Patent GB-906082-A (GB)
Title: Improvements in or relating to anilino alkane sulphonates and cyclammonium salts andcyanine dyes therefrom
IPC: C07D277/64
Filed: 1958-11-21
Abstract: N-alkylated compounds having the general formula <FORM:0906082/IV (b)/1> or <FORM:0906082/IV (b)/2> wherein R is hydrogen, a C1-4 alkyl group, a C1-2 alkoxy group, a mononuclear aromatic group of the benzene series, a tertiary amino group or a halogen atom, R1 is hydrogen or a C1-4 alkyl group n is 2 or 3, m is 1, 2 or 3, X is oxygen or sulphur and M is an alkali metal are prepared by reacting together a compound of the general formula <FORM:0906082/IV (b)/3> with a compound of the general formula <FORM:0906082/IV (b)/4> or <FORM:0906082/IV (b)/5> wherein Hal represents chlorine or bromine. The products of the second above general formula are obtained in the form of their hydrochloride or bromide salts unless excess of the anilino reactant is used.  Reaction is accelerated by heat and may be effected in the presence of a solvent and under an inert atmosphere. Cyclammonium compounds having the general formula <FORM:0906082/IV (b)/6> or <FORM:0906082/IV (b)/7> wherein R, R1, X, M, n and m are as above defined and X1 represents an acetate, chloride or bromide anion are prepared by reacting N-alkylated compounds as above defined, including the hydrobromide and hydrochloride salts of the second class of the N-alkylated compounds, with acetic anhydride or acetyl chloride.  The sulpho-betaine type products may be reacted with an alkali metal halide e.g. sodium iodide, yielding a non-betaine type quaternary salt.  The cyclammonium compounds may be converted into cyanine dyes (see Group IV(c)).  In Examples: (1) 2-methyl-3 - (4 - sulphobutyl)benzothiazolium iodide, sodium salt, is prepared by reacting o-aminothiophenol with 1 : 4-butane sultone, refluxing the product with acetic anhydride, extracting the resulting cyclammonium compound with ether and converting it into the desired iodide by reaction with sodium iodide; (2) 2-methyl-3 - b  - sulphoethyl benzoxazolium bromide, sodium salt, is prepared by heating o-aminophenol with sodium b -bromoethane sulphonate and heating the reacted mixture with acetic anhydride; the quaternary compound may be converted into 2-b -acetanilidovinyl-3-b -sulphoethyl benzoxazolium bromide by reaction with diphenyl formamidine.  Other starting materials may be used wherein R represents methyl, ethyl, propyl, butyl, phenyl, chlorphenyl, tolyl, methoxyl, dimethylamino, or diethylamino and R1 may be methyl or ethyl.  Specifications 344,409, 654,683, 654,690 and 669,174 are referred to.ALSO:Carbo cyanine and mero cyanine dyes are prepared from cyclammonium compounds having the general formula <FORM:0906082/IV (b)/1> or <FORM:0906082/IV (b)/2> wherein R represents hydrogen, a C1-4 alkyl, a C1-2 alkoxy, a mono nuclear aromatic group of the benzene series, a tertiary amino group or a halogen atom, X is oxygen or sulphur, n is 2 or 3, m is 1, 2 or 3, R1 is hydrogen or a C1-4 alkyl, M is an alkali metal and X1 is an acetate, chloride or bromide ion, by a method known to be suitable for the preparation of a carbo cyanine or mero cyanine dye from a cyclo ammonium quaternary compound containing a reactive methyl group, for example, the methods described in Specifications 344,409 and 669,174.  The sulpho-betaines defined above are preferably first converted into the non-betaine type of quaternary salt by treatment with an alkali metal halide, e.g. NaI.  Specified values for R are methyl, ethyl, propyl, butyl, phenyl, chlorphenyl, tolyl, methoxy, ethoxy, dimethylamino and di-ethyl amino; R1 may be methyl or ethyl. The quaternary compounds used as starting materials are prepared in specified manner (see Group IV(b)).  In examples: (3) anhydro-3:31-di-b -sulphoethyl oxacarbocyanine hydroxide is prepared by reacting 2-methyl-3-b -sulphoethyl benzoxazolium bromide, sodium salt, with diethoxymethyl acetate in pyridine; (4) anhydro-31-ethyl-3-b -sulpho ethyl oxathia carbocyanine hydroxide is prepared by reacting 2-methyl-3-b -sulphoethyl benzoxazolium bromide, sodium salt, with 2-b -acetanilido vinyl-3-ethyl benzothiazolium iodide in ethyl alcohol in the presence of triethylamine; (5) 3-methyl-4-[(3-b -sulphoethyl-2(3H)- benzoxazolylidine) -ethylidene]-1- p-sulphophenyl-2- pyrazolin-5-one is prepared by similarly reacting 3-methyl-1- p-sulpho phenyl-2- pyrazolin-5-one with 2-b -acetanilido vinyl-3-b -sulphoethyl benzoxazolium bromide, sodium salt, obtained by reacting the 2-methyl-3-b -sulphoethyl benzoxazolium bromide, sodium salt, with diphenyl formamidine in acetic anhydride; (6) anhydro-3-ethyl-9-methyl-31-(4-sulpho butyl)-thia carbo cyanine hydroxide is prepared by reacting 2-methyl-3-(4-sulpho butyl) benzo thiazolium bromide, sodium salt, with 3-ethyl-2-(2-methyl-mercapto propenyl)-benzo thiazolium p-toluene sulphonate.  Specifications 654,683 and 654,690 also are referred to.