Patent GB-1019117-A (GB)
Title: New thiophene compounds and their use as colour couplers for magenta dyestuffs
IPC: C07D333/36
Filed: 1964-01-20
Abstract: Dodecylbenzene and dodecyldiphenyl are prepared from lauroyl benzene and lauroyl diphenyl respectively by reduction with hydrazine hydrate.ALSO:The invention comprises thiophene or condensed ring thiophene compounds in which the thiophene ring is substituted by two cyanoacetyl groups.  The compounds are formed by reacting corresponding thiophene dicarboxylic acid diesters with an excess of acetonitrile in the presence of a condensing agent.  The examples describe the preparation of 2,5-di(cyanoacetyl)-3 - phenyl - 4 - para - dodecylphenyl - thiophene, 2,5 - di - (cyanoacetyl) - 3 - phenyl - 4 - para - dodecyldiphenyl - thiophene, 2,5 - di - (cyanoacetyl) - 3 - alpha - naphthyl - 4 - para - diphenyl - thiophene, 2,5 - di - (cyanoacetyl) - 3 - phenyl - 4 - para - terphenylyl - thiophene, 2,5 - di - (cyanoacetyl) - 3 - alpha - naphthyl - 4 - para - dodecyldiphenylyl - thiophene, 2 - methylmercapto - 3,5 - di - (cyanoacetyl) - 4 - lauroyl-amino - thiophene, 2,5 - di - (cyanoacetyl) - 3,4 -phenanthreno - (91,101) - thiophene and 2,5 - di - (cyanoacetyl) - 3,4 - diphenyl - thiophene.  Thiophene dicarboxylic acid and thiophene dicarboxylic acid dimethyl diester intermediates from which the products of the first five examples are obtained are prepared by reacting thiodiglycollic acid ethyl ester respectively with phenyl - dodecylphenyl - diketone, phenyl - dodecyldiphenylyl - diketone, alpha - naphthyl - diphenylyl - diketone, phenyl - terphenylyl - diketone and alpha - naphthyl - dodecyldiphenylyl-diketone, followed by esterification with methanol and hydrogen chloride.  3,4 - Phenanthreno - (91,101) - thiophene 2,5 - dicarboxylic acid dimethyl ester and 3,4-diphenylthiophene - 2,5 - dicarboxylic acid dimethyl ester are prepared by esterifying the corresponding dicarboxylic acids with methanol and hydrogen chloride. 2 - Cyano - 2 - mercapto - 2 - methylmercapto - acetic acid ethyl ester is prepared by reacting carbon disulphide with cyanoacetic ester in presence of sodium methylate to give a sodium salt which is then reacted with dimethyl sulphate.  2 - Methylmercapto - 4 - aminothiophene - 3,5 - dicarboxylic acid diethyl ester is prepared by reacting 2 - cyano - 2 - mercapto - 2 - methylmercapto-acetic acid ethyl ester with sodium methoxide and then ethyl bromoacetate.  2 - Methylmercapto - 4 - lauroylamino - thiophene - 3,5 - dicarboxylic acid diethyl ester is prepared by reacting the corresponding amine with lauroyl chloride.  Phenacetyl - dodecylbenzene, phenacetyl - dodecyldiphenyl, a  - naphthacetyl - diphenyl, phenacetyl - terphenyl and a  - naphthacetyl - dodecyldiphenyl are prepared by reacting phenacetyl chloride or naphthacetyl chloride with dodecylbenzene, dodecyl-diphenyl, diphenyl or terphenyl in presence of aluminium chloride.  Phenyl - dodecylphenylyl - diketone, phenyl - dodecyldiphenylyl - diketone, a  - naphthyl - diphenylyl - diketone, phenyl - terphenylyl - diketone and a  - naphthyl - dodecyldiphenylyl - diketone are prepared by selenium dioxide oxidation of phenacetyl - dodecylbenzene, phenacetyl - dodecyldiphenyl, a  - naphthacetyl - diphenyl, phenacetyl - terphenyl and a  - naphthacetyl - dodecyldiphenyl respectively.  Dodecyl - diphenylylmethyl - diketone, dodecylphenylmethyl - diketone, dodecylphenyl - naphthyl - diketone and diphenylyl - diphenylyl - diketone are prepared similarly.