Processs for preparing aromatic olefins using palladacycle catalysis
AssigneeAventis
InventorsWolfgang Anton Herrmann, Matthias Beller, Ahmed Tafesh
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Abstract
The invention relates to a process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR1## wherein a palladium compound of the formula (IV) ##STR2## is used as a catalyst in the preparation of the compounds of the formula (I).
Claims21
A process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR9## where R.sup.1a to R.sup.7a are, independently of one another, hydrogen, C.sub.1 -C.sub.8 -alkyl, alkoxy-(C.sub.1 -C.sub.8), acyloxy-(C.sub.1 -C.sub.8), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO.sub.2, OSO.sub.2 CF.sub.3, CN, COOH, CHO, SO.sub.3 H, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.8), N-alkyl.sub.2 -(C.sub.1 -C.sub.8), NHCO-alkyl-(C.sub.1 -C.sub.4), N-alkyl-(C.sub.1 -C.sub.4)-CO-alkyl-(C.sub.1 -C.sub.4), COO-alkyl-(C.sub.1 -C.sub.8), CONH.sub.2, CO-alkyl-(C.sub.1 -C.sub.8), NHCOH, NCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, PO-phenyl.sub.2, or PO-alkyl.sub.2 -(C.sub.1 -C.sub.4), where one of the radicals R.sup.1a to R.sup.7a can also be ##STR10## R.sup.8a is hydrogen, alkyl-(C.sub.1 -C.sub.8), phenyl, O-alkyl-(C.sub.1 -C.sub.8), or fluorine
- R.sup.9a and R.sup.10a are, independently of one another, hydrogen, CN, CO.sub.2 H, CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), CONH.sub.2, CONH-alkyl-(C.sub.1 -C.sub.4), CON(alkyl).sub.2 -(C.sub.1 -C.sub.4), fluorine, CO.sub.2 -phenyl, alkyl, (C.sub.1 -C.sub.8)phenyl, PO(phenyl), PO(alkyl-(C.sub.1 -C.sub.4)).sub.2, CO-phenyl, CO-alkyl-(C.sub.1 -C.sub.4), O-alkyl-(C.sub.1 -C.sub.4), NH-alkyl-(C.sub.1 -C.sub.4), PO.sub.3 H, SO.sub.3 H, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), SO.sub.2 -alkyl-(C.sub.1 -C.sub.4), or O-phenyl, by reaction of haloaromatics of the formula (II) ##STR11## with olefins of the formula (III) ##STR12## where R.sup.1a to R.sup.10a are as defined above, where one of the radicals R.sup.1a to R.sup.7a can also be X and X is iodine, bromine, chlorine, or OSO.sub.2 CF.sub.3, in the presence of a dipolar aprotic solvent wherein a palladium compound of the formula (IV) ##STR13## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are, independently of one another, hydrogen, (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, fluorine, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.4), N-(alkyl).sub.2 -(C.sub.1 -C.sub.4), CO.sub.2 alkyl-(C.sub.1 -C.sub.4), OCO-alkyl-(C.sub.1 -C.sub.4) or phenyl,
- or R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6 together form an aliphatic or aromatic ring, and R.sup.7 and R.sup.8 are (C.sub.1 -C.sub.8)-alkyl, (C.sub.3 -C.sub.12)-cycloalkyl, or substituted or unsubstituted aryl, and
- Q is an anion of an inorganic or organic acid, is used as a catalyst in the reaction between II and III.
A process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR14## where R.sup.1a to R.sup.7a are, independently of one another, hydrogen, C.sub.1 -C.sub.8 -alkyl, alkoxy-(C.sub.1 -C.sub.8), acyloxy-(C.sub.1 -C.sub.8), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO.sub.2, OSO.sub.2 CF.sub.3, CN, COOH, CHO, SO.sub.3 H, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.8), N-alkyl.sub.2 -(C.sub.1 -C.sub.8), NHCO-alkyl-(C.sub.1 -C.sub.4), N-alkyl-(C.sub.1 -C.sub.4)-CO-alkyl-(C.sub.1 -C.sub.4), COO-alkyl-(C.sub.1 -C.sub.8), CONH.sub.2, CO-alkyl-(C.sub.1 -C.sub.8), NHCOH, NCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, PO-phenyl.sub.2, or PO-alkyl.sub.2 -(C.sub.1 -C.sub.4), where one of the radicals R.sup.1a to R.sup.7a can also be ##STR15## where R.sup.8a is hydrogen, alkyl-(C.sub.1 -C.sub.8), phenyl, O-alkyl-(C.sub.1 -C.sub.8), or fluorine, and
- R.sup.9a and R.sup.10a are, independently of one another, hydrogen, CN, CO.sub.2 H, CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), CONH.sub.2, CONH-alkyl-(C.sub.1 -C.sub.4), CON(alkyl).sub.2 -(C.sub.1 -C.sub.4), fluorine, CO.sub.2 -phenyl, alkyl, (C.sub.1 -C.sub.8)phenyl, PO(phenyl), PO(alkyl-(C.sub.1 -C.sub.4)).sub.2, CO-phenyl, CO-alkyl-(C.sub.1 -C.sub.4), O-alkyl-(C.sub.1 -C.sub.4), NH-alkyl-(C.sub.1 -C.sub.4), PO.sub.3 H, SO.sub.3 H, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), SO.sub.2 -alkyl-(C.sub.1 -C.sub.4), or O-phenyl, by reaction of haloaromatics of the formula (II) ##STR16## with olefins of the formula (III) ##STR17## where R.sup.1a to R.sup.10a are as defined above, where one of the radicals R.sup.1a to R.sup.7a can also be X and X is iodine, bromine, chlorine, or OSO.sub.2 CF.sub.3, in the presence of a dipolar aprotic solvent and at least one of a base and 2,6-di-tert-butyl phenol, wherein a palladium compound of the formula (IV) ##STR18## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are, independently of one another, hydrogen, (C.sub.1 -C.sub.4)-alkyl, (C.sub.1 -C.sub.4)-alkoxy, fluorine, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.4), N-(alkyl).sub.2 -(C.sub.1 -C.sub.4), CO.sub.2 alkyl-(C.sub.1 -C.sub.4), OCO-alkyl-(C.sub.1 -C.sub.4) or phenyl,
- or R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6 together form an aliphatic or aromatic ring,
- and R.sup.7 and R.sup.8 are (C.sub.1 -C.sub.8)-alkyl, (C.sub.3 -C.sub.12)-cycloalkyl, or substituted or unsubstituted aryl, and
- Q is an anion of an inorganic or organic acid, is used as a catalyst in the reaction between II and III.
Dependencies are inferred from the claim text.