Patent GB-555936-A (GB)
Title: Improvements in or relating to dyestuffs
IPC: C09B23/02
Filed: 1942-03-02
Abstract: 555,936. Methine dyes. KENDALL, J. D. March 2, 1942, No. 2700. Samples furnished. [Class 2 (iii)] - Dyes are produced by condensing a compound of the general formula wherein D1 is the residue of a 5- or 6-membered heterocyclic nitrogen ring, R is H or alkyl, aryl, or aralkyl, R1 is alkyl or aralkyl, R2 is alkyl, aryl, or aralkyl, X is an acid radical, and n is 0 or 1) with a compound containing a reactive CH 2  or NH group, in the presence of a base and a solvent for the reactants. Compounds of the general formula are described in Specification 555,935 and may have substituents e.g. alkyl, aryl, amino, alkoxy, or methylene-dioxy groups or halogen atoms. The second compound may be (a) a 5-membered ring compound of general formula (where R is H or a hydrocarbon group and D is the residue of a nitrogen keto-methylene nucleus), e.g. rhodanine, N - hydrocarbon substituted rhodanines, 2 - thio - 4 - keto - tetrahydro - oxazole and N - hydrocarbon substituted derivatives, oxindoles, 5 - pyrazolones, hydantoin, thiohydantoin, # - hydantoin, and # - thiohydantoin (some of the products may be further reacted as described in Specification 489,335) ; (b) a quaternary salt of a 5- or 6- membered heterocyclic nitrogen compound having a reactive methyl, mono-substituted methyl, external methylene, amino, or imino group in the α- or γ- position to the heterocyclic quaternary nitrogen atom (e.g. thiazoles, oxazoles, selenazoles and their polycyclic homologues of the benzene, naphthalene, acenaphthene, and anthracene series, pyridine and its polycyclic homologues such as quinoline and α - and # - naphthaquinoline, lepidines, indolenines, diazines such as pyrimidines and and quinazolines, diazoles, e.g. thio - # : #<SP>1</SP> - diazole, oxazolines, thiazolines, and selenazolines); (c) a compound containing the grouping (where R 3'  R 4  and R 5  may be alkyl, aryl, or aralkyl groups, or R 3  and R 4  may be part of an arylene ring), e.g. cyclopentadiene and indene; (d) carbocyclic compounds containing a ketomethylene group, e.g. 1 : 3 - indane-dione and hydrindones; (e) acids of formula HOOC - CH  2  - (CH=CH) n  - COOH, where n is 0 or 1, e.g. malonic and glutaconic acids; (f) ammonia, amidines, hydrazines, diamines or their salts, e.g. ammonium nitrate and p - phenylenediamine; (g) quaternary salts of compounds of general formula (where R 6 , R 7 , R 8 , and R 9  are H or substituent groups of which two may form part of an aromatic fused-on nucleus, R 10 , R 11 , and R 12  are H or hydrocarbon groups, X is O, S, or Se, and n - is a positive integer greater than 1 as described in Specification 546,565; (h) compounds of general formula where R is H or a hydrocarbon group, D is the residue of a nitrogen keto-methylene group, and R 13  is H or an alkyl, aryl, or aralkyl group as described in Specification 513,596; and (i) compounds of general formula A - CH  2  - (CH =CH)n-A 1  (where A and A, are selected from the groups - CN, - COR 14 , and - COOR", R 14  being a hydrocarbon group, and n is 0 or 1),  e.g. acetylacetone, acetoacetic esters, cyanacetic esters, malonitrile, and malonic esters. The compound of the general formula produced as in Specification 555,935 need not be isolated from the reaction solution. If the latter contains acetic or propionic anhydride, the basic substance used according to the present invention should be one not reacting with the anhydride, e.g. triethylamine or sodium acetate. With an isolated compound pyridine may be used as both solvent and basic condensing agent. The compound may be used as halide, alkyl sulphate, perchlorate, or alkyl- or aralkyl-ptoluenesulphonate. In Example 1, 2 - ethyl- 2<SP>1</SP>-methyl-oxathiacarbocyanine iodide is prepared by fusing together 1 - methylbenzthiazole and methyl p-toluenesulphonate, adding acetic anhydride and ethyl trithio - orthoformate and boiling, adding 1 - methylbenzoxazole ethiodide and triethylamine and boiling, and pouring into ethyl alcohol. 2 : 6<SP>1</SP> -dimethyl - 1<SP>1</SP>- ethyl - thiaquino - 1 : 2<SP>1</SP> carbocyanide iodide, 2 - methyl - 1<SP>1</SP> - ethyl - thiaquino - 1 : 4 1-carbocyanine iodide, 2 - - methyl - dihydrobenzthiazolylidone 1: 5<SP>1</SP> - ethylidene - 3<SP>1</SP> - ethylrhodanine, 2 : 2<SP>1</SP> diethyl - thiacarbocyanine iodide, 2 : 3<SP>1</SP>- dimethyl - thiathiazolino - carbocyanine iodide, 2:2<SP>1</SP>-diethyl-oxaselenacarbocyanine iodide, 1:1<SP>1</SP>- diethyl - 2 :4<SP>1</SP>- carbocyanine iodide, 1 : 3 : 3 : 2<SP>1</SP>- tetramethyl - 6 - ethoxy - indothiacarbocyanine iodide, 2 : 1<SP>1</SP> - dimethyl - oxaquino - 1 : 2<SP>1</SP>- carbocyanine iodide, 2 : 2<SP>1</SP> - 7 - trimethyl - thiacarbocyanine iodide,- # - - (2 - methyldihydrobenzthiazolylidene) 1 : 5<SP>1</SP> - propylidene - 3<SP>1</SP> - ethylrhodanine, 1 - phenyl - 3 - - methyl - 4 - ( N - methylbenzthiazolyidene) - butadienylidene - - 5 - - pyrazolone, - 2 - (# -N - ethylbenzthiazolyzidene) - ethylidene-indanedione, # - ( N - methyldihydroquinolylidene-2) - acetaldazine hydriodide, 5 - - (3<SP>1</SP> - methylthiazolinylidene - ethylidene) 3 - - phenylrhodanine, 1 : 2<SP>1</SP> - dimethyl - 9 : 11 - trimethylene - quinothia - dicarbocyanine iodide, 1- #- diacetyl-methylene - vinyl - N- ethythdihydrobenzthiazole, 1 : : 1<SP>1</SP> dimethyl - 2 : 2<SP>1</SP>- dicarbocyanine iodide, and 1 - # - (N - methyldihydrobenzthiazolylidene)-ethylidene-indene are similarly prepared. The Provisional Specification describes also the use as the second compound of anhydrides of acids of the general formula CH. - (CR 8 )n = CH-COOH wherein R 8  is H or a monovalent grouping and n is 0 or 1 (e.g. crotonic anhydride). The intermediates used may contain hydroxy substituents.