Patent ID: 6291383
Filing Date: 2001-09-18
Classification: C07B,C07C

Abstract:
A process for preparing monofunctional, bifunctional or/and polyfunctional olefins of the formulae (Ia), (Ib), (Ic) or/and (Id), ##STR7##whereR.sup.1 to R.sup.3 are, independently of one another, hydrogen, (C.sub.1 -C.sub.8)-alkyl, CN COOH, COO-alkyl-(C.sub.1 -C.sub.8), aryl-(C.sub.6 -C.sub.10), COO-aryl-(C.sub.6 -C.sub.10), CO-aryl-(C.sub.6 -C.sub.10), O-alkyl-(C.sub.1 -C.sub.8), O--CO-alkyl-(C.sub.1 -C.sub.8), N-alkyl.sub.2 -(C.sub.1 -C.sub.8) and aryl is an aromatic radical containing up to 14 carbon atoms, where this radical may bear up to five substituents which are, independently of one another, hydrogen, (C.sub.1 -C.sub.8)-alkyl, O-alkyl-(C.sub.1 -C.sub.8), OCO-alkyl-(C.sub.1 -C.sub.8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO.sub.2, Si(alkyl-(C.sub.1 -C.sub.8)).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), P-alkyl.sub.2 -(C.sub.1 -C.sub.8), SO.sub.2 -alkyl-(C.sub.1 -C.sub.6), SO-alkyl-(C.sub.1 -C.sub.6), CF.sub.3, NHCO-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, NHCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, CHCH--CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), P(phenyl).sub.2, CHCHCO.sub.2 H, PO-phenyl.sub.2, POalkyl.sub.2 -(C.sub.1 -C.sub.4), PO.sub.3 H.sub.2, PO(O-alkyl-(C.sub.1 -C.sub.6)).sub.2, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4) where aryl is as defined above, and whereR.sup.1a to R.sup.7a are, independently of one another, hydrogen, (C.sub.1 -C.sub.8)-alkyl, O-alkyl-(C.sub.1 -C.sub.8), OCO-alkyl-(C.sub.1 -C.sub.8), O-phenyl, phenyl, aryl, fluorine, chlorine, OH, NO.sub.2, Si(alkyl-(C.sub.1 -C.sub.8)).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), P-alkyl.sub.2 -(C.sub.1 -C.sub.8), SO.sub.2 -alkyl-(C.sub.1 -C.sub.6)-alkyl-(C.sub.1 -C.sub.6), CF.sub.3, NHCO-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, NHCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, CHCH--CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), P(phenyl).sub.2, CHCHCO.sub.2 H, PO-phenyl.sub.2, POalkyl.sub.2 -(C.sub.1 -C.sub.4), PO.sub.3 H.sub.2, PO(O-alkyl-(C.sub.1 -C.sub.6)).sub.2, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), where aryl is as defined above, and is a heteroaromatic, where the heteroaromatic Ar can be a substituted 5-, 6- or 7-membered ring containing, if desired, nitrogen, oxygen or sulfur atoms in the ring, where further aromatic, heteroaromatic and/or aliphatic rings can be fused onto the ring, and where the heteroaromatic can have substituents which are, independently of one another, hydrogen, (C.sub.1 -C.sub.8)-alkyl, O-aryl, aryl, fluorine, chlorine, OH, NO.sub.2, CN, CO.sub.2 H, CHO, SO.sub.3 H, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.12), N-alkyl.sub.2 -(C.sub.1 -C.sub.12), CHCHCO.sub.2 H, NHCO-alkyl-(C.sub.1 -C.sub.12), CO-alkyl-(C.sub.1 -C.sub.12), NHCHO, COaryl, CO.sub.2 aryl, CF.sub.3, CONH.sub.2, POaryl.sub.2, POalkyl.sub.2 -(C.sub.1 -C.sub.12), Si(alkyl-(C.sub.1 -C.sub.2)).sub.3,O-alkyl-(C.sub.1 -C.sub.8), OCO-alkyl-(C.sub.1 -C.sub.8), O-phenyl, phenyl, NH-alkyl-(C.sub.1 -C.sub.4), COO-alkyl-(C.sub.1 -C.sub.8), NHCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, CHCH--CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), PO-phenyl.sub.2, PO.sub.3 H.sub.2, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), SO.sub.2 -alkyl-(C.sub.1 -C.sub.4), SO-alkyl-(C.sub.1 -C.sub.4), where aryl is as defined above, and whereR.sup.8a to 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)yl, phenyl, aryl, PO(phenyl).sub.2, 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), CONH-alkyl-(C.sub.1 -C.sub.8), CONH-alkyl-(C.sub.1 -C.sub.8).sub.2,NH-alkyl-(C.sub.1 -C.sub.4), PO.sub.3 H.sub.2, SO.sub.3 H, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), SO.sub.2 -alkyl-(C.sub.1 -C.sub.4), O-phenyl, where aryl is as defined above,by reacting haloaromatics, haloolefins or/and heterohaloaromatics of the formulae (IIa), (IIb), (IIc) or/and (IId) ##STR8##with olefins of the fornula (III), ##STR9##where, in the formulae of the type II and III, R.sup.1 to R.sup.3 and R.sup.1a to R.sup.10a are as defined above for the formulae of the type (I) andwhere X is iodine, bromine, chlorine, OSO.sub.2 CF.sub.3, OSO.sub.2 -phenyl, OSO.sub.2 -tolyl, OSO.sub.2 -alkyl-(C.sub.1 -C.sub.8), wherein a mixture of a palladium(0) complex or a palladium(II) salt with phosphite ligands of the formulae (IVa) or/and (IVb), ##STR10##the formula (IVb) represents a chelating phosphite ligand and where the radicals R.sup.11a to R.sup.14a are identical or different and are each, independently of one another, (C.sub.1 -C.sub.18)-alkyl or/and a substituted (C.sub.1 -C.sub.18)-alkyl group having the substituents hydrogen, O-alkyl-(C.sub.1 -C.sub.8), O--CO-alkyl-(C.sub.1 -C.sub.8), O-phenyl, phenyl, fluorine, chlorine, OH, NO.sub.2, CN, COOH, CHO, SO.sub.3 H, SO.sub.2 -alkyl-(C.sub.1 -C.sub.8), SO-alkyl-(C.sub.1 -C.sub.8), 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), CF.sub.3, COO-alkyl-(C.sub.1 -C.sub.8), CONH.sub.2, CO-alkyl-(C.sub.1 -C.sub.8), NHCOH, NHCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, CHCH--CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), CHCHCO.sub.2 H, PO-phenyl.sub.2, POalkyl.sub.2 -(C.sub.1 -C.sub.8),or the radicals R.sup.11a to R.sup.14 are an aromatic Ar', where Ar' is a substituted phenyl, naphthyl, anthryl, phenanthryl or biphenyl radical or/and a 5-, 6- or 7-membered heteroaromatic containing, optionally nitrogen, oxygen or sulfur atoms in the ring,where the aromatics may contain up to ten substituents which are (C.sub.1 -C.sub.8)-alkyl, OAr', Ar', fluorine, chlorine, OH, NO.sub.2, CN, CO.sub.2 H, CHO, SO.sub.3 H, NH.sub.2, NH-alkyl-(C.sub.1 -C.sub.12), N-alkyl.sub.2 -(C.sub.1 -C.sub.12), NHCO-alkyl-(C.sub.1 -C.sub.12), CO-alkyl-(C.sub.1 -C.sub.12), NHCHO, COAr', CO.sub.2 Ar', CF.sub.3, CONH.sub.2, CHCHCO.sub.2 H, POAr's, POalkyl.sub.2 -(C.sub.1 -C.sub.12), Si(alkyl-(C.sub.1 -C.sub.12)).sub.3,O-alkyl-(C.sub.1 -C.sub.8), OCO-alkyl-(C.sub.1 -C.sub.8), O-phenyl, phenyl, COO-alkyl-(C.sub.1 -C.sub.8), NHCOO-alkyl-(C.sub.1 -C.sub.4), CO-phenyl, COO-phenyl, CHCH--CO.sub.2 -alkyl-(C.sub.1 -C.sub.8), PO-phenyl.sub.2, PO.sub.3 H.sub.2, SO.sub.3 -alkyl-(C.sub.1 -C.sub.4), SO.sub.2 -alkyl-(C.sub.1 -C.sub.4), SO-alkyl-(C.sub.1 -C.sub.8), where the carbon bridge of the phosphite ligand C.sub.2 to C.sub.4 may have up to four substituents which are identical or different and are, hydrogen, (C.sub.1 -C.sub.4)-alkyl, O-alkyl-(C.sub.1 -C.sub.4), OH, aryl or/and phenyl, where aryl is as defined above.