Patent GB-625245-A (GB)
Title: Improvements in and relating to the manufacture of dyestuffs their use for sensitizing photographic silver halide emulsions
IPC: C07D215/26
Filed: 1940-03-05
Abstract: Quaternary cyclammonium salts of the formula <FORM:0625245/IV (b)/1> wherein V, X and Y are H or an organic group (e.g. aryl, alkoxy or alkyl), or V and X taken together are phenylene, or X and Y taken together are phenylene, R is alkyl or substituted alkyl, R1 is halogen, Z is O or S, and wherein the CH2 groups may be substituted, are prepared by heating together an aliphatic or substituted aliphatic carboxylic acid halide and a 1 : 2 : 3 : 4 - tetrahydro - 8 - hydroxy- (or 8 - mercapto-) quinoline of formula <FORM:0625245/IV (b)/2> wherein B is OH or SH.  2-Methyl-3 : 4-trimethylenebenzoxazole chloride or bromide is prepared by heating 1 : 2 : 3 : 4 - tetrahydro - 8 - hydroxyquinoline with acetyl chloride or bromide in a sealed tube.  2-Methyl-3 : 4-trimethylenebenzthiazole chloride or bromide is similarly prepared.  Substituted compounds are obtained by using tetrahydroquinaldine, b -naphtho-tetrahydroquinoline, and thallin. Quaternary cyclammonium salts of the above formula, where Z is S, are prepared by oxidizing with a halogen (e.g. bromine) a N-thioacyltetrahydroquinoline of formula <FORM:0625245/IV (b)/3> wherein A is thioacyl.  2 - Methyl - 3 : 4 - trimethylenebenzthiazole bromide is prepared by oxidizing thioacetyl-1 : 2 : 3 : 4-tetrahydroquinoline with bromine in chloroform.  N-Thioacetyl-1 : 2 : 3 : 4-tetrahydroquinoline is prepared by boiling N-acetyl-1 : 2 : 3 : 4-tetrahydroquinoline in toluene with phosphorus pentasulphide. Compounds of formula <FORM:0625245/IV (b)/4> wherein R is H, alkyl, substituted alkyl, or aryl, R1 is alkyl, substituted alkyl, or aryl, Q is O or S, and wherein the CH2 groups may be substituted are prepared by reacting a cyclammonium salt of the formula given previously with an acyl halide, or with an acyl halide in presence of P2S5 as in Specification 592,482, and the products may be reacted with esters such as dimethyl sulphate, methyl bromide, or benzyl bromide as in Specification 592,483.  Intermediates of the formula <FORM:0625245/IV (b)/5> wherein R is H, alkyl, substituted alkyl, or aryl, R1 is alkyl or substituted alkyl, and wherein the CH2 groups may be substituted are prepared by reacting the cyclammonium quaternary salts with an alkyl ester of an arylthioimido acid of formula  <FORM:0625245/IV (b)/6> Intermediates may also be prepared by reacting the cyclammonium salts with diphenylformamidine.  2 - b - Anilinovinyl - 3 : 4-trimethylenebenzthiazole bromide is prepared by reacting 2 - methyl - 3 : 4 - trimethylenebenzthiazole bromide with diphenylformamidine.  2 - Methyl - 3 : 4 - (a  - methyltrimethylene)-benzthiazole bromide is prepared by acetylating N-acetyl-2-methyl-1 : 2 : 3 : 4-tetrahydroquinoline, reacting with P2S5 to obtain N-thioacetyl-2 - methyl - 1 : 2 : 3 : 4 - tetrahydroquinoline, and oxidizing with a solution of bromine in chloroform. Specification 412,309 also is referred to.ALSO:2 - b  - Anilinovinyl - 3 : 4 - trimethylenebenzthiazole bromide is prepared by reacting 2-methyl - 3 : 4 - methylenebenzthiazole bromide with diphenylformamidine.  Cyanine, merocyanine and styryl dyes are prepared in the usual manner from quaternary cyclammonium salts of the formula <FORM:0625245/IV (c)/1> wherein V, X and Y are H or an organic group (e.g. aryl, alkoxy or alkyl), or V and X taken together are phenylene, or X and Y taken together are phenylene, R is alkyl or substituted alkyl, R1 is halogen, Z is O or S, and wherein the CH2 groups may be substituted, from compounds derived from the corresponding bases by replacing R by a =CR1-CH2 =Q group, wherein R1 is H, alkyl, substituted alkyl, or aryl, R2 is alkyl, substituted alkyl or aryl, and Q is O or S, from compounds wherein R is replaced by a -CR1 = CR3-S- alkyl group, wherein R1 is as before, and R3 is alkyl or substituted alkyl, or from the anilinovinyl derivatives obtained by reacting the quaternary cyclammonium salts with diphenylformamidine.  3 : 4 : 31 : 41-Di-(trimethylene)-oxacarbocyanine iodide is prepared by boiling together 2-methyl-3 : 4 - trimethylenebenzoxazole chloride or bromide with acetic anhydride and ethyl orthoformate, and treating with aqueous KI. 3 : 4 : 31 : 41\h - Di-(trimethylene)-thiacarbocyanine bromide, 9-methy)- and 9-ethyl-3 : 4 : 31 : 41-di-(trimethylene) - thiacarbocyanine bromide and 3 : 4 : 31 : 41 - di - (trimethylene) - 6 : 61-dimethoxythiacarbocyanine bromide are similarly prepared. 31-Ethyl-3 : 4-trimethyleneoxathiazolino-carbocyanine iodide is prepared by boiling together 2-methyl-3 : 4-trimethylenebenzoxazole chloride or bromide, 2-b -anilinovinylthiazoline ethiodide, acetic anhydride and anhydrous sodium acetate, and treating with aqueous KI. 1 - Ethyl - 6 - methoxy - 31 : 41 - trimethylenequinothiapseudocyanine bromide is prepared by heating together 2-methyl-3 : 4-trimethylenebenzthiazole bromide, 2-ethylmercapto-6-meth oxyquinoline ethobromide, alcohol and triethylamine.  3-Ethyl-31 : 41-trimethylenethiapseudocyanine bromide is similarly prepared.  2-p-Dimethylaminostyryl - 3 : 4 - trimethylenebenzthiazole bromide is prepared by boiling together 2 - methyl - 3 : 4 - trimethylenebenzthiazole bromide, p-dimethylaminobenzaldehyde, alcohol and piperidine.  3 : 4-Trimethylene-31-methyl-41 : 51-benz-9-ethylthiacarbocyanine iodide is prepared by boiling together 3 : 4-trimethylenebenzthiazole bromide or chloride, a compound of formula <FORM:0625245/IV (c)/2> alcohol and triethylamine, and treating with aqueous KI.  3 : 4 - Trimethylene - 31 - methyl-9-ethylthiacarbocyanine iodide and 3-methyl-31 : 41-trimethylene - 9 - ethylselenathiacarbocyanine iodide are similarly prepared.  3 : 4 : 31 : 41-Di-(trimethylene) - thiatricarbocyanine iodide is prepared by reacting together 3 : 4-trimethylenebenzthiazole bromide or chloride, glutacondianilide hydrochloride, pyridine and piperidine, and treating with aqueous KI. 5-(3 : 4-Trimethylenebenzthiazolylidene-ethylidene)-rhodanine is prepared by boiling together 2-(b -anilinovinyl)-3 : 4-trimethylbenzthiazole bromide, rhodanine and acetic anhydride. Samples have been furnished under Sect. 2(5) of (a) 3 : 4 : 31 : 41 - di - (a  - methyltrimethyl 9-ethylthiacarbocyanine iodide, (b) 1-ethyl-31 : 41-(a  - methyltrimethylene) - quinothiapseudocyanine iodide, and (c) 3-ethyl-31 : 41-(a -methyltrimethylene)-thiapseudocyanine bromide. Specifications 412,309, 592,482 and 592,483 are referred to.