Diaryl acetylenes, their preparation and use

Claim 1

A process for the preparation of a diarylacetylene of the formula I where R 1 and R 2 are each hydrogen or methyl, R 3 is hydrogen, methyl, hydroxyl or C l -C 6 -alkoxy, R 4 is hydrogen, methyl or methoxy, R 5 is hydrogen, halogen, methoxy or C 1 -C 4 -alkyl, A is a methylene or ethylene radical which is unsubstituted or substituted by C 1 -C 4 -alkyl or is -CH=CH-, ―CHOH―CH 2 ― or ―CO―CH 2 ―, and R 6 is hydrogen, methyl, nitrile, tetrazolyl, 2-oxazolinyl, C 2 -C 10 -ketal or a radical ―CHR 7 ―OR 8 , ―CHR 7 ―NR 9 R 10 , ―COR 11 , ―CR 12 =CH―COOR 13 or ―CR 12 =CH―CO―NR 14 R 15 , where R 7 is hydrogen or C 1 -C 4 -alkyl, R 8 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 20 -alkanoyl, unsubstituted or substituted benzoyl or a radical ―P(O)(OR 13 ) 2 or ―P(O)(NR 14 R 15 ) 2 (where R 13 is hydrogen, unsubstituted or hydroxyl-substituted C 1 -C a -alkyl, unsubstituted or substituted aryl or aralkyl which is unsubstituted or substituted in the aryl moiety, and R 14 and R 15 are each hydrogen, unsubstituted or hydroxyl-substituted C 1 -C 6 -alkyl, or an unsubstituted or substituted aralkyl or aryl group, or R 14 and R 15 , together with the nitrogen atom to which they are bonded, form a heterocyclic radical, R 9 and R 10 are each hydrogen, C 1 -C 4 -alkyl, C 1 -C 6 - alkanoyl or unsubstituted or substituted benzoyl or R 9 and R 10 , together with the nitrogen atom to which they are bonded, form a heterocyclic radical, R" is hydrogen, halogen, C 1 -C 4 -alkyl or a radical NR 14 R 15 or -OR 13 (where R 13 , R 14 and R 15 have the above meanings) and R 12 is hydrogen or methyl, and, where relevant, its physiologically tolerated salts, wherein a) where R 6 is cyano, a stilbene of the formula II where R 1 , R 2 , R 3 , R 4 , R 5 and A have the above meanings, is halogenated and 2 moles of hydrogen halide are then eliminated, or b) where R 6 is hydrogen, carboxyl, nitrile or formyl, an a-chlorobenzylphosphonate of the formula III where R 1 , R 2 , R 3 , R 4 , R 5 and A have the above meanings, and R 21 is C 1 -C 3 -alkyl, is reacted with an aldehyde of the formula IV or c) where R 6 is methyl, nitrile or 1,3-dioxolan-2-yl, an a-chlorobenzylphosphonate of the formula V where R 21 has the above meanings, is reacted with an aldehyde of the formula VI where R 1 , R 2 , R 3 , R 4 , R 5 and A have the above meanings, or d) where R 6 has the same meanings as stated under b), a monoarylacetylene of the formula VII where R 1 , R 2 , R 3 , R 4 , R 5 and A have the above meanings, is reacted with an aryl halide of the formula VIII in the presence of a catalyst and of a base, and, if desired, the resulting compound is converted to a further compound of the formula I by a standard method.