Patent GB-562756-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B23/16
Filed: 1942-07-13
Abstract: Dyes of the formula <FORM:0562756/IV/1> (wherein R1 and R11 are aryl radicals, e.g. of the benzene or naphthalene series, substituted or not and the same or different and R111 is H or a non-reactive substituent, e.g. an aryl, alkyl, or acylamino radical) are prepared by condensing a 5-nitroso-2 : 4-diarylpyrrole with a compound XCH2Y, other than a 2 : 4-diarylpyrrole, which contains one or more reactive methylene or methyl groups.  5-Nitroso-2 : 4-diarylpyrroles specified are 5 - nitroso - 2 : 4 - diphenylpyrrole, 5 - nitroso - 2 - phenyl - 4 - (p - methoxyphenyl) - pyrrole, 5 - nitroso - 2 - (p - methoxyphenyl)-4-phenylpyrrole, 5-nitroso-2-(m-hydroxyphenyl)-4-phenylpyrrole, 5-nitroso-2-(o-chlorophenyl)-4-phenylpyrrole, 5-nitroso-2-(p - acetylaminophenyl) - 4 - phenylpyrrole, 5-nitroso - 2 - a  - naphthyl - 4 - phenylpyrrole, 5-nitroso - 2 - phenyl - 4 - b  - naphthylpyrrole, 5-nitroso-2 : 3 : 4-triphenylpyrrole, 5-nitroso-3-benzoylamino-2 : 4-diphenylpyrrole, 5-nitroso-3-acetylamino-2 : 4-diphenylpyrrole, 5-nitroso-3-benzoylamino - 2 : 4 - di - p - tolylpyrrole, and 5 - nitroso - 3 - acetoacetylamino - 2 : 4 - diphenylpyrrole, and the corresponding sulphonic acids.  Reactive methylene compounds specified are indoxyl, thioindoxyl, 6-ethoxythioindoxyl, 2-alkylindoles, N-methyloxindole, a  : g -diketohydrindine, 2-quinaldine methiodide, 6-ethoxyquinaldine methiodide, 4-phenyl-2-quinaldine methiodide, 2-methylbenzoxazole methiodide, 2-methylbenzthiazole methiodide, 1 : 3 : 3-trimethyl - 2 - methylenedihydroindole, 6 - nitro - 1 : 3 : 3 - trimethyl - 2 - methylene - dihydroindole, 1 - phenyl - 3 - methyl - 5 - pyrazolone, cyanacetic ester, chloroacetonitrile, phenylsulphonylacetonitrile, 2 : 4-dinitrotoluene, N-phenylrhodanine, barbituric acids, sulphazones, lepidine ethiodide, 2 : 4 - dihydroxyquinolines, dihydroresorcinol, benzyl cyanide, cyanoacetophenone, b -naphthol, desoxy-benzoin, a -naphthol, 2-keto-2 : 3-dihydrobenzthiazine, and 3 : 31-dinitro-4 : 41-dimethylazobenzene.  If compounds containing more than one reactive methylene or methyl group are used, more than one molecular proportion of the nitroso-compound will react therewith.  The reactants may be heated together in a mutual solvent, e.g. ethanol, in the presence of a base, e.g. piperidine.  Water-soluble derivatives of the dyes are obtained by forming salts with sulphamic acid, by forming quaternary ammonium salts, by sulphonation of the dyes with fuming sulphuric acid or chlorsulphonic acid to yield water-soluble sulphonic acids or salts thereof, or by using reactants, one or both of which contain water-solubilizing groups, e.g. sulphonic acid groups.  In example 1, 1-(p-sulphophenyl)-3-methyl-5-pyrazolone, 5 - nitroso - 2 : 4 - diphenylpyrrole, ethanol, and piperidine are refluxed together. The piperidine salt may be converted to the sodium salt.  In example 2, 5-nitroso-2 : 4-diphenylpyrrole hydrochloride, 1 : 3 : 3 - tri - methyl - 2 - methyl - dihydroindole, and benzene are heated together. The dye obtained may be converted to a water-soluble sulphamate by dissolving in ethanol and pouring into boiling aqueous sulphamic acid solution, or by forming the anhydro-base by adding aqueous caustic soda to the ethanol solution and adding sulphamic acid to a suspension of the anhydrobase in boiling ethanol.  A dye may be similarly obtained from 5-nitroso-2-phenyl-4-(o-chlorophenyl)-pyrrole.  In example 3, quinaldine methiodide, 5 - nitroso - 2 : 4 - diphenylpyrrole, ethanol, and piperidine are refluxed together.  The dye may be converted to the anhydro-base, the sulphamate, and the hydrochloride. Dyes may be similarly obtained from 5-nitroso-2-phenyl-4-(o-chlorophenyl)-pyrrole, 5-nitroso-2-(p - methoxyphenyl) - pyrrole, and 5 - nitroso - 2 : 3 : 4 - triphenylpyrrole, using quinaldine methochloride in the first two cases and quinaldine ethiodide in the third.  In example 4, 4-phenylquinaldine methiodide, 5-nitroso-2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together.  In example 5, 6-ethoxyquinaldine methochloride, 5 - nitroso - 2 : 4 - diphenylpyrrole, methanol, and piperidine are refluxed together. In example 6, 2-methylbenzthiazole methiodide, 5 - nitroso - 2 : 4 - diphenylpyrrole, ethanol, and piperidine are boiled together. Dyes may be similarly obtained from 5-nitroso-2-phenyl-4-(o-chlorophenyl) - pyrrole and 5-nitroso-2-(p-methoxyphenyl) - 4 - phenylpyrrole with 2 - methylbenzthiazole ethiodide.  In example 7, 5-nitroso-2 : 4-diphenylpyrrole, lepidine ethiodide, ethanol and piperidine are refluxed together.  In example 8, 1 - phenyl - 3 - methyl - 5 - pyrazolone, 5 - nitroso - 2 : 4 - diphenylpyrrole, ethanol, and piperidine are refluxed together.  In example 9, 6-ethoxythioindoxyl, 5-nitroso-2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together.  In example 10, b -naphthol, 5-nitroso-2 : 4-diphenylpyrrole, acetic acid, and acetic anhydride are refluxed together.  In example 11, N-methyloxindole, 5-nitroso-2 : 4-diphenylpyrrole, ethanol, and piperidine are refluxed together, or N-methyloxindole and 5-nitroso-2 : 4-diphenylpyrrole are heated in o-dichlorobenzene.  In example 12, N-ethylrhodanine, 5 - nitroso - 2 - (p - methoxyphenyl) - 4 - phenyl - pyrrole, ethanol, and piperidine are refluxed together. In example 13, 6-nitro-1 : 3 : 3-trimethyl - 2 - methylene - dihydroindole methobromide, 5-nitroso-2 : 4-diphenylpyrrole, acetic acid, and acetic anhydride are refluxed together. Specification 554,103 is referred to.  The Provisional Specification also refers to dyes of the general formula wherein R111 may be an alkylamino or benzylideneamino radical.