Process for the Pd-catalyzed arylation of olefins with aryl halides
AssigneeCiba-Geigy Corporation
InventorAlwyn Spencer
Life of this patent
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Abstract
Compounds of the formula I ##STR1## in which A is C.sub.2-12 -alkenyl, C.sub.4-8 -cycloalkenyl or a grouping--C(R).dbd.C(R')--Y and Y, R, R', R.sub.1, R.sub.2, R.sub.3 and R.sub.3 ' are as defined in patent claim 1, can be prepared in high yields in a simple and economical manner by reacting corresponding bromobenzenes or iodobenzenes with a compound HA in the presence of an alkali metal salt or alkaline earth metal salt of an aliphatic monocarboxylic acid having 1-12 C atoms or benzoic acid, of a cyclic or N,N-disubstituted amide as the solvent, particularly N,N-dimethylformamide, and of a palladium compound which can, if desired, contain arsenic or phosphorus, as the catalyst.
Claims19
A process for the preparation of a compound of formula I ##STR16## in which A is ##STR17## wherein Y is cyano;
- R is selected from the group consisting of hydrogen, methyl, cyano, and --COOR";
- R' is selected from the group consisting of hydrogen, methyl, and --CH.sub.2 COOR";
- R" is selected from the group consisting of C.sub.1 -C.sub.12 -alkyl and phenyl;
- R.sub.1, R.sub.2, and R.sub.3, independently of one another, are selected from the group consisting of hydrogen, phenyl, C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.5 -alkoxy, --CH(OCH.sub.3).sub.2, --CH(OC.sub.2 H.sub.5).sub.2, ##STR18## OH, halogen, nitro, cyano, --CHO, --CO, --(C.sub.1 -C.sub.4)-alkyl, --COO--(C.sub.1 -C.sub.4)-alkyl, --NHCO--(C.sub.1 -C.sub.4)-alkyl, amino, --NH--(C.sub.1 -C.sub.4)-alkyl, --N((C.sub.1 -C.sub.4)-alkyl).sub.2 and SO.sub.3 M;
- R.sub.2 being further selected from the group consisting of --CH.dbd.N-phenyl, p-bromophenyl, and --C(R.sub.4).dbd.C(R.sub.5)(R.sub.6);
- R.sub.3 ' is selected from the group consisting of hydrogen, methyl, cyano, --CHO, and SO.sub.3 -phenyl;
- R.sub.4 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 -alkyl, cyano, --COO--(C.sub.1 -C.sub.4)-alkyl;
- R.sub.5 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.4 -alkyl, --NHCHO, --(CH.sub.2).sub.m --COO--(C.sub.1 -C.sub.4)alkyl and --(CH.sub.2).sub.m --CN, is which m is 1-4;
- R.sub.6 is selected from the group consisting of cyano and --COO--(C.sub.1 -C.sub.4)-alkyl;
- or
- R.sub.1 and R.sub.2 are both hydrogen and R.sub.3 and R.sub.3 ' together are --CH.dbd.CH--CH.dbd.CH--;
- and
- M is a monovalent metal cation;
- which process comprises reacting a compound of formula II ##STR19## with a compound HA in the presence of (i) an alkali salt or alkaline earth metal salt of
- (a) an aliphatic monocarboxylic acid having 1 to 12 carbon atoms or
- (b) benzoic acid;
- (ii) a cyclic or N,N-di-substituted amine as a solvent;
- and
- (iii) a palladium catalyst containing arsenic or phosphorous,
- X being selected from the group consisting of iodine and bromine;
- A, Y, R, R', R.sub.1, R.sub.2, R.sub.3, and R.sub.3 ' being as defined above, said palladium catalyst being present in an amount of 0.1 to 0.0001 mole percent based on the compound of formula II, said reaction taking place at a temperature between 50.degree. and 200.degree. C.
Dependencies are inferred from the claim text.