Patent GB-606141-A (GB)
Title: Photographic silver salt emulsions containing dyes and processes of producing such dyes
IPC: G03C1/22
Filed: 1945-11-19
Abstract: <PICT:0606141/IV(b)/1> <PICT:0606141/IV(b)/2> Merocyanine dyes of the general formula shown in Fig. 1, wherein R and R1 are unsubstituted or substituted alkyl or aryl groups, L is an unsubstituted or substituted methine group, n is 0 or 1, m and d are 0, 1, or 2, Q is 0, S or NR11 (R11 being an unsubstituted or substituted alkyl or aryl group), Z represents the non-metallic atoms to complete a 5- or 6-membered heterocyclic nucleus, and Z1 represents the non-metallic atoms to complete a 5-membered ring containing at least one sulphonic acid and/or carboxylic acid group are prepared by condensing with a 5-membered heterocyclic compound containing a reactive methylene group adjacent to a ketonic carbony group and also at least one SO3H and/or COOH group, (a) in the case where m and d are both 0, a cyclammonium quaternary salt containing in the a - or g -position to the quaternary N atom a thioether group or halogen atom, or a quinoline quaternary salt unsubstituted in the 4-position; (b) in the case where m is 1 and d 0, a cyclammonium quaternary salt containing in the a - or g -position a b -arylaminovinyl or b -acylarylamino vinyl group, or a mixture of a cyclammonium quaternary salt containing in the a - or g -position a -CH2-R4 group (R4 is H, alkyl, alkoxy or aryloxy) and an orthoester of a carboxylic acid, or, where the dimethine chain is a -substituted, a cyclammonium quaternary salt containing in the a - or g -position a b -alkyl- (or b -aryl-) -b -alkylmercaptovinyl group; (c) in the case where m is 2 and d 0, a cyclammonium quaternary salt containing in the a - or g -position a 4-arylamino-1 : 3-butadienyl group, or (d) in the case where d is 1 or 2, a quaternary alkylmercapto compound obtained by treating a merocyanine dye of the formula shown in Fig. 5, wherein R, R1, L, n, m, Q and Z have the meanings previously given and d is 1 or 2 with an alkyl salt.  4-(3-Ethyl-2-benzthiazolylidene) - 3 - methyl - 1 - (p - sulphophenyl) - 5 - pyrazolone is prepared by refluxing together 2-phenylmercaptobenzthiazole ethiodide, 3-methyl-1-(p-sulphophenyl)-5-pyrazolone and triethylamine in ethyl alcohol. 3-(p-Carboxyphenyl)-5-(3-methyl-2-benzoxazolylidene)-rhodanine is similarly prepared.  4 - [(5 - Chloro - 3 - ethyl - 2 - benzthiazolylidene) - ethylidene] - 3 - methyl - 1 - (p - sulphophenyl) - 5 - pyrazolone is prepared by heating together 2-(b -acetanilidovinyl) - 5 - chlorobenzthiazole ethio - dide, 3-methyl - 1 - (p-sulphophenyl)-5-pyrazolone, triethylamine and ethyl alcohol. The corresponding 3-ethyl-5-phenyl-2-benzoxazolylidene, 1-ethyl-2-b -naphthathiazolylidene, 1 : 3 : 3-trimethyl-2-indolylidene, 1-ethyl-2-quinolylidene, 1 : 6-dimethyl-2-quinolylidene, 1-ethyl-4-quinolylidene, 3 - ethyl - 4 - methyl - 2 - thiazolylidene), and 3-methyl-2-thiazolinylidene derivatives and 1-(p-carboxyphenyl)-4-((3-ethyl-2-benzthiazolylidene)-ethylidene) -3-methyl-5-pyrazolone are similarly prepared.  3 - (p - Carboxyphenyl) - 5 - [(3 - ethyl - 2 - benzthia - zolylidene)-ethylidene]-rhodanine is prepared by refluxing together 2-(b -acetanididovinyl)-benzthiazole ethiodide, 3-(p-carboxyphenyl)-rhodanine, triethylamine, and ethyl alcohol. The corresponding 3 - ethyl - 2 - benzoxazolylidene, 3 - carboxy - 4 - hydroxyphenyl and 2 : 5-disulphophenyl derivatives and 5 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene] - 3 - (p - sulphophenyl) - rhodanine, 5 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene] - 3 - (p - sulphophenyl) - 2 - thio - 2 : 4 - oxazoledione, 4 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene]-3-carboxymethyl-1-phenyl-5-pyrazolone, and 4 - [(1 : 3 : 3 - trimethylindolylidene) - ethylidene]-3-carboxymethyl-1-phenyl-5-pyrazolone are similarly prepared.  3-Carboxymethyl-5-(3-ethyl-2-benzthiazolylidene)-rhodanine is prepared by the reaction of 2-ethylmercaptobenzthiazole ethiodide, 3-carboxymethylrhodanine, methyl alcohol and triethylamine.  The 3-b -sulphoethyl- and 1-n-4-quinolylidene derivatives and the corresponding benzselenazolylidene derivative are similarly prepared. 3-Carboxymethyl-5-[(3-methyl-2-thiazolylidene) -ethylidene]-2-thio-2 : 4-oxazoledione is prepared by refluxing together 2-b -anilinovinyl thiazole methiodide, 3 - carboxymethyl - 2 - thio - 2 : 4 - oxazoledione, ethyl alcohol and triethylamine.  3 - b  - Carboxyethyl - 5 - [(3 - ethyl - 2 - benzoxazolylidene)-ethylidene]-rhodanine and the corresponding a  - carboxyethyl : benzthiazolylidene, carboxy - methyl : benzthiazolylidene, carboxymethyl: benzoxazolylidene and b -sulphoethyl: benzoxazolylidene derivatives and 5-[(3-ethyl-2-benzoxazolylidene)-ethylidene]-3-sulphomethyl- and -3-b -sulphoethyl - 2 - thio - 2 : 4 - oxazole dione and 1 - carboxymethyl - 5 - [(3 - ethyl - 2 - benzoazolylidene) - ethylidene] - 3 - phenyl - 2 - thiohydantoin are similarly prepared.  4 - [(5 - Chloro - 3 - ethyl - 2 - benzthiazolylidene) - a  - ethylethylidene] - 3 - methyl - 1 - (p-sulphophenyl) - 5 - pyrazolone is prepared by heating together 5 - chloro - 3 - ethyl - 2 - thiopropionylmethylene - benzthiazoline and methyl p-toluenesulphonate, adding 3-methyl-1-(p-sulphophenyl)-5-pyrazolone, ethyl alcohol and triethylamine, and refluxing.  The corresponding 1-ethyl-2-b -naphthathiazolylidene - a  - phenylethylidene derivative, 1-(p-carboxyphenyl)-4-[(3-ethyl-2-benzthiazolylidene) -isopropylidene]-3-methyl-5-pyrazolone and the corresponding 1-p-sulphophenyl derivative, 4 - [(1 - ethyl - 2 - b  - naphthathiazolylidene) - isopropylidene]-3-methyl-1-(p-sulphophenyl)-5-pyrazolone, 5 - [(3 - ethyl - 2 - benzthiazolylidene) - isopropylidene]-3-(p-sulphophenyl)-rhodanine and the corresponding b -sulphoethyl derivative and 3-(b -sulphoethyl) and 3-carboxymethyl derivatives from 2-thio-2 : 4-oxazoledione, 1-carboxymethyl-5-[(3-ethyl-2-benzoxazolylidene) -ethylidene]-3-phenyl-2-thiohydantoin are similarly prepared.  4-[(3 - Ethyl-2-benzthiazolylidene) - 2 - butenylidene] - 3-methyl-1-(p-sulphophenyl)-5-pyrazolone is prepared by refluxing together 2-(4-acetanilido-:3-butadienyl)-benzthiazole ethiodide and 3-methyl-1-p-sulphophenyl-5-pyrazolone. 3-(p-Carboxyphenyl)-5-[(3-ethyl-2-benzoxazolylidene) -2-butenylidene]-rhodanine and the corresponding carboxymethyl derivative, and 5-[(3-ethyl-2-benzthiazolylidene) -2-butenylidene]-3-b -sulphoethylrhodanine are similarly prepared.  5 - [(3 - Methyl - 2 - thiazolinylidene) - isopro - pylidene]-3-b -sulphoethylrhodanine is prepared by refluxing together 2 - methylthiazoline methiodide, 3 - b  - sulphoethylrhodanine, ethyl alcohol, ethyl orthoacetate and triethylamine.  The corresponding 3-carboxymethyl derivative is similarly prepared.  3 - Ethyl - 5 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene]-2-[3-methyl-5-oxo-1-(p-sulphophenyl-4-(2 -pyrazolinylidene)]-4-thiazolidone is prepared by refluxing together 5 - [(3 - ethyl - 2 - benz - oxazolylidene)-ethylidene]-2-methylmercapto-4 - thiazolone etho - p - toluenesulphonate and 3-methyl-1-(p-sulphophenyl)-5-pyrazolone in pyridine.  The corresponding benzthiazolylidene derivative, 2 - [3 - (p - carboxyphenyl) - 4 - oxo - 2 - thione-5-thiazolylidylidene]-3-ethyl-5-[(3-ethyl-2 -benzoxazolylidene)-ethylidene]-4-thiazolidone and the corresponding carboxymethyl derivative and 3 - ethyl - 5 - [(3 - ethyl - 2 - benzoxazolylidene) - ethylidene]-2-(4-oxo-3-b -sulphoethyl-2-thione-5 -thiazolidylidene) - 4 - thiazolidone are similarly prepared.  Dyes containing 4-phenylthiazole, a -naphthathiazole, benzselenazole, 4-methylselenazole, 4-phenylselenazole and b -naphthaselenazole, 4-methyloxazole, 4-phenyloxazole, a - and b -naphthoxazole and 2- and 4-pyridine nuclei may be similarly obtained.  The dimethine chain of the merocarbocyanines may be substituted by a cyclopropyl group.  3 - (p-Sulphophenyl) - 2 - thio - 2 : 4-oxazoledione is prepared p  by reacting together potassium sulphanilate and acetamidocarbothiolonglycollic acid.  3-(p-Carboxyphenyl)-rhodanine is prepared by heating together sodium p-aminobenzoate and di - (carboxymethyl) trithiocarbonate. 3 - (3 - Carboxy-4-hydroxyphenyl)-rhodanine, 3-(2 : 5-disulphophenyl) - rhodanine and 3 - (p - sulpho - phenyl)-rhodanine are similarly prepared, using sodium 5-aminosalicylate, sodium 1-aminobenzene - 2 : 5 - disulphonate and sodium sulphanilate respectively. 3-Methyl-1-(4-sulpho-1-naphthyl)-5-pyrazolone is prepared by heating together 1-hydrazinonaphthalene - 4 - sulphonic acid, ethyl acetoacetate, sodium acetate and ethyl alcohol.  Di-(carboxymethyl) trithiocarbonate is prepared by refluxing together sodium sulphide, carbon disulphide and water, and adding sodium chloracetate.  3 - Sulphomethyl - 2 - thio - 2 : 4 - oxazoledione is prepared by reacting together potassium aminoethanesulphonate and acetamidocarbothiolonglycollic acid.  3-Carboxymethyl-2-thio-2 : 4-oxazoledione is prepared similarly using sodium aminoacetate.  3-a -Carboxyethylrhodanine is prepared by successively adding to a sodium hydroxide solution of a -alanine, carbon disulphide and a solution of sodium chloracetate.  3-b -Carboxyethylrhodanine, 3 - (1 : 3 - dicarboxy - n - propyl) - rhodanine, 3 - carboxymethylrhodanine and 3-b -sulphoethylrhodanine are similarly prepared, using sodium b -aminopropionate, sodium glutamate, sodium aminoacetate and sodium b -aminoethylsulphonate respectively. 1-Carbethoxymethyl-3-phenyl-2-thiohydantoin is prepared by heating together diethyl iminodiacetate and phenyl iso-thiocyanate. 1-Carboxymethyl-3-phenyl-2-thiohydantoin is prepared by hydrolysing 1-carbethoxymethyl-3-phenyl - 2 - thiohydantoin by warming with aqueous sodium hydroxide.  Specifications 489,335, 585,666, 597,329 and 599,693 are referred to.ALSO:<FORM:0606141/IV (c)/1> <FORM:0606141/IV (c)/2> Merocyanine dyes of the general formula shown in Fig. 1, wherein R and R1 are unsubstituted or substituted alkyl or aryl groups, L is an unsubstituted or substituted methine group, n is 0 or 1, m and d are 0, 1,