Patent GB-663440-A (GB)
Title: Bis acetone compounds and carbocyanine dyes made therefrom
IPC: C09B23/06
Filed: 1949-09-03
Abstract: Dyes of the general formula <FORM:0663440/IV (c)/1> p  wherein Z and Z1 each represent the nonmetallic atoms to complete a heterocyclic nucleus containing 5 or 6 atoms in the heterocyclic ring, Q is O, S, or Se, d and n each represent 0 or 1, R2 and R3 each represent H or alkyl, and R and R1 are alkyl or, when Z or Z1 or both complete a heterocyclic nucleus of the thiazole, benzthiazole, thiazoline, or 3 : 3-dialkylindolenine series, R or R1 or both may be aryl, are prepared by reacting compounds of the general formula <FORM:0663440/IV (c)/2> wherein R4 is alkyl, Q1 is S or Se, and X is an anion, with a metal oxide, hydroxide, sulphide, hydrosulphide, selenide, or hydroselenide.  The metal compound may be a sodium, potassium, calcium, strontium, or barium compound.  Bis-(3 - ethyl - 2 - benzthiazolylidene) - thioacetone is prepared by refluxing together 3 : 31-diethyl-9 - methylmercaptothiacarbocyanine iodide, ethyl alcohol, sodium sulphide, and water.  Bis - (3 - ethyl - 2 - benzthiazolylidene) - selenoacetone, bis - (3 - ethyl - 2 - benzthiazolylidene)-acetone, 1 - (1 - ethyl - 2 - b  - naphthathiazolylidene) - 3 - (1 - ethyl - 2 - quinolylidene) - thioacetone, 1 - (3 - ethyl - 2 - benthiazolylidene) - 3-(1 - ethyl - 6 - methoxy - 2 - quinolylidene) - thioacetone, bis - (3 - ethyl - 2 - d - naphthathiazolylidene) - thioacetone, 1 - (3 - ethyl - 2 - benzselenazolylidene) - 3 - (3 - ethyl - 2 - benzthiazolylidene)-thioacetone, 1 - (5 - chloro - 3 - ethyl - 2 - benzthiazolylidene) - 3 - (3 - methyl - 2 - benzoxazolylidene) - thioacetone, 1 - (5 - chloro - 3 - ethyl - 2-benzthiazolylidene) - 3 - methyl - 3 - (3 - methyl-2 - benzthiazolylidene) - thioacetone, bis - (3-ethyl - 2 - benzthiazolylidene) - thioacetone, bis-(3 - ethyl - 2 - benzthiazolylidene) - acetone, 1-(5 - chloro - 3 - ethyl - 2 - benzthiazolylidene) - 3-(3 - methyl - 2 - benzoxazolylidene) - acetone, and 1 - (3 - ethyl - 2 - benzthiazolylidene) - 3 - (3 : 4-trimethylene - 2 - benzthiazolylidene) - selenoacetone are similarly prepared.  The bis-acetone dyes may be condensed with a compound XR5, wherein X is an anion and R5 an organic radical, to give carbocyanine dyes meso-substituted by -OR5, -SR5, or -SeR5 groups.  The compound XR5 may be an alkyl halide, sulphate, benzenesulphonate, or p-toluenesulphonate, including n-decyl bromide, lauryl bromide, and cetyl bromide, b  - hydroxyethyl bromide, g  - hydroxypropyl bromide, b -methoxyethyl bromide, b -ethoxyethyl bromide, bromacetic acid, a - or b -bromopropionic acid, ethyl bromoacetate, ethyl b -iodopropionate, 2 - chloroquinoline, 2 - chlorobenzthiazole, 4 - chloroquinoline, 2 - chloropyridine, or 2 : 4-dinitrochlorobenzene.  3 : 31-Diethyl - 9 - ethylselenylthiacarbocyanine iodide is prepared by heating together bis-(3-ethyl-2-benzthiazolylidene) - selenoacetone and ethyl p-toluenesulphonate, and treating the product with hot aqueous KI.  3 : 31-Diethyl-9-methylselenylthiacarbocyanine iodide, 9 - carbethoxymethylmercapto - 3 : 31 - diethylthiacarbocyanine iodide, 9 - b  - carboxyethylmercapto - 3 : 31-diethylthiacarbocyanine iodide, and 9-(2-benzthiazolyl) - mercapto - 3 : 31 - diethylthiacarbocyanine iodide are similarly prepared.  Meso-alkylmercapto carbocyanine dyes are prepared (a) by condensing, in the presence of a basic condensing agent (e.g. pyridine, triethylamine, dimethylaniline, tri-n-butylaniline, or sodium or potassium carbonate), a cyclammonium quaternary salt of the general formula <FORM:0663440/IV (c)/3> with a cyclammonium alkyl quaternary salt of the general formula <FORM:0663440/IV (c)/4> wherein R, R1, R2, R3, R4, Z, Z1, X, n, and d are as above defined; (b) by condensing a cyclammonium quaternary salt of the general formula <FORM:0663440/IV (c)/5> with a trithiocarbonate R4-S-C(=S)-S-R4; and (c) by condensing a cyclammonium quaternary salt as in (b) with a cyclammonium quaternary salt of the general formula  <FORM:0663440/IV (c)/6> 5 - Chloro - 3 - ethyl - 31 - methyl - 9 - methylmercaptothiacarbocyanine perchlorate is prepared by refluxing together 5-chloro-2-(2-methylmercaptobutenyl) - benzthiazole etho - p - toluenesulphonate and 2-methylmercaptobenzthiazole metho-p-toluenesulphonate in pyridine, and converting to the perchlorate.  Meso-alkylselenyl carbocyanine dyes are prepared by reacting a cyclammonium quaternary salt of the general formula <FORM:0663440/IV (c)/7> with a cyclammonium quaternary salt of the general formula <FORM:0663440/IV (c)/8> wherein R7 is a halogen atom or R6-Q1-, wherein R6 is an alkyl or aralkyl group and Q1 is a sulphur or selenium atom.  Specifications 533,425, 546,705, 613,458, 647,542 and 649,725, [all in Group XX], are referred to.  Reference has been directed by the Comptroller to Specification 684,088.