Patent EP-0146439-B1 (EP)
IPC: C07C2/00
Filed: 1984-11-13
Granted: 1987-05-20
Abstract: 1. Claims for the contracting States BE CH DE FR GB IT LI LU NL SE A process for the preparation of acetylene derivatives of general formula :  see diagramm : EP0146439,P21,F1  in which : - R1 denotes a hydrogen atom, a phenyl radical or a radical of general formula : see diagramm : EP0146439,P21,F2  in which : - R2 and R3 , which are identical or different, denote a hydrogen atom or a saturated or unsaturated aliphatic radical substituted if desired by a 5- or 6-membered alicyclic radical containing, if desired, one or two double bonds and being substituted, if desired, by one or more alkyl radicals containing 1 to 4 carbon atoms, at least one of the symbols R2 and R3 denoting a saturated or unsaturated aliphatic radical or else R2 and R3 together form a 5- or 6-membered alicyclic radical containing, if desired, one or two double bonds and being substituted, if desired, by one or more alkyl radicals containing 1 to 4 carbon atoms, - R4 denotes a hydrogen atom or a saturated or unsaturated aliphatic radical or a hydroxy radical, an alkoxy radical in which the alkyl part contains 1 to 4 carbon atoms, an alkylcarbonyloxy radical in which the alkyl part contains 1 to 4 carbon atoms, or a methanesulphonyloxy, benzenesulphonyloxy or p-toluenesulphonyloxy radical, - R5 denotes a hydrogen atom or a saturated aliphatic radical and - R6 denotes a hydrogen atom or a saturated or unsaturated aliphatic radical or an acetyl radical, a formyl radical, if desired in acetal form, a hydroxy radical, if desired in ether or ester form, or an alkoxycarbonyl radical, it being understood that the saturated aliphatic radicals contain 1 to 11 carbon atoms and that the unsaturated aliphatic radicals contain 2 to 11 carbon atoms and one or more double bonds and are substituted, if desired, by one or more identical or different radicals chosen from acetyl radicals, formyl radicals, if desired in acetal form, hydroxy radicals, if desired in ether or ester form, or alkoxycarbonyl radicals by the reaction of an acetylene derivative of general formula : R1 - C -= C - H in which R1 is defined as above, with an allyl derivative of general formula :  see diagramm : EP0146439,P21,F3  or  see diagramm : EP0146439,P21,F4  in which R5 and R6 are defined as above and X denotes a halogen atom or a methanesulphonyloxy, benzenesulphonyloxy or p-toluenesulphonyloxy radical or quaternary ammonium, characterized in that the reaction is carried out in the presence of 0.1 to 20% on a molar basis relative to the allyl derivative of a copper derivative chosen from cuprous salts and copper (I) complexes or cupric salts or copper (II) complexes which are reduced beforehand and of 1 to 20 moles per mole of allyl derivative employed of an anhydrous organic base chosen from triethylamine, tributylamine, pyridine, lutidine and collidine at a temperature of between 20 and 100 degrees C. 1. Claims for the contracting States AT A process for the preparation of acetylene derivatives of general formula :  see diagramm : EP0146439,P22,F2  in which : - R1 denotes a hydrogen atom, a phenyl radical or a radical of general formula :  see diagramm : EP0146439,P22,F3  in which : - R2 and R3 , which are identical or different, denote a hydrogen atom or a saturated or unsaturated aliphatic radical substituted, if desired, by a 5- or 6-membered alicyclic radical containing, if desired, one or two double bonds and being substituted, if desired, by one or more alkyl radicals containing 1 to 4 carbon atoms, at least one of the symbols R2 and R3 denoting a saturated or unsaturated aliphatic radical or else R2 and R3 together form a 5- or 6-membered alicyclic radical containing, if desired, one or two double bonds and being substituted, if desired, by one or more alkyl radicals containing 1 to 4 carbon atoms, - R4 denotes a hydrogen atom or a saturated or unsaturated aliphatic radical or a hydroxy radical, an alkoxy radical in which the alkyl part contains 1 to 4 carbon atoms, an alkylcarbonyloxy radical in which the alkyl part contains 1 to 4 carbon atoms, or a methanesulphonyloxy, benzenesulphonyloxy or p-toluenesulphonyloxy radical, - R5 denotes a hydrogen atom or a saturated aliphatic radical and - R6 denotes a hydrogen atom or a saturated or unsaturated aliphatic radical or an acetyl radical, a formyl radical, if desired in acetal form, a hydroxy radical, if desired in ether or ester form, or an alkoxycarbonyl radical, it being understood that the saturated aliphatic radicals contain 1 to 11 carbon atoms and that the unsaturated aliphatic radicals contain 2 to 11 carbon atoms and one or more double bonds and are substituted, if desired, by one or more identical or different radicals chosen from acetyl radicals, formyl radicals, if desired in acetal form, hydroxy radicals, if desired in ether or ester form, or alkoxycarbonyl radicals by the reaction of an acetylene derivative of general formula : R1 - C -= C - H in which R1 is defined as above, with an allyl derivative of general formula :  see diagramm : EP0146439,P23,F1  or  see diagramm : EP0146439,P23,F2  in which R5 and R6 are defined as above and X denotes a halogen atom or a methanesulphonyloxy, benzenesulphonyloxy or p-toluenesulphonyloxy radical or quaternary ammonium, characterized in that the reaction is carried out in the presence of 0.1 to 20% on a molar basis relative to the allyl derivative of a copper derivative chosen from cuprous salts and copper(I) complexes or cupric salts or copper (II) complexes which are reduced beforehand and of 1 to 20 moles per mole of allyl derivative employed of an anhydrous organic base chosen from triethylamine, tributylamine, pyridine, lutidine and collidine at a temperature of between 20 and 100 degrees C.