Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2000-09-14
2002-07-09
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C564S337000, C568S316000, C568S323000, C568S328000, C568S331000, C568S632000, C568S642000, C568S928000, C585S427000, C585S435000
Reexamination Certificate
active
06417357
ABSTRACT:
This application is a 371 of PCT/EP99/01474, filed Mar. 8, 1999.
The present invention relates to a novel, inventive process for the preparation of biphenyls or aromatic olefins by coupling reactions using allyl palladium catalysts and novel allyl palladium catalysts.
Biphenyls and aromatic olefins can have versatile uses as chemical specialities for the preparation of liquid crystals, as photoinitiators, UV absorbers, fluorescent whitening agents, ligands for catalysts and as starting materials for the preparation of intermediates for agro-chemicals and pharmaceutical products.
A frequently used method for the synthesis of biphenyls is the palladium-catalysed cross-coupling (so-called Suzuki coupling) in which iodine aromatic compounds or bromine aromatic compounds or arylsulfonates are reacted with arylboron derivatives in the presence of palladium catalysts. This method is described, inter alia, in N. Miyaura et al.,
Synthetic Communications
, 11 (1981), 513; A. Suzuki in Metal-catalyzed Cross-coupling Reactions, chapter 2, Wiley—VCH, Weinheim 1998, in U.S. Pat. No. 5,130,439 and in EP-A-470 795.
A frequently used method for the synthesis of aromatic olefins is the palladium-catalysed coupling reaction, the socalled Heck reaction, in which iodine aromatic compounds or bromine aromatic compounds are reacted with olefins in the presence of palladium catalysts. This method is described, inter alia, in R. F. Heck, acc.
Chem. Res
. 1979, 12, 146; R. F. Heck,
Org. React
. 1982, 27, 345; and in R. F. Heck,
Palladium Reactions in Synthesis
, Academic Press, London 1985, S. Bräse and A. De Meijere in Metal-catalyzed Cross-coupling Reactions, chapter 3, Wiley—VCH, DE-Weinheim 1998.
In spite of their interesting broad utility, these methods have drawbacks regarding the synthesis. For example, if one does not want to use the catalyst in amounts of more than 1 mol %, then only small amounts of product can be produced on a laboratory scale by the cited coupling reactions. In the Suzuki reaction, the use of conventional palladium catalysts, e.g. Pd(PPh
3
)
4
, Pd(OAc)
2
and triphenyl phosphine, results in undesirable side reactions through aryl transference from the catalyst to the substrate; D. F. O'Keefe et al.
Tetrahedron Left
., 1992, 6679. The recovery of the palladium catalyst is elaborate in the case of the cited coupling reactions, the separation of the palladium residue from the reaction mixture requiring first the conversion of that residue into a palladium salt, e.g. palladium chloride or palladium acetate.
It is the object of this invention to find suitable catalysts for coupling reactions of biphenyls of the Suzuki cross-coupling type and of aromatic olefins of the Heck coupling type which promise improved turnover numbers (mol product/mol catalyst) and enhanced reactivity and selectivity over the catalysts used in such coupling reactions.
This object is achieved by the present invention which provides a novel, inventive process for the preparation of biphenyls and aromatic olefins using olefinic palladium complex compounds.
This invention relates to a process for the preparation of biphenyls of formula
wherein A and B define substituents; m and n define integers from 0 to 5 and the number of substituents at the phenyl radicals D and E; or
of aromatic olefins of formula
wherein C defines substituents, o defines integers from 0 to 5 as well as the number of substituents at the phenyl radical F, and R
6
, R
7
and R
8
are hydrogen or substituents, which process comprises
a) subjecting a phenyl derivative of formula
wherein A, B, m and n have the meanings cited for formula I and X is a leaving group, for the preparation of the biphenyls (I) to a coupling reaction with an arylboronic acid derivative of formula
wherein A, B, m and n have the meanings cited for formula I and Y is the—B(OH)
2
group or mono- or diester derivatives of—B(OH)
2
; and
b) subjecting a phenyl derivative of formula
wherein C and o have the meanings cited for formula II and X is a leaving group, for the preparation of the aromatic olefins (II) to a coupling reaction with an olefin of formula
wherein R
6
, R
7
and R
8
have the meanings cited for formula 11, each in the presence of a catalytically effective amount of an olefinic palladium complex compound of formula
wherein L is a neutral ligand having electron-donor properties, Z is an anionic ligand and D is a substituent, and p is an integer from 0 to 5 and defines the number of substituents at the allyl group; or
a′) subjecting a phenyl derivative (III a) or (IIIb), wherein A, B, m and n have the meanings cited for formula I and X is chloro, bromo or iodo, for the preparation of the biphenyls (I) to a coupling reaction with an arylboronic acid derivative (IV a) or (IV b), wherein A, B, m and n have the meanings cited for formula I and Y is the—B(OH)
2
group or mono- or diester derivatives of—B(OH)
2
; or
b′) subjecting a phenyl derivative (V), wherein C and o have the meanings cited for formula II and X is bromo or iodo, for the preparation of the aromatic olefins (II) to a coupling reaction with an olefin (VI), wherein R
6
, R
7
and R
8
have the meanings cited for formula II, in the presence of a catalytically effective amount of an olefinic, ionic palladium complex compound of formula
wherein Z
1
and Z
2
are anionic ligands and K
+
is a non-coordinating cation and D and p have the cited meanings, and isolating the biphenyl (I) or the condensed aromatic olefin (II) after the completion of the process variants a), b), a′) or b′).
The catalysts used in this process can be easily obtained by simple synthesis, for example by the method of B.{dot over (A)}kermark et al.,
Organometallics
1987, 6, 620-628, and have substantially improved reactivity and selectivity. After the reaction is complete, the dissolved olefinic palladium complex compounds can be degraded to palladium black using atmospheric oxygen. Using the method of Y. Inoue et al.
Synthesis
1984, 3, 244, this residue can be used again directly for the catalyst synthesis without any detour over the conversion into a palladium salt, such as palladium chloride or palladium acetate.
The terms and denotations used in this description of the invention preferably have the following meanings:
Biphenyls (I) are preferably substituted at the phenyl ring D by 1 to 5 substituents from the group A containing the substituents R
1
, R
2
, R
3
, R
4
and R
5
, and at the phenyl ring E also preferably by 1 to 5 substituents from the group B containing the substituents from the group R
6
, R
7
, R
8
, R
9
and R
10
. Suitable substituents are listed in the List of Radical Names, which is valid according to IUPAC Rules, and remain unchanged under the conditions of the coupling reactions. Any of the substituents may be selected. Suitable substituents A from the group R
1
, R
2
, R
3
, R
4
and R
5
are selected, for example, from the group consisting of the functional groups or derivatised functional groups consisting of amino, C
1
-C
4
alkylamino, C
1
-C
4
dialkylamino, hydroxy, oxo, thio, -NO
2
, carboxy, carbamoyl, sulfo, sulfamoyl, ammonio, amidino, cyano, formylamino, formamido and halogen, or are saturated or unsaturated aliphatic, cycloaliphaflc or heterocycloaliphatic radicals, carbocyclic or heterocyclic aryl radicals, condensed carbocyclic, heterocyclic or carbocyclic-heterocyclic radicals, which may in turn be combined with any others of these radicals and which may be substituted by the cited functional groups or derivatised functional groups.
The cited substituents and radicals can additionally be interrupted by one or more than one bivalent radical selected from the group consisting of —O—, —S—, —C (═O)—O—, —O—C(═O)—, —(═O)—N (C
1
-C
4
alkyl)—, —N(C
1
-C
4
alkyl)—C(═O)—, —S(═O)—, —S(═O)
2
—, —S(═O)—O—,—S(═O)
2
—O—, —O—S(═O)—, —O—S(═O)
2
—, —S(═O)—N(C
1
-C
4
alkyl)—, —S(═O)
2
—N(C
1
-C
4
alkyl)—, —(C
1
-C
4
alkyl)N—S(═O)—, —(C
1
-C
4
alkyl)N
Hafner Andreas
Tinkl Michael
Ciba Specialty Chemicals Corporation
Mansfield Kevin T.
Raymond Richard L.
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