Patent GB-549202-A (GB)
Title: Improvements in or relating to dyestuffs and dyestuff intermediates
IPC: C09B23/12
Filed: 1941-04-07
Abstract: 549,202. Cyanine dyes. KENDALL, J. D. April 7, 1941, No. 4602. Samples furnished. [Class 2 (iii)] [Also in Group XX] Cyanine dyes are produced by condensing a compound of the general formula where Rand R 2  are alkyl or aralkyl groups, R 1  is a hydrogen atom or an alkyl group, D 1  is the residue of a heterocyclic nitrogen compound, X is an acid residue, and n is 0 or 1, with (a) a five-membered ring compound of formula where D 2  is the residue of a heterocyclic nitrogen keto-methylene compound and R 3  is hydrogen or a hydrocarbon group ; or (b) with an alkyl or aralkyl quaternary salt of a heterocyclic nitrogen compound containing in the α or y position to the quaternary nitrogen atom a reactive methyl, monosubstituted methyl, external methylene, amino, or imino group ; or (c) with an alkyl or aralkyl quaternary salt of a compound of the general formula wherein A is the residue,of a thiazole, oxazole, or selenazole nucleus (including the benz and benzbenz compounds of this type) or of a thiazoline, oxazoline, or selenazoline nucleus, R 6 , R 7 , and R 8  are hydrogen atoms or hydrocarbon groups, and m. is a positive integer greater than 1 (X being an oxygen, sulphur, or selenium atom) ; or (d) a five-membered ring compound of formula wherein D  2  is the residue of a heterocyclic nitrogen keto-methylene compound and R 3  and R 9  are hydrogen atoms or hydrocarbon groups. After further condensation with a compound of type (a) conforming to the general formula (R 3  being a hydrogen atom or a hydrocarbon group and X being an oxygen or sulphur atom), the dye obtained may be treated with an alkyl or aralkyl salt and thereafter further condensed with a compound of any of the types (a) to (d). The condensation may be repeated as often as desired. Hydrocarbon groups may be alkyl (methyl, ethyl, propyl, butyl, and higher alkyl), aryl (phenyl and naphthyl), aralkyl (benzyl and naphthylmethyl), or unsaturated groups such as allyl or cinnamyl. Aryl residues therein may be substituted with alkyl, aralkyl, hydroxyalkyl, alkyloxy, amino, or hydroxy groups or by halogen atoms. Compounds of type (a) are rhodanic acid and N-hydrocarbon substituted rhodanic acids, 2-thio-4-keto-tetrahydro-oxazole and N-hydrocarbon substituted derivatives, oxindoles, 5-pyrazolones, hydantoin, thiohydantoin, pseudo-hydantoin, and pseudo-thiohydantoin. Compounds of type (b) are thiazoles, oxazoles, selenazoles and their polycyclic homologues such as those of the benzene, naphthalene, acenaphthene, and anthracene series ; pyridine and its polycyclic homologues such as quinoline and α- and #- naphthaquinolines ; lepidines ; indolenines; diazines such as thio-##<SP>1</SP>-diazole; oxazolines, thiazolines, and selenazolines. The polycyclic compounds may also be substituted in the carbocyclic rings with one or more groups such as alkyl, aryl, amino, hydroxy, alkoxy, or methylene-dioxy groups or halogen atoms. Compounds of type (c) are described in Specification 546,565 and compounds of type (d) in Specification 513,596. The dyes may be obtained by heating the reagents together, preferably in the presence of a solvent and a base, such as pyridine, piperidine, diethylamine, triethylamine, triethanolamine, or a solution of sodium or sodium acetate in ethyl alcohol. The conversion of the heterocyclic nitrogen base to the quaternary salt by treatment with an alkyl or aralkyl salt may be effected simultaneously with the formation of the dye. The dyes may' be obtained by fusing together a compound of the type described in Specification 549,204, a heterocyclic nitrogen compound containing an external reactive methyl group in the α or γ position to the heterocyclic nitrogen atom, and an alkyl sulphate or alkyl p-toluenesulphonate. In an example, a dye is prepared by boiling together N-ethylrhodanic acid, #-1-bismethylthio-vinyl-benzthiazole ethiodide, and absolute alcohol. Triethylamine is added and the mixture further boiled. Pyridine is added and the dye precipitates. Dyes are obtained similarly from lepidine methiodide, 1-methyl-4-chlorbenzthiazole, ethiodide, p-toluquinaldine methiodide, quinaldine methiodide, 1-methylbenzthiazole ethiodide, #<SP>1</SP>-cyclohexenylbenzthiazole, N- methyloxindole, 1:4-dimenthylbenzthiazole, 2- methyl-#-naphthathiazole, 1-methylbenzoxazole, 1-aminobenzthiazole, and 1-phenyl-3- methyl-4-isopropylidene-5-pyrazolone. The dyes may be used for sensitizing silver chloride, bromide, chlorobromide, and iodobromide emulsions. The dye intermediates are prepared by reacting a compound having the general formula with a compound of the formula R 2 X, where R and R 2  are alkyl or aralkyl groups, R 1  is a hydrogen atom or an alkyl group, D 1  is the residue of a heterocyclic nitrogen compound, X is an acid residue, and n is 0 or 1. #-1-bis-methylthio-vinyl-benzthiazole ethiodide is prepared by boiling a mixture of (N-ethyldihydrobenzthiazolylidene-1) - dithioacetic acid; methyl iodide, methyl alcohol, and benzene, filtering, adding methyl ioidide and methyl alcohol to the filtrate, and re-boiling. #-1-bis-methylthio-vinyl-benzthiazole methiodide is. prepared by heating a mixture of (N - methyldihydrobenzthiazolylidene - 1) - dithioacetic acid, methyl iodide, and methyl alcohol in a sealed tube. Samples have been furnished under Sect. 2 (5) of (a) 1-(#-methylthio-#-ethylthio-vinyl)- benzthiazole ethiodide prepared by fusing together 1 - ( w - methylthio - # - thiovinyl) - N - ethyldihydrobenzthiazole and ethyl p-toluenesulphonate, dissolving in ethyl alcohol and pouring into aqueous alcoholic potassium iodide ; (b) 1-(#- ,rizethylihio - w - benzylthio - vinyl) benzthiazole ethiodide prepared by fusing together 1-(#- methylthio - # - thio -vinyl)-N-ethyldihydrobenzthiazole and benzyl chloride, dissolving in ethyl alcohol, and pouring into aqueous alcoholic potassium iodide ; (c) 2-(#-bis-methylthiovinyl)-thiazoline methiodide prepared by fusing together 2-methylthiazoline and methyl ptoluenesulphonate, dissolving in ethyl alcohol, adding carbon disulphide and triethylamine, and warming to give (N-methyldihydrothiazoline-2)-dithioacetic acid methyl ester, and heating this compound with methyl alcohol and methyl iodide ; (d) the dye prepared by heating 1-methylbenzthiazole methyl-p-toluenesulphonate, 2 - ( # - bis - methylthio - vinyl) - thiazoline methiodide, and pyridine together and pouring the reaction solution into aqueous alcoholic potassium iodide solution ; and (e) 4-(#-bismethylthio-vinyl)-6-ethoxyquinoline methiodide prepared by fusing together 6-ethoxylepidine and methyl p-toluenesulphonate, adding dimethyl trithiocarbonate and triethylamine to the product dissolved in pyridine, and refluxing and pouring into aqueous potassium iodide to give (1-methyl-6-ethoxyquinoline-4)-dithioacetic acid methyl ester, which is then refluxed with methyl iodide. The Provisional Specification refers also to intermediates in which R 1  is an aryl or aralkyl group, and to dyes produced by condensing the intermediates with (a) compounds containing the grouping wherein R 1 , R  2 , and R  3  may be alkyl, aryl or aralkyl groups, or R 1  and R 2  may be part of the same arylene ring ; (b) carbocyclic compounds containing a ketomethylene group ; (c) acids or esters of the type COOR-CH 2 - (CX=CH) n -COOR, where X is hydrogen or a monovalent substituent, R is hydrogen or an alkyl or similar group, and n is O or 1 ; (d) anhydrides of acids of the general formula CH 3 -(CX) 2n -1=CH-COOH, where X is H or a monovalent group, and n is 1 or 2 ; and (e) ammonia or amidines or hydrazines or diamines or their salts. Compounds referred to are cyclopentadiene, indene, 1:3-indane-dione, hydrindones malonic acid, glutaconic acid, crotonic anhydride, ammonium nitrate, hydrazines and substituted hydrazines. Specifications 426,718 and 549,201 also are referred to.