recrystallized from ethanol and toluene to obtain 0.72 g (43%) of
the target compound as white crystals.
[0209] Melting point: 162-163.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 0.86-2.18 (m, 22H), 1.23 (d, J=7.0 Hz, 6H), 2.63-2.92 (m,
1H), 7.05-7.33 (m, 10H) .sup.31P-NMR (CDCl.sub.3) .delta. -1.46
EXAMPLE 9
Synthesis of 1,2,2-Triphenyl-1-(dicyclohexylphosphino)ethylene
(Exemplified Compound 99)
[0210] (1) Synthesis of 1,1,2-Triphenylethylene
[0211] Into a reactor was introduced 47 mL (55 mmol; 1.06 M THF
solution) of benzylmagnesium chloride under a nitrogen atmosphere.
The contents were cooled to 0.degree. C. Thereafter, a solution
prepared by mixing 9.11 g (50.0 mmol) of benzophenone with 18 mL of
THF was gradually added dropwise thereto, and this mixture was
stirred at room temperature for 1 hour. The resultant reaction
mixture was washed with 0.1 M hydrochloric acid, saturated aqueous
sodium hydrogen carbonate solution, and saturated aqueous sodium
chloride solution and then dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was dissolved in 46 mL of toluene, and 0.18 g of
p-toluenesulfonic acid monohydrate was added thereto. Azeotropic
dehydration was conducted for 2 hours with toluene refluxing. After
being cooled, the reaction mixture was washed with saturated
aqueous sodium hydrogen carbonate solution and saturated aqueous
sodium chloride solution, subsequently dried with anhydrous
magnesium sulfate, and then concentrated under reduced pressure to
obtain 12.5 g (98%) of a transparent oily substance.
[0212] .sup.1H-NMR (CDCl.sub.3) 6.94-7.37 (m, 16H)
[0213] (2) Synthesis of 1-Bromo-1,2,2-triphenylethylene
[0214] Into a reactor were introduced 12.5 g (48.8 mmol) of the
1,1,2-triphenylethylene and 50 mL of 1,2-dichloroethane under a
nitrogen atmosphere. The contents were cooled to 0.degree. C., and
7.80 g (48.8 mmol) of bromine was gradually added dropwise thereto.
This mixture was stirred at room temperature for 1 hour. The
resultant reaction mixture was washed with saturated aqueous sodium
hydrogen carbonate solution, saturated aqueous sodium thiosulfate
solution, and saturated aqueous sodium chloride solution and then
dried with anhydrous magnesium sulfate. Thereafter, the solvent was
removed under reduced pressure. The resultant concentrate was
recrystallized from ethanol and ethyl acetate to obtain 11.3 g
(69%) of the target compound as white crystals.
[0215] Melting point: 116-118.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 6.91-7.42 (m, 15H)
[0216] (3) Synthesis of
1,2,2-Triphenyl-1-(dicyclohexylphosphino)ethylene (Exemplified
Compound 99)
[0217] Into a reactor were introduced 1.68 g (5.0 mmol) of the
1-bromo-1,2,2-triphenylethylene, 0.134 g (5.5 mmol) of magnesium,
and 13 mL of THF under a nitrogen atmosphere. Iodine and
bromobenzene were added to the mixture in a slight amount to
ascertain initiation of a reaction. Thereafter, the reaction
mixture was refluxed for 2 hours and then cooled. Thereto were
added 0.520 g (5.3 mmol) of copper chloride and 1.2 mL (5.5 mmol)
of chlorodicyclohexylphosphine. This reaction mixture was refluxed
for 17 hours and then cooled to room temperature. Thereto was added
17 mL of heptane. The crystals yielded were taken out by filtration
and dissolved in 40 mL of ethyl acetate. The resultant solution was
washed with 28% ammonia water and an aqueous sodium chloride
solution and then dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was recrystallized from ethanol to obtain 1.34 g (59%)
of the target compound as white crystals.
[0218] Melting point: 121-123.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 0.94-2.00 (m, 22H), 6.84-7.40 (m, 15H) .sup.31P-NMR
(CDCl.sub.3) .delta. -0.979
EXAMPLE 10
Synthesis of 1,1-Bis(4-methoxyphenyl)-2-(diphenylphosphino)propene
(Exemplified Compound 103)
[0219] (1) Synthesis of 1,1-Bis(4-methoxyphenyl)propanol
[0220] Into a reactor were introduced 31.9 mL (30.9 mmol; 0.97 M
THF solution) of ethylmagnesium chloride and 20 mL of THF under a
nitrogen atmosphere. The contents were cooled to 4.degree. C.
Thereafter, a solution prepared by mixing 5.00 g (20.6 mmol) of
4,4'-dimethoxybenzophen- one with 20 mL of THF was gradually added
dropwise thereto, and this mixture was stirred at room temperature
for 1 hour. Saturated aqueous ammonium chloride solution was added
to the reaction mixture. The organic layer was extracted with ethyl
acetate, and the extract was dried with anhydrous magnesium sulfate
and then concentrated under reduced pressure. The concentrate was
purified by column chromatography to obtain 3.06 g (55%) of the
target compound as a light-yellow oily substance.
[0221] .sup.1H-NMR (CDCl.sub.3) .delta. 0.86 (t, J=7.4 Hz, 3H),
1.96 (br-s, 1H), 2.22 (q, J=7.4 Hz, 2H), 3.79 (s, 6H), 6.80-6.89
(m, 4H), 7.25-7.33 (m, 4H)
[0222] (2) Synthesis of 1,1-Bis(4-methoxyphenyl)propene
[0223] Into a reactor were introduced 2.86 g (10.5 mmol) of the
1,1-bis(4-methoxyphenyl)propanol, 40 mL of toluene, and 28 mg of
p-toluenesulfonic acid monohydrate under a nitrogen atmosphere.
Azeotropic dehydration was conducted for 2 hours with toluene
refluxing. After being cooled, the reaction mixture was washed with
saturated aqueous sodium hydrogen carbonate solution and saturated
aqueous sodium chloride solution, subsequently dried with anhydrous
magnesium sulfate, and then concentrated under reduced pressure to
obtain 2.60 g (97%) of the target compound as light-yellow
crystals.
[0224] Melting point: 99-100.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.75 (d, J=7.0 Hz, 3H), 3.79 (s, 3H) 3.84 (s, 3H), 6.03 (q,
J=7.0 Hz, 1H), 6.78-6.81 (m, 2H), 6.90-6.92 (m, 2H), 7.09-7.11 (m,
2H), 7.13-7.16 (m, 2H)
[0225] (3) Synthesis of 1,1-Bis(4-methoxyphenyl)-2-bromopropene
[0226] Into a reactor were introduced 2.50 g (9.82 mmol) of the
1,1-bis(4-methoxyphenyl)propene and 25 ml of 1,2-dichloroethane
under a nitrogen atmosphere. The contents were cooled to
-20.degree. C. A mixture of 1.57 g (9.82 mmol) of bromine and 13 mL
of 1,2-dichloroethane was gradually added dropwise thereto, and the
resultant mixture was stirred overnight at room temperature. This
reaction mixture was washed with saturated aqueous sodium hydrogen
carbonate solution and saturated aqueous sodium chloride solution
and then dried with anhydrous magnesium sulfate. Thereafter, the
solvent was removed under reduced pressure to obtain 3.26 g (100%)
of the target compound as a light-yellow oily substance.
[0227] .sup.1H-NMR (CDCl.sub.3) .delta. 2.43 (s, 3H), 3.78 (s, 6H),
6.81-6.84 (m, 4H), 7.05-7.09 (m, 2H), 7.16-7.19 (m, 2H)
[0228] (4) Synthesis of
1,1-Bis(4-methoxyphenyl)-2-(diphenylphosphino)prop- ene
(Exemplified Compound 103)
[0229] Into a reactor were introduced 2.00 g (6.00 mmol) of the
1,1-bis(4-methoxyphenyl)-2-bromopropene and 30 mL of THF under a
nitrogen atmosphere. The contents were cooled to -65.degree. C.,
and 4.0 mL (6.0 mmol; 1.5 M hexane solution) of butyllithium was
gradually added dropwise thereto. The resultant mixture was stirred
for 30 minutes. Thereafter, 0.90 mL (5.0 mmol) of
chlorodiphenylphosphine was added, and this mixture was stirred at
that temperature for 1 hour and then at room temperature for 1
hour. Saturated aqueous ammonium chloride solution was added to the
reaction mixture. The resultant mixture was extracted with ethyl
acetate, and the extract was dried with anhydrous magnesium
sulfate. Thereafter, the solvent was removed under reduced
pressure. The concentrate was recrystallized from ethanol to obtain
1.45 g (66%) of the target compound as white crystals.
[0230] Melting point: 123-125.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.71 (d, J=2.9 Hz, 3H) , 3.76 (s, 3H) 3.79 (s, 3H),
6.74-6.77 (m, 2H), 6.82-6.85 (m, 2H), 7.05-7.10 (m, 4H), 7.32-7.40
(m, 10H) .sup.31P-NMR (CDCl.sub.3) .delta. -3.73
EXAMPLE 11
Synthesis of 1,1-Bis(4-fluorophenyl)-2-(diphenylphosphino)propene
(Exemplified Compound 107)
[0231] (1) Synthesis of 1,1-Bis(4-fluorophenyl)propanol
[0232] Into a reactor were introduced 10.0 g (40.6 mmol) of cerium
chloride and 80 mL of THF under a nitrogen atmosphere. This mixture
was stirred at room temperature for 20 hours and then cooled to
0.degree. C. Thereto was added dropwise 25.1 mL (24.3 mmol; 0.97 M
THF solution) of ethylmagnesium chloride over 30 minutes.
Subsequently, a solution prepared by mixing 3.54 g (16.2 mmol) of
4,4'-difluorobenzophenone with 20 mL of THF was added dropwise
thereto over 40 minutes, and this mixture was stirred for 1 hour.
To the resultant reaction mixture was added 10% aqueous acetic acid
solution. Thereafter, the mixture was extracted with ethyl acetate,
and the resultant organic layer was washed with saturated aqueous
sodium hydrogen carbonate solution and saturated aqueous sodium
chloride solution, subsequently dried with anhydrous magnesium
sulfate, and then concentrated under reduced pressure. The
concentrate was purified by column chromatography to obtain 3.12 g
(78%) of the target compound as a light-yellow oily substance.
[0233] .sup.1H-NMR (CDCl.sub.3) .delta. 0.85 (t, J=7.4 Hz, 3H),
2.05 (s, 1H), 2.26 (q, J=7.4 Hz, 2H), 6.95-7.00 (m, 4H), 7.32-7.37
(m, 4H)
[0234] (2) Synthesis of 1,1-Bis(4-fluorophenyl)propene
[0235] Into a reactor were introduced 2.80 g (11.3 mmol) of the
1,1-bis(4-fluorophenyl)propanol, 60 mL of toluene, and 14 mg of
p-toluenesulfonic acid monohydrate under a nitrogen atmosphere.
Azeotropic dehydration was conducted for 1 hour with toluene
refluxing. After being cooled, the reaction mixture was washed with
saturated aqueous sodium hydrogen carbonate solution and saturated
aqueous sodium chloride solution, subsequently dried with anhydrous
magnesium sulfate, and then concentrated under reduced pressure to
obtain 2.39 g (92%) of the target compound as white crystals.
[0236] Melting point: 43-44.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.74 (d, J=7.0 Hz, 3H), 6.09 (q, J=7.0 Hz, 1H), 6.91-6.96
(m, 2H), 7.04-7.08 (m, 2H), 7.10-7.17 (m, 4H)
[0237] (3) Synthesis of 1,1-Bis(4-fluorophenyl)-2-bromopropene
[0238] Into a reactor were introduced 2.00 g (8.69 mmol) of the
1,1-bis(4-fluorophenyl)propene and 25 mL of 1,2-dichloroethane
under a nitrogen atmosphere. The contents were cooled to
-20.degree. C. A mixture of 1.39 g (8.69 mmol) of bromine and 12 mL
of 1,2-dichloroethane was added dropwise thereto over 1 hour, and
the resultant mixture was stirred at that temperature for 1 hour
and then at room temperature for 16 hours. Subsequently, a solution
prepared by mixing 0.703 mL (8.69 mmol) of pyridine with 20 mL of
toluene was added dropwise thereto over 15 minutes, and this
mixture was stirred at 100.degree. C. for 2 hours and then cooled.
Saturated aqueous sodium hydrogen carbonate solution was added to
the resultant reaction mixture, which was then extracted with
toluene. The resultant organic layer was washed with saturated
aqueous sodium chloride solution and then dried with anhydrous
magnesium sulfate. Thereafter, the solvent was removed under
reduced pressure. The concentrate was recrystallized from ethanol
to obtain 1.21 g (45%) of the target compound as white
crystals.
[0239] Melting point: 53-54.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 2.42 (s, 3H), 6.98-7.03 (m, 4H), 7.11-7.13 (m, 2H),
7.19-7.23 (m, 2H)
[0240] (4) Synthesis of
1,1-Bis(4-fluorophenyl)-2-(diphenylphosphino)prope- ne (Exemplified
Compound 107)
[0241] Into a reactor were introduced 0.907 g (2.93 mmol) of the
1,1-bis(4-fluorophenyl)-2-bromopropene and 20 mL of THF under a
nitrogen atmosphere. The contents were cooled to -65.degree. C.,
and 2.0 mL (2.9 mmol; 1.5 M hexane solution) of butyllithium was
gradually added dropwise thereto. The resultant mixture was stirred
for 40 minutes. Thereafter, a mixture of 0.58 mL (3.2 mmol) of
chlorodiphenylphosphine and 5 mL of THF was added thereto, and the
resultant mixture was stirred at that temperature for 2 hours and
then heated to room temperature. Saturated aqueous ammonium
chloride solution was added to the reaction mixture, which was then
extracted with ethyl acetate. The resultant organic layer was
washed with water and saturated aqueous sodium chloride solution
and then dried with anhydrous magnesium sulfate. Thereafter, the
solvent was removed under reduced pressure. The concentrate was
recrystallized from methanol to obtain 0.687 g (57%) of the target
compound as white crystals.
[0242] Melting point: 88-90.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 1.63 (d, J=2.8 Hz, 3H) , 6.81-6.87 (m, 2H), 6.90-6.96 (m,
2H), 7.00-7.08 (m, 4H), 7.25-7.32 (m, 10H) .sup.31P-NMR
(CDCl.sub.3) .delta. -4.40 .sup.19F-NMR (CDCl.sub.3) .delta.-115.0,
-114.9
EXAMPLE 12
[0243] Into a reactor were introduced 0.85 g (5.0 mmol) of
diphenylamine and 0.76 g of o-terphenyl as an internal standard
substance under a nitrogen atmosphere. Thereto was added 10 mL of
toluene to dissolve those ingredients. To this solution were added
0.53 g (5.5 mmol) of sodium t-butoxide, 0.95 mL (5.5 mmol) of
1-bromo-4-tert-butylbenzene, 2.8 mg (0.25 mol % based on the amine)
of palladium acetate, and 23.2 mg (1.0 mol % based on the amine) of
the 1,1-bis(4-dimethylaminophenyl)-2-(diphen- ylphosphino)propene
obtained in Example 4. This mixture was stirred at 100.degree. C.
for 8 hours and then cooled. The resultant reaction mixture was
analyzed by gas chromatography to determine the amount of
diphenyl(4-tert-butylphenyl)amine as the target compound by the
internal-standard determination method. The results obtained are
shown in Table 18.
[0244] .sup.1H-NMR (CDCl.sub.3) .delta. 1.31 (s, 9H), 6.92-7.30 (m,
14H)
EXAMPLE 13
[0245] The same procedure as in Example 12 was conducted, except
that the palladium compound was replaced with 2.3 mg (0.25 mol %
based on the amine) of (.pi.-allyl)palladium chloride. The amount
of diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 18.
EXAMPLE 14
[0246] The same procedure as in Example 12 was conducted, except
that the palladium compound was replaced with 4.8 mg (0.25 mol %
based on the amine) of dichlorobis(benzonitrile)palladium. The
amount of diphenyl(4-tert-butylphenyl)amine as the target compound
was determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 18.
EXAMPLE 15
[0247] The same procedure as in Example 12 was conducted, except
that the palladium compound was replaced with 3.8 mg (0.25 mol %
based on the amine) of palladium acetylacetonate. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 18.
EXAMPLE 16
[0248] The same procedure as in Example 12 was conducted, except
that the palladium compound was replaced with 14.4 mg (0.25 mol %
based on the amine) of tetrakis(triphenylphosphine)palladium. The
amount of diphenyl(4-tert-butylphenyl)amine as the target compound
was determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 18.
EXAMPLE 17
[0249] The same procedure as in Example 12 was conducted, except
that the palladium compound was replaced with 5.7 mg (0.25 mol %
based on the amine) of tris(dibenzylideneacetone)dipalladium. The
amount of diphenyl(4-tert-butylphenyl)amine as the target compound
was determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 18.
18 TABLE 18 Example Palladium Yield (%) Example 12 Pd(OAc).sub.2 85
Example 13 [(n-allyl)PdCl].sub.2 83 Example 14
(C.sub.6H.sub.5CN).sub.2PdCl.- sub.2 86 Example 15 Pd(acac).sub.2
78 Example 16 Pd(PPh.sub.3).sub.4 83 Example 17 Pd.sub.2(dba).sub.3
78
EXAMPLE 18
[0250] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 20.7 mg (1.0 mol % based on
the amine) of the
1,1-bis(4-dimethylaminophenyl)-2-(diphenylphosphino)propene
obtained in Example 4. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
EXAMPLE 19
[0251] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 18.9 mg (1.0 mol % based on
the amine) of the 1,1-diphenyl-2-(diphenylphosphino)propene
obtained in Example 1. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
EXAMPLE 20
[0252] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 19.5 mg (1.0 mol % based on
the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene
obtained in Example 2 and that the reaction time was changed to 3
hours. The amount of diphenyl(4-tert-butylphenyl)amine as the
target compound was determined by the internal-standard
determination method by gas chromatography. The results obtained
are shown in Table 19.
EXAMPLE 21
[0253] The same procedure as in Example 12 was conducted, except
that the phosphine and palladium acetate were replaced with 19.5 mg
(1.0 mol % based on the amine) of the
1,1-diphenyl-2-(di-t-butylphosphino)propene obtained in Example 3
and 2.3 mg (1.0 mol % based on the amine) of (.pi.-allyl)palladium
chloride, respectively, and that the reaction time was changed to 3
hours. The amount of diphenyl(4-tert-butylphenyl)amine as the
target compound was determined by the internal-standard
determination method by gas chromatography. The results obtained
are shown in Table 19.
EXAMPLE 22
[0254] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 18.2 mg (1.0 mol % based on
the amine) of the 2,2-diphenyl-1-(diphenylphosphino)ethylene
obtained in Example 7. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
EXAMPLE 23
[0255] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 23.8 mg (1.0 mol % based on
the amine) of the
1,1-bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)propene
obtained in Example 5 and that the reaction time was changed to 3
hours. The amount of diphenyl(4-tert-butylphenyl)amine as the
target compound was determined by the internal-standard
determination method by gas chromatography. The results obtained
are shown in Table 19.
EXAMPLE 24
[0256] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 21.2 mg (1.0 mol % based on
the amine) of the
1,1-bis(4-dimethylaminophenyl)-2-(di-t-butylphosphino)propene
obtained in Example 6. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
EXAMPLE 25
[0257] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 20.9 mg (1.0 mol % based on
the amine) of the
1,1-diphenyl-2-(dicyclohexylphosphino)-3-methylbutene obtained in
Example 8. The amount of diphenyl(4-tert-butylphenyl)amine as the
target compound was determined by the internal-standard
determination method by gas chromatography. The results obtained
are shown in Table 19.
EXAMPLE 26
[0258] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 22.6 mg (1.0 mol % based on
the amine) of the 1,2,2-triphenyl-1-(dicyclohexylphosphino)ethylene
obtained in Example 9. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
COMPARATIVE EXAMPLE 1
[0259] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 13.1 mg (1.0 mol % based on
the amine) of triphenylphosphine. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
COMPARATIVE EXAMPLE 2
[0260] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 15.2 mg (1.0 mol % based on
the amine) of tris(o-tolyl)phosphine. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
COMPARATIVE EXAMPLE 3
[0261] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 11.7 mg (1.0 mol % based on
the amine) of BINAP (2,2-bis(diphenylphosphino)-1,1'-binaphthyl).
The amount of diphenyl(4-tert-butylphenyl)amine as the target
compound was determined by the internal-standard determination
method by gas chromatography. The results obtained are shown in
Table 19.
COMPARATIVE EXAMPLE 4
[0262] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 14.0 mg (1.0 mol % based on
the amine) of triscyclohexylphosphine. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
COMPARATIVE EXAMPLE 5
[0263] The same procedure as in Example 12 was conducted, except
that the phosphine was replaced with 10.6 mg (1.0 mol % based on
the amine) of vinyldiphenylphosphine. The amount of
diphenyl(4-tert-butylphenyl)amine as the target compound was
determined by the internal-standard determination method by gas
chromatography. The results obtained are shown in Table 19.
19 TABLE 19 Time Yield Phosphine (hr) (%) Example 18
(4-Me.sub.2N--C.sub.6H.sub.4).sub.- 2C.dbd.C(Me)PPh.sub.2 8 85
Example 19 Ph.sub.2C.dbd.C(Me)PPh.sub.2 8 88 Example 20
Ph.sub.2C.dbd.C(Me)PCy.sub.2 3 96 Example 21
Ph.sub.2C.dbd.C(Me)P--tBu.sub.2 3 89 Example 22
Ph.sub.2C.dbd.C(H)PPh.sub.2 8 45 Example 23
(4-Me.sub.2N--C.sub.6H.sub.4).sub.2C.dbd.C(Me)PCy.sub.2 3 87
Example 24
(4-Me.sub.2N--C.sub.6H.sub.4).sub.2C.dbd.C(Me)P--tBu.sub.2 8 88
Example 25 Ph.sub.2C.dbd.C(iPr)PCy.sub.2 8 45 Example 26
Ph.sub.2C.dbd.C(Ph)PCy.sub.2 8 40 Comparative Ph.sub.3P 8 10
Example 1 Comparative (o-tolyl).sub.3P 8 30 Example 2 Comparative
BINAP 8 22 Example 3 Comparative Cy.sub.3P 8 37 Example 4
Comparative Vinyl-PPh.sub.2 8 1 Example 5
[0264] Table 19 shows that when the 2,2-(diaryl)vinylphosphine
compounds according to the invention (Examples 18 to 26) were used
to conduct an amination reaction, the target arylamine could be
obtained in high yield. In contrast, when triphenylphosphine
(Comparative Example 1), tris(o-tolyl)phosphine (Comparative
Example 2), BINAP (Comparative Example 3), triscyclohexylphosphine
(Comparative Example 4), and vinyldiphenylphosphine (Comparative
Example 5) were used as phosphines in place of the
2,2-(diaryl)vinylphosphine compounds of the invention to conduct
the reaction, the yield of the target arylamine was as low as 37%
at the most.
[0265] As demonstrated above, those 2,2-(diaryl)vinylphosphine
compounds according the invention are exceedingly useful phosphines
in completing the amination reaction of the invention.
EXAMPLE 27
Synthesis of N-p-Methoxyphenyl-N-p-tolylamine
[0266] Into a reactor were introduced 0.214 g (2.00 mmol) of
p-toluidine and 4 mL of dioxane under a nitrogen atmosphere. The
amine was dissolved in the solvent. To this solution were added
0.515 g (2.2 mmol) of p-iodoanisole, 0.231 g (2.4 mmol) of sodium
t-butoxide, 4.5 mg (1 mol % based on the amine) of palladium
acetate, and 15.6 mg (2 mmol % based on the amine) of the
1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example
2. The resultant reaction mixture was stirred at 100.degree. C. for
8 hours and then cooled. Saturated aqueous ammonium chloride
solution was added thereto, and this mixture was extracted with
toluene. The extract was dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was purified by column chromatography to obtain 0.351 g
(82%) of N-p-methoxyphenyl-N-p-tolylamine as yellow crystals. The
results obtained are shown in Table 20.
[0267] Melting point: 81-82.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 2.74 (s, 3H) , 3.79 (s, 3H), 5.38 (br-s, 1H), 6.78-6.91 (m,
4H), 6.96-7.09 (m, 4H)
EXAMPLE 28
Synthesis of N-p-Methoxyphenyl-N-p-tolylamine
[0268] Into a reactor were introduced 0.330 g (1.93 mmol) of
p-tolyl bromide and 4 mL of toluene under a nitrogen atmosphere.
The bromide was dissolved in the solvent. To this solution were
added 0.266 g (2.16 mmol) of p-anisidine, 0.226 g (2.35 mmol) of
sodium t-butoxide, 8.5 mg (1 mol % based on the amine) of
tris(dibenzylidene)dipalladium, and 32.3 mg (2 mmol % based on the
amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)p- ropene
obtained in Example 2. The resultant reaction mixture was stirred
at 100.degree. C. for 5 hours and then cooled. Saturated aqueous
ammonium chloride solution was added thereto, and this mixture was
extracted with toluene. The extract was dried with anhydrous
magnesium sulfate. Thereafter, the solvent was removed under
reduced pressure. The concentrate was purified by column
chromatography to obtain 0.366 g (89%) of
N-p-methoxyphenyl-N-p-tolylamine. The results obtained are shown in
Table 20.
EXAMPLE 29
Synthesis of N-(Diphenylmethylene)-4-aminobiphenyl
[0269] Into a reactor were introduced 0.466 g (2.00 mmol) of
4-bromobiphenyl and 4 mL of toluene under a nitrogen atmosphere.
The bromobiphenyl was dissolved in the solvent. To this solution
were added 0.399 g (2.2 mmol) of benzophenonimine, 0.231 g (2.4
mmol) of sodium t-butoxide, 13.5 mg (3 mol % based on the amine) of
palladium acetate, and 46.9 mg (6 mmol % based on the amine) of the
1,1-diphenyl-2-(dicycloh- exylphosphino)propene obtained in Example
2. The resultant reaction mixture was stirred at 100.degree. C. for
16 hours and then cooled. Saturated aqueous ammonium chloride
solution was added thereto, and this mixture was extracted with
toluene. The extract was dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was purified by column chromatography to obtain 0.409 g
(61%) of N-(diphenylmethylene)-4-aminobiphenyl as a yellow oily
substance. The results obtained are shown in Table 20.
[0270] .sup.1H-NMR (CDCl.sub.3) 6.74-7.88 (m, 19H)
EXAMPLE 30
Synthesis of N-(4-Cyanophenyl)morpholine
[0271] Into a reactor were introduced 0.275 g (2.00 mmol) of
4-chlorobenzonitrile and 4 mL of toluene under a nitrogen
atmosphere. The nitrile was dissolved in the solvent. To this
solution were added 0.192 g (2.2 mmol) of morpholine, 0.231 g (2.4
mmol) of sodium t-butoxide, 4.5 mg (1 mol % based on the amine) of
palladium acetate, and 15.6 mg (2 mmol % based on the amine) of the
1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example
2. The resultant reaction mixture was stirred at 100.degree. C. for
14 hours and then cooled. Saturated aqueous ammonium chloride
solution was added thereto, and this mixture was extracted with
toluene. The extract was dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was purified by column chromatography to obtain 0.304 g
(81%) of N-(4-cyanophenyl)morpholine as light-yellow crystals. The
results obtained are shown in Table 20.
[0272] Melting point: 80-81.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 3.23-3.33 (m, 4H), 3.80-3.90 (m, 4H), 6.81-6.92 (m, 2H),
7.47-7.57 (m, 2H)
EXAMPLE 31
Synthesis of Ditolylamine
[0273] Into a reactor were introduced 0.503 g (2.10 mmol) of
p-tolyl triflate and 4 mL of dioxane under a nitrogen atmosphere.
The triflate was dissolved in the solvent. To this solution were
added 0.246 g (2.29 mmol) of p-toluidine, 0.658 g (3.10 mmol) of
potassium phosphate, 19.9 mg (2.1 mol % based on the triflate) of
tris(dibenzylideneacetone)dipalladiu- m, and 58.7 mg (7.2 mmol %
based on the triflate) of the
1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example
2. The resultant reaction mixture was stirred at 100.degree. C. for
12 hours and then cooled. Saturated aqueous ammonium chloride
solution was added thereto, and this mixture was extracted with
toluene. The extract was dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was purified by column chromatography to obtain 0.268 g
(65%) of ditolylamine. The results obtained are shown in Table
20.
[0274] Melting point: 78-82.degree. C. .sup.1H-NMR (CDCl.sub.3)
.delta. 2.32 (s, 6H), 5.51 (br-s, 1H), 6.88-7.17 (m, 8H)
EXAMPLE 32
Synthesis of N-(3-Thiophenyl)-N,N-diphenylamine
[0275] Into a reactor were introduced 0.358 g (2.20 mmol) of
3-bromothiophene and 4 mL of toluene under a nitrogen atmosphere.
The bromothiophene was dissolved in the solvent. To this solution
were added 0.343 g (2.03 mmol) of diphenylamine, 0.229 g (2.39
mmol) of sodium t-butoxide, 4.4 mg (1 mol % based on the amine) of
palladium acetate, and 30.6 mg (2 mmol % based on the amine) of the
1,1-diphenyl-2-(dicyclohexyl- phosphino)propene obtained in Example
2. The resultant reaction mixture was stirred at 100.degree. C. for
10 hours and then cooled. Saturated aqueous ammonium chloride
solution was added thereto, and this mixture was extracted with
toluene. The extract was dried with anhydrous magnesium sulfate.
Thereafter, the solvent was removed under reduced pressure. The
concentrate was purified by column chromatography to obtain 0.257 g
(50%) of N-(3-thiophenyl)-N,N-diphenylamine. The results obtained
are shown in Table 20.
[0276] Melting point: 79-82.degree. C. .sup.1H-NMR (CDCl3) .delta.
6.66 (d/d, J=1.4, 3.1 Hz, 1H), 6.88 (d/d, J=1.4, 5.1 Hz, 1H),
6.94-7.36 (m, 11H)
COMPARATIVE EXAMPLE 6
Synthesis of N-p-Methoxyphenyl-N-p-tolylamine
[0277] The same procedure as in Example 27 was conducted, except
that the phosphine was replaced with 4.2 mg (1.0 mol % based on the
amine) of vinyldiphenylphosphine. The amount of
N-p-methoxyphenyl-N-p-tolylamine as the target compound was
determined by the internal-standard determination method by gas
chromatography. As a result, the yield was found to be 5%. The
results obtained are shown in Table 20.
COMPARATIVE EXAMPLE 7
Synthesis of N-p-Methoxyphenyl-N-p-tolylamine
[0278] The same procedure as in Example 28 was conducted, except
that the phosphine was replaced with 4.2 mg (1.0 mol % based on the
amine) of vinyldiphenylphosphine. The amount of
N-p-methoxyphenyl-N-p-tolylamine as the target compound was
determined by the internal-standard determination method by gas
chromatography. As a result, the yield was found to be 5%. The
results obtained are shown in Table 20.
20TABLE 20 Aryl Yield Example compound Amine Product (%) Example 27
4 5 6 82 Comparative Example 6 7 8 9 5 Example 28 10 11 12 89
Comparative Example 7 13 14 15 5 Example 29 16 17 18 61 Example 30
19 20 21 81 Example 31 22 23 24 65 Example 32 25 26 27 50
[0279] Table 20 shows that when the 2,2-(diaryl)vinylphosphine
compound according to the invention (Examples 27 to 32) was used to
conduct amination reactions, the target arylamines could be
obtained in high yields. In contrast, when vinyldiphenylphosphine
(Comparative Examples 6 and 7) was used as a phosphine in place of
the 2,2-(diaryl)vinylphosphine compound of the invention to conduct
amination reactions, the yield of the target arylamines was as low
as 5%.
[0280] As demonstrated above, that 2,2-(diaryl)vinylphosphine
compound according the invention is an exceedingly useful phosphine
in completing the amination reaction of the invention.
EXAMPLE 33
Synthesis of
[1,1-Diphenyl-2-(di-tert-butylphosphino)propene](.pi.-allyl)p-
alladium Chloride
[0281] Into a reactor were introduced 0.183 g (0.5 mmol) of
(.pi.-allyl)palladium chloride dimer, 0.338 g (1.0 mmol) of the
1,1-diphenyl-2-(di-t-butylphosphino)propene obtained in Example 3,
and 3 mL of toluene under a nitrogen atmosphere. The contents were
stirred at room temperature for 62 hours. To the resultant reaction
mixture was added 3 mL of heptane. This mixture was stirred for 30
minutes. The crystals yielded were taken out by filtration and
dried to obtain 0.25 g (48%) of the target compound.
[0282] .sup.31P-NMR (CDCl.sub.3) .delta. 63.83 MS (El): 519,
521
EXAMPLE 34
[0283] The same procedure as in Example 12 was conducted, except
that the palladium compound and phosphine were replaced with the
[1,1-diphenyl-2-(di-tert-butylphosphino)propene](.pi.-allyl)palladium
chloride (palladium-phosphine catalyst) obtained in Example 33. The
amount of diphenyl(4-tert-butylphenyl)amine as the target compound
was determined by the internal-standard determination method by gas
chromatography. As a result, the yield of the target compound was
90%.
Example 35
Synthesis of 4-Methylbiphenyl
[0284] Into a reactor were introduced 0.123 ml (1.0 mmol) of
1-bromotoluene, 0.1829 g (1.5 mmol) of phenylboric acid, 87.2 mg
(1.5 mmol) of potassium fluoride, 4.5 mg (0.02 mmol) of palladium
acetate, 11.7 mg (0.03 mmol) of the
1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example
2, and 3.0 ml of dioxane under a nitrogen atmosphere. The resultant
reaction mixture was stirred at room temperature for 20 hours. The
amount of 4-methylbiphenyl as the target compound was determined by
the internal-standard determination method by gas chromatography.
As a result, the yield was found to be 70%.
[0285] .sup.1H-NMR (CDCl.sub.3) .delta. 2.39 (s, 3H), 7.19-7.65 (m,
9H)
Example 36
Synthesis of 4-Methylbiphenyl
[0286] Into a reactor were introduced 0.123 ml (1.0 mmol) of
1-bromotoluene, 0.1829 g (1.5 mmol) of phenylboric acid, 87.2 mg
(1.5 mmol) of potassium fluoride, 4.5 mg (0.02 mmol) of palladium
acetate, 11.7 mg (0.03 mmol) of the
1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example
2, and 3.0 ml of dioxane under a nitrogen atmosphere. The resultant
reaction mixture was stirred at 80.degree. C. for 4 hours. The
amount of 4-methylbiphenyl as the target compound was determined by
the internal-standard determination method by gas chromatography.
As a result, the yield was found to be 95%.
Example 37
Synthesis of 2-Phenylpyridine
[0287] Into a reactor were introduced 0.79 g (5.0 mmol) of
2-bromo-pyridine, 0.73 g (6.0 mmol) of phenylboric acid, 1.38 g
(10.0 mmol) of potassium carbonate, 11.2 mg (0.05 mmol) of
palladium acetate, 39.1 mg (0.1 mmol) of the
1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example
2, 5.0 ml of water, and 15.0 ml of toluene under a nitrogen
atmosphere. The resultant reaction mixture was stirred at
80.degree. C. for 4 hours and then cooled. Thereafter, the solvent
was removed under pressure. The concentrate was purified by column
chromatography to obtain 0.66 g (85%) of 2-phenylpyridine as the
target compound.
[0288] .sup.1H-NMR (CDCl.sub.3) .delta. 7.15-7.29 (m 1H), 7.34-7.55
(m, 3H), 7.68-7.80 (m, 2H), 7.92-8.04 (m. 2H), 8.65-8.74 (m,
1H)
Example 38
Synthesis of 4-(4-Cyanophenyl)-2-methyl-3-butyne-2-ol
[0289] Into a reactor were introduced 1.38 g (10.0 mmol) of
4-chlorobenzonitrile, 1.68 g (20.0 mmol) of 2-methyl-3-butyne-2-ol,
2.7 mg (0.015 mmol) of palladium, 1.4 mg (0.0075 mmol) of copper
iodide, 17.6 mg (0.045 mmol) of the
1,1-diphenyl-2-(dicyclohexylphosphine)propene obtained in Example
2, 4.0 mL (0.055 mmol) of diisopropylamine, and 4.0 ml of
N,N-dimethylformamide under a nitrogen atmosphere. The resultant
reaction mixture was stirred at 100.degree. C. for 23 hours and
then cooled. Thereafter, the solvent was removed under pressure.
The concentrate was purified by column clromatography to obtain
1.56 g (84%) of 4-(4-cyanophenyl)-2-methyl-3-butyne-2-ol as white
crystals.
[0290] .sup.1H-NMR (CDCl.sub.3) .delta. 1.63 (s, 6H), 2.23 (br-s,
1H), 7.44-7.65 (m, 4H)
[0291] While the invention has been described in detail and with
reference to specific embodiments thereof, it will be apparent to
one skilled in the art that various changes and modifications can
be made therein without departing from the spirit and scope
thereof.
[0292] This application is based on Japanese patent application No.
2000-194690 filed on Jun. 28, 2000, the entire contents thereof
being hereby incorporated by reference.
* * * * *