Patent GB-610566-A (GB)
Title: Improvements in and relating to the manufacture of naphtha-4:5-selenazole compounds and to the manufacture of dyes containing the naphtha-4:5-selenazole nucleus
IPC: C09B23/02
Filed: 1946-03-19
Abstract: 3 - Alkyl - 2 - iminonaphtha - 4 : 5 - selenazolines are prepared by oxidizing with a halogen (bromine or iodine) 1-alkyl-1-(11-naphthyl)-2-selenoureas.  2 - Imino - 3 - methylnaphtha - 4 : 5 - selenazoline is prepared by oxidizing 1-methyl-1-(1-naphthyl)-2-selenourea with bromine in glacial acetic acid.  2-Imino-3-ethylnaphtha-4 : 5-selenazoline and the corresponding 3-propyl- and 3-butylcompounds are similarly prepared.  1-Methyl-1-(11-naphthyl)-2-selenourea is prepared by passing dry hydrogen selenide and ammonia into an ethyl alcohol solution of N-methyl-1-naphthylcyanamide. 1-Ethyl-1-(11-naphthyl)-2-selenourea is similarly prepared.  3 - Alkyl - 2 - nitrosoiminonaphtha - 4 : 5-selenazolines are prepared by treating 3-alkyl-2-iminonaphtha-4 : 5-selenazolines with nitrous acid.  3 - Methyl - 2 - nitrosoiminonaphtha - 4 : 5-selenazoline is prepared by adding aqueous sodium nitrite to a glacial acetic acid solution of 2 - imino - 3 - methylnaphtha - 4 : 5 -selenazoline. 3-Ethyl-, 3-propyl-, and 3-butyl-2-nitroso-iminonaphtha-4 : 5-selenazolines are similarly prepared.  3 - Alkylnaphtha - 4 : 5 - selenazol - 2 - ones are prepared by heating 3-alkyl-2-nitrosoiminonaphtha-4 : 5-selenazolines to a temperature at which nitrogen is evolved.  3 - Methylnaphtha - 4 : 5 - selenazol - 2 - one is prepared by adding 3-methyl-2-nitrosoiminonaphtha-4 : 5-selenazoline to boiling xylene.  3-Ethyl-, 3-propyl-, and 3-butyl-naphtha-4 : 5-selenazol-2-ones are similarly prepared.  3 - Alkylnaphtha - 4 - 5 - selenazol - 2 - thiones are prepared by treating 3-alkylnaphtha-4 : 5-selenazol-2-ones with phosphorus pentasulphide.  3 - Methylnaphtha - 4 : 5 - selenazol - 2 - thione is prepared by heating 3-methylnaphtha-4 : 5-selenazol-2-one with phosphorus pentasulphide in dry xylene in the presence of pyridine. 3-Ethyl-, 3-propyl, and 3-butyl-naphtha-4 : 5-selenazol-2-thiones are similarly prepared.  3 - Alkyl - 2 - alkylmercaptonaphtha - 4 : 5-selenazolium quaternary salts are prepared by heating 3-alkylnaphtha-4 : 5-selenazol-2-thiones with alkyl salts.  3 - Methyl - 2 - methylmercaptonaphtha - 4 : 5-selenazolium p-toluenesulphonate is prepared by heating together 3-methyl-naphtha-4 : 5-selenazol-2-thione with methyl p-toluenesulphonate.  3 - Ethyl - 2 - ethylmercaptonaphtha - 4 : 5-selenazolium p-toluenesulphonate and the corresponding 3 - propyl - 2 - propylmercapto - and 3-methyl-2-butylmercaptocompounds are similarly prepared.  3 - Alkyl - 2 - methylnaphtha - 4 : 5 - selenazolium quaternary salts are prepared by condensing 3 - alkyl - 2 - alkylmercaptonaphtha-4 : 5-selenazolium quaternary salts with malonic ester (e.g. diethyl-dimethyl-, or dipropyl-malonate), hydrolyzing the condensation product and heating to split off CO2.  2 : 3 - Dimethylnaphtha - 4 : 5 - selenazolium chloride is prepared by refluxing together 3-methyl - 2 - methylmercaptonaphtha - 4 : 5-selenazolium p-toluenesulphonate, ethyl malonate, sodium ethylate, and ethyl alcohol, and heating the product with HCl.  3-Ethyl-, 3-n-propyl-, and 3-n-butyl-2-methylnaphtha-4 : 5-selenazolium quaternary salts are similarly prepared.ALSO:11 : 3-Dialkyl-4 : 5-benzselenz-21-cyanines are prepared by condensing 3-alkyl-2-methylnaphtha-4 : 5-selenazolium quaternary salts with 2-iodoquinoline alkyl quaternary salts.  11:3 - Dimethyl-4 : 5 - benzselena - 21 - cyanine iodide is prepared by refluxing together 2 : 3-dimethylnaphtha-4 : 5-selenazolium chloride, 2-iodoquinoline methiodide, triethylamine, and ethyl alcohol.  11 : 3-Diethyl, 11-ethyl-3-methyl-, 11 : 3-di-n-propyl-, and 11 : 3-di-n-butyl-4 : 5-benzselena-21-cyanine iodides are similarly prepared.  11 : 3-Dialkyl-4 : 5-benzselena-41-cyanines are prepared by condensing 3-alkyl-2-alkylmercaptonaphtha - 4 : 5 - selenazolium quaternary salts with lepidine alkyl quaternary salts.  11 : 3 - Dimethyl - 4 : 5 - benzselena - 41 - cyanine iodide is prepared by refluxing 1-methyl-2-methylmercaptonaphtha - 4 : 5 - selenazolium p-toluenesulphonate, lepidine methiodide, triethylamine, and ethyl alcohol.  11 : 3-Diethyl, 11-ethyl-3-methyl-, 11 : 3-di-n-propyl-, and 11 : 3-di-n-butyl-4 : 5-benzselena-41-cyanine iodides are similarly prepared.  3 : 31 - Dialkyl - 4 : 5 : 41 : 51 - dibenzselenacyanines are prepared by condensing together 3-alkyl - 2 - alkylmercaptonaphtha - 4 : 5 - selenazolium quaternary salts and 3-alkyl-2-methylnaphtha-4 : 5-selenazolium quaternary salts.  3 : 31 - Dimethyl - 4 : 5 : 41 : 51 - dibenzselenacyanine chloride is prepared by refluxing together 3-methyl-2-methylmercaptonaphtha-4 : 5 - selenazolium p - toluenesulphonate, 2 : 3-dimethylnaphtha - 4 : 5 - selenazolium chloride, triethylamine, and ethyl alcohol.  3 : 31-Diethyl-, 3 : 31-di-n-propyl-, 3 : 31-di-n-butyl-, and 3-ethyl-31 - methyl - 4 : 5 : 41 : 51 - dibenzselenacyanine chlorides are similarly prepared.  3 : 31 - Dialkyl - 4 : 5 : 41 : 51 - dibenzselenacarbocyanines are prepared by condensing 2 molecular proportions of 3-alkyl-2-alkylmercaptonaphtha-4 : 5-selenazolium quaternary salts with 1 molecular proportion of glutaconic acid.  3 : 31 - Dimethyl - 4 : 5 : 41 : 51 - dibenzselenacarbocyanine bromide is prepared by refluxing together 3-methyl-2-methylmercaptonaphtha-4 : 5-selenazolium p-toluenesulphonate, glutaconic acid, and pyridine and adding aqueous potassium bromide to a hot pyridine solution of the product.  3 : 31-Diethyl-, 3 : 31-di-n-propyl, and 3 : 31-di-n-butyl-4 : 5 : 41 : 51-dibenzselenacarbocyanine bromides are similarly prepared.