Patent GB-656515-A (GB)
Title: Improvements in and relating to cyanine and styryl dyestuffs or dye bases and to thepreparation thereof and to photographic emulsions containing the same
Inventor: DORMAEL ANDRE EMILE VAN
IPC: C09B23/14
Filed: 1947-04-02
Abstract: Dye intermediates are prepared by reacting a malonic ester chloride or a cyanacetic acid ester with a substituted or unsubstituted o-amino-phenol, -thiophenol, or -selenophenol or o-phenylenediamine. 2-Benzoylmethylbenzthiazole is prepared by reacting together ethyl benzoylacetate and o-aminothiophenol or by reducing o : o1-di-(benzoylacetamido)-diphenyl disulphide. Benzyl 2-benzthiazolylacetate is prepared by heating together ethyl benzyl malonate and o-aminothiophenol, or by refluxing together benzyl cyanacetate and o-aminothiophenol.  Ethyl 2-benzthiazolylacetate is prepared by heating together o-aminothiophenol and mono-ethyl malonyl chloride in CO2 atmosphere.  Benzthiazole-2-acetamide is prepared by reacting 2-carbethoxymethylbenzthiazole with ammonium hydroxide. 2-Thiocarbanilidomethylbenzthiazole is prepared by heating 2-carbanilidomethylbenzthiazole with phosphorus pentasulphide in pyridine.  Ethyl benzyl malonate is prepared by refluxing together benzyl bromide and potassium ethyl malonate in ethanol.  Benzyl cyanacetate is prepared by reacting benzyl alcohol in pyridine with cyanacetyl chloride.  2-Acetylmethyl-4-phenyloxodiazole is prepared by reacting acetoacetic ester with the oxime of benzamide. Ethyl 2-benzthiazolylpyruvate is prepared from 2-methylbenzthiazole and diethyl oxalate.  2-Benzthiazolylacetanilide is prepared by refluxing together ethyl 2-benzthiazolylacetate and aniline in xylene and pyridine.  Specification 609,033 is referred to.ALSO:<FORM:0656515/IV (c)/1> <FORM:0656515/IV (c)/2> <FORM:0656515/IV (c)/3> <FORM:0656515/IV (c)/4> <FORM:0656515/IV (c)/5> <FORM:0656515/IV (c)/6> Dye bases of the formula of Fig. 2, wherein Z represents the formula of Fig. 3 or -CH-aryl, Y and Y1 represent the atoms to complete a 5- or 6-membered heterocyclic ring, which may carry fused-on rings, L is a methine or substituted methine group, m and m1 are 0 or 1, R1 is alkyl, aralkyl, aryl, alkylene, arylene, which may be substituted, and R is alkyl, aralkyl, aryl, O-alkyl, O-aralkyl, O-aryl, COO-alkyl, COO-aralkyl, COO-aryl, NH2, or substituted NH2, or the corresponding cyclammonium salts (dyes), are prepared by reacting compounds of the formula of Fig. 4 with a cyclammonium salt containing in a - or g -position to the N-atom a reactive group (e.g. a halogen atom or thioether group) or with an aromatic aldehyde, the dyes being obtained either by quaternating the bases or by starting with the cyclammonium salts of the compounds of Fig. 4.  The dye base 2-(a -p-dimethylaminobenzal) - benzoylmethylbenzthiazole is prepared by refluxing together 2-benzoylbenzthiazole and p-dimethylaminobenzaldehyde in acetic anhydride. 2-(a -p-Dimethylaminobenzal)-acetylmethyl-4-phenyloxodiazole, 2-(a -p-dimethylaminobenzal) - ethoxyalylmethylbenzthiazole, ethyl benzthiazolyl - (2) - (p - dimethylaminobenzal) - acetate, the dye base of Fig. 25, o -benzthiazolyl-(2) : o  - p - dimethylaminobenzal - acetanilide, benzyl o  - benzthiazolyl - (2) : o  - p - dimethylaminobenzal-acetate, the dye base of Fig. 31, ethyl quinolyl - (4) - (p - dimethylaminobenzal) - acetate, and o  - benzthiazolyl - (2) : o  - p - dimethylaminobenzal-thioacetanilide are similarly prepared.  2 - (p - Dimethylamino - a  - phenylcarbamyl - styryl) - benzthiazole methiodide is prepared by heating together in a sealed tube o -benzthiazolyl - (2) : o  - p - dimethylaminobenzal - acetanilide.  Samples have been furnished under Sect. 2 (5) of ethyl benzthiazolyl-(p-methoxybenzal)-acetate, prepared by heating together in a sealed tube anisaldehyde, ethyl benzthiazolyl - 2 - acetate, and anhydrous zinc chloride, and of the dye base of Fig. 43, prepared by boiling together in absolute alcohol containing triethylamine ethyl benzthiazolyl-2-acetate and N : N1 - pentamethylene - di - (2 - methylmercaptobenzthiazole-bromide).  Specification 609,033 is referred to.