Patent GB-975932-A (GB)
Title: Improvements in or relating to the production of colour photographic images
Inventor: WILLEMS JOZEF FRANS
IPC: C07D217/22
Filed: 1959-11-13
Abstract: Sulphonyl hydrazones of one of the following formulae <FORM:0975932/C1/1> , <FORM:0975932/C1/2> , <FORM:0975932/C1/3> wherein Y and Z are the non-metallic atoms required to complete a heterocyclic ring, X1 is alkyl or substituted phenyl, R2 is alkyl sulphonyl, R3 and R4 are alkyl, allyl, or phenyl and R5 is phenyl, substituted phenyl, benzyl or a heterocyclic radical are prepared by heating a sulphonyl hydrazide with a methyl mercapto cycloammonium salt or by refluxing a sulphonyl chloride with an unsubstituted hydrazone. Sulphonyl hydrazones prepared include those wherein X1 is cetyl, or 4-carboxyphenyl-4-methylphenyl or 3-decanoyl-amino-phenyl, R3 and R4 are methyl or ethyl, R5 is phenyl, thienyl or alkoxy- or chloro-phenyl, Z completes a thiazoline, benzothiazoline, benzoxazoline, quinoline or benzimidazoline ring and Y completes a piperazine or morpholine ring.  N;N1 - dimethyl - N;N1-diphenyl-N1 -aminoguanidine is prepared by heating N,N1-dimethyl-N,N1-diphenyl-S-methyl-isothiouranium iodide with hydrazine hydrate.  N11, N11, N111, N111-diethylene - di (N-n-hexadecylsulphonylbenzamidrazone) is prepared by refluxing N:N-dibenzoyl piperazine with phosphorus pentasulphide to give N:N-dibenzothiopiperazide which is reacted with methyl iodide to give the salt.  The salt is reacted with n-hexadecylsulphonylhydroxide to produce the desired compound.  3-methyl-2-benzothiazolone semicarbazone is prepared by refluxing semicarbazide hydrochloride with 2-methyl-thio-3-methylbenzothiazolium methylsulphate under alkaline conditions.  1-phenyl-3-N-carbethoxythioureido-5-pyrazolone is prepared by refluxing 1-phenyl-3-amino-5-pyrazolone with carbethoxyisothiocyanate.  p-Hexadecyloxyacetophenone is prepared by refluxing p-hydroxy acetophenone with hexadecylbromide in caustic potash.  p-Hexadecylphenacylbromide is prepared by heating the acetophenone with bromine.  1-Phenyl-3-\sT 31-carbethoxy-41-(411-hexadecyloxyphenyl) -thiazolylidene-21\sV-amino-5-pyrazolone is prepared by refluxing p-hexadecylphenacylbromide with 1-phenyl-3-N-carbethoxythioureido -5-pyrazolone.  N - ethyl - benzothiazolone - (m - nitrophenyl)-sulphonyl hydrazone is produced by refluxing N-ethyl-benzothiazolone with m-nitrobenzene sulphochloride.  The amino compound is prepared by reduction with iron filings.  Cetyl sulphonyl hydrazide is prepared by adding hydrazine hydrate to cetyl sulphonyl chloride.  4 - (alpha - methylthiothienylidene) - morpholinium iodide is prepared by heating sulphur, 2-thiophene-2-aldehyde and morpholine to produce 4-(thiothienoyl)-morpholine which on refluxing with methyl iodide gives the desired product.  1-a -methylthio-3-methoxy -4- n - hexadecyloxybenzylidene-piperidinium iodide is prepared by refluxing sodium, 3-methoxy-4-hydroxybenzaldehyde and n-hexadecylbromide to give 3-methoxy-4-n-hexadecyloxybenzaldehyde. This aldehyde is heated with sulphur and piperidine to give 3-methoxy-4-n-hexadecyloxy-benzothiopiperide which is reacted with methyl iodide to give the piperidinium iodide. 3-methoxy-4-hydroxy-benzothiopiperidide is produced by heating sulphur, piperidine and 3-methoxy-4-hydroxy benzaldehyde.  The iodide is prepared as above.  4-methoxybenzothiomorpholide is prepared by heating sulphur, morpholine and p-methoxybenzaldehyde.  2, 4-dichlorobenzothiomorpholide is prepared by adding 2, 4-dichlorobenzoylchloride to morpholine in alkaline solution to obtain 2, 4-dichlorobenzomorpholide which is refluxed with phosphorus pentasulphide to give the thiomorpholide. 2-chlorobenzothiomorpholide is prepared as above using o-chloro-benzoyl chloride.  a -methylthio -3, 4-dimethoxybenzylidene - N - methyl-N-n-hexadecyl-ammonium iodide is prepared by adding 3, 4-dimethoxybenzoylchloride to N-methyl-N-n-hexadecylamine in alkali to give 3, 4-dimethoxy-benzoic acid-N-methyl-N-n-hexadecylamide. This is reacted with phosphorus pentasulphide to give 3, 4-dimethoxy-benzothio-N-methyl-N-n-hexadecylamide which is quaternized with methyl iodide.  a -methylthio -4- methoxybenzylidene-N-methyl-N-n-hexadecyl ammonium iodide is prepared as above using p-methoxybenzoylchloride instead of 3, 4-dimethoxybenzoyl chloride.  a -methylthiobenzylidene-N-allylanilinium iodide is prepared by refluxing N-allylaniline with benzoylchloride to give N-aleylbenzanilide.  This anilide is reacted with phosphorus pentasulphide to give N-allyl-benzothioanilide which is quaternized with methyliodide.  4-Carboxybenzene sulphonylhydrazide is prepared from hydrazine and 4-carboxybenzene sulphonyl chloride. Specifications 502,665, 880,862, 975,930, 975,939 and 975,940 are referred to.