Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-06-27
2002-09-24
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C568S017000, C568S008000, C564S305000, C502S162000
Reexamination Certificate
active
06455720
ABSTRACT:
FIELD OF THE INVENTION
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
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).
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”.)
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).
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).
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.
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
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.
The invention includes the following.
1. A 2,2-(diaryl)vinylphosphine compound represented by the following general formula (1):
(wherein R
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
2
and R
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
4
, R
5
, R
6
, and R
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
4
and R
5
taken together and/or R
6
and R
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 described in 1 above.
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.
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
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
1
is a halogen atom, a trifluoromethanesulfonyloxy 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 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
1
(2)
(wherein Ar and X
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 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
1
(2)
(wherein Ar and X
1
have the same meanings as defined above with an alkyne compound in the presence of a base).
DETAILED DESCRIPTION OF THE INVENTION
The invention will be explained below in detail.
In the compound (1) of the invention, R
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
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.
Specific examples of R
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 dimet
Hagiwara Toshimitsu
Hori Yoji
Kobayashi Tohru
Nishikawa Takenobu
Suzuki Ken
Fitzpatrick ,Cella, Harper & Scinto
Takasago International Corporation
Vollano Jean F.
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