Patent GB-631124-A (GB)
Title: Methine dye intermediates
Filed: 1946-12-16
Abstract: Compounds of the general formula <FORM:0631124/IV (b)/1> wherein Y represents the atoms to complete a 5-membered heterocyclic nucleus, A is O, S, or Se, G is a reactive group, aryl represents a group of the benzene or naphthalene series, X is an acid radical, and m is a small positive integer, are prepared by reacting a compound of formula <FORM:0631124/IV (b)/2> with an aryloxyalkyl, arylthioalkyl, or arylselenoalkyl p-toluenesulphonate.  The heterocyclic nucleus may be a benzoxazole, naphthoxazole, benthiazole, thiazoline, benzselenazole, selenazole, or 3 : 3-dimethylindolenine nucleus, and the aryl group may be phenyl, naphthyl or phenyl substituted by chlorine, methyl, methoxy, di-isopropyl, di-isobutyl, tert.-butyl, or cyclohexyl.  G may be methyl, anilinovinyl, b -acetanilidovinyl, methylmercapto, ethylmercapto, phenylmercapto, ethylmercaptovinyl, formylmethylene, acetylmethylene, 2-chloropropenyl, or 2-bromopropenyl.  2-Methylbenzthiazole phenoxyethyl p-toluenesulphonate is prepared p  by heating together 2-methylbenzthiazole and phenoxyethyl p-toluenesulphonate. 2-Methyl-5 : 6-methylenedioxybenzthiazole phenylthioethyl p-toluenesulphonate, and 2-methylbenzselenazole phenylselenoethyl p-toluenesulphonate are similarly prepared, and similar compounds may be obtained from 2 - methylbenzoxazole, 2 - methyl - 6-methoxybenzselenazole, 2 - methyl - 6 : 7-benzbenzthiazole, 2 - methyl - 4 - phenylthiazole, 2 - methyl - 4 - phenylselenazole, 2-methyl - 4 - phenyloxazole, 2 - methylthiazole, 2 - methylmercaptobenzthiazole, and 2-phenylmercaptobenzthiazole, and from p-di-isobutylphenoxyethyl, p - methylphenoxyethyl, p - cyclohexylphenoxyethyl, p - chlorophenoxyethyl, and p-phenylphenoxyethyl p-toluenesulphonates, the corresponding phenoxypropyl compounds, and the corresponding sulphur and selenium compounds.  The p-toluenesulphonates may be converted into other quaternary salts by treatment with solutions of soluble halides or perchlorates (e.g. KBr, KI, or NaClO4), and thiocyanates and sulphates may also be formed.  P-Toluene-sulphonates of the general formula <FORM:0631124/IV (b)/3> are prepared by reacting the corresponding alcohol with p-toluenesulphonyl chloride in the presence of a base. P-(tert.-butyl)-phenoxyethyl, p-di-isobutylphenoxyethyl, p-methylphenoxyethyl-p-cyclohexylphenoxyethyl, p-chlorophenoxyethyl, and p-phenylphenoxyethyl p-toluenesulphonates are so so prepared.  b -(P-tert.-butylphenoxy)-ethyl alcohol is prepared by reacting p-tert.-butylphenol with ethylene chlorohydrin in the presence of alkali.  b  - (P - chlorophenoxy) - ethyl alcohol, b  - (p-di-isobutylphenoxy) - ethyl alcohol, b  - (p-methylphenoxy) - ethyl alcohol, b  - (p - cyclohexylphenoxy) - ethyl alcohol, and b  - (2 - chloro-6-phenylphenoxy)-ethyl alcohol are similarly prepared. The corresponding arylthioalkyl and arylselenoalkyl alcohols are prepared by reacting thio- or seleno-phenols or substituted thio- or seleno-phenols with a halohydrin (e.g. ethylene or trimethylene chlorohydrin) in presence of sodium alcoholate.  Compounds of the first general formula, wherein G is an anilinovinyl group are prepared by reacting compounds wherein G is a methyl group with a diarylformamidine (e.g. diphenyl, dinaphthyl, or dixylyl formamidine).  If the reaction is carried out in presence of an organic acid anhydride (e.g. acetic, propionic, or benzoic anhydride), compounds wherein G is an acylanilidovinyl group are obtained. 2-a -Acetanilidovinylbenzthiazole phenoxyethyl p-toluenesulphonate and iodide are obtained by refluxing the corresponding 2-methyl compounds with di-phenylformamidine and acetic anhydride.  Compounds of the first general formula wherein G is an anilino- or acylanilido-butadienyl or hexatrienyl group are similarly obtained using b -anilinoacrolein anil hydrochloride or glutaconic aldehyde dianilide respectively.  Compounds of the first general formula, wherein G is an alkylmercapto or arylmercapto group are prepared by reacting the corresponding compounds of the second general formula with an aryloxyalkyl, arylthioalkyl, or arylselenolkyl p-toluenesulphonate.  2-Methylmercaptobenzthiazole phenoxyethyl - p - toluenesulphonate is so prepared, and the corresponding 2 - phenylmercaptobenzthiazole, and the 2-methylmercapto-, 2-ethylmercapto-, and 2-phenylmercaptobenzselenazole and 5 : 6-methylenedioxybenzthiazole compounds are similarly obtained.  Compounds of the first general formula, wherein G is a b -alkyl : b -alkylmercapto-vinyl group are prepared by reacting the corresponding methyl compounds with ethylisothioacetanilide in presence of acetic anhydride.  2 - (b  - methyl : b  - ethylmercaptovinyl) - benzthiazole phenoxyethyl p - toluenesulphonate is obtained by refluxing together 2-methylbenzthiazole phenoxyethyl - p - toluenesulphonate, ethylisothioacetanilide, and acetic anhydride.  The corresponding benzselenazole and 5 : 6-methylenedioxybenzthiazole compounds are similarly obtained.  Compounds of the first general formula, wherein G is a =CH-CHO or =CH-CH= CH-CHO group are obtained by hydrolysing, e.g. in alkali, the corresponding anilino- or acylanilido-vinyl or butadienyl compounds.  N - Phenoxyethyl - 2 - formylmethylenebenzthiazoline and N-phenoxypropylbenzthiazoline-2-trimethine-o -aldehyde are so obtained using alcoholic potassium hydroxide.  Compounds of the first general formula, wherein G is an acylmethylene group are prepared by reacting the corresponding methyl compounds with an acyl halide in presence of an acid-binding agent such as pyridine.  N-Phenoxyethyl - 2 - acetylmethylenebenzthiazoline, the corresponding benzselenazoline and 5 : 6-methylenedioxybenzthiazoline compounds, and the corresponding compounds from propionyl, crotonyl, cinnamoyl, benzoyl, furoyl, and phenylacetyl chlorides are so obtained.  Compounds of the first general formula, wherein G is a halogenovinyl group are obtained by reacting the corresponding acylmethylene compounds with a phosphorus oxyhalide, preferably in a diluent while chilling the reaction mixture.  2 - (2 - Chloropropenyl) - benzthiazole phenoxyethyl chloride is prepared by adding phosphorus oxychloride to a chilled benzene solution of N-phenoxyethyl-2-acetylmethylenebenzthiazoline.  The corresponding phenylthioethyl chloride and 2-(2-chloropropenyl)-benzselenazole phenylselenoethyl chloride are similarly prepared.  Specifications 465,823, [Group XX), and 627,521 are referred to.