Patent GB-509898-A (GB)
Title: Manufacture of dioxazine dyestuffs
IPC: C09B19/02
Filed: 1938-01-22
Abstract: 509,898. Dyes ; dyeing. GROVES, W. W. (I.G. Farbenindustrie Akt.-Ges.). Jan. 22, 1938, No. 2176. [Classes 2 (iii) and 15 (ii)] Dioxazine dyes are made by (a) heating a 2.5-diarylamino-1.4-benzoquinone which contains in 3- and 6- positions hydrogen, halogen or methyl and in which the aryl groups differ from one another in a high-boiling organic solvent and in presence or absence of an organic or inorganic oxidizing agent, a metal chloride or an acylating agent; (b) heating a 2-monoarylamino-5-alkoxy-1.4-benzoquinone or a 2- monoarylamino-5-halogen-1.4-benzoquinone at above 120‹C. preferably in a highboiling organic solvent,.in presence or absence of an acid-binding agent, an organic or inorganic oxidizing agent, a metal chloride or an acylating agent, with a primary aromatic amine different from the amine whose radical is already present in the benzoquinone ; (c) heating a 2.5-diarylamino- 1.4-benzoquinone in which the aryl groups differ with concentrated sulphuric acid, fuming sulphuric acid or chlorsulphonic acid, in presence or absence of an oxidizing agent, at a temperature at which ring closure occurs.. The product of (a) or (b) may be sulphonated. The aryl radicals may contain substituents such as hydroxy, carboxy, sulpho, alkyl, amino or acylamino, and the products may contain no sulphonic groups or up to 8 sulphonic groups. The 2.5-diarylamino-1.4-benzoquinones may be prepared from aminoaryl sulphonic acids or by sulphonating 2.5-diarylamino-1.4-benzoquinones or from 1 mol of an aromatic diamine and 2 mols of a 2-monoarylamino-5-alkoxy (or 5-halogen)- 1.4-benzoquinone prepared according to Specification 509,893. The products may be used as pigment dyestuffs in lacquers, tapestry, paper, rubber or plastics or in the dyeing of animal, vegetable or artificial fibres or mixed fibres. The dyestuff sulphonic acids may be used in the form of their barium or calcium salts as pigments. The parent materials may contain groups which make the products vat-dyes, or groups capable of forming complexes such as the salicylic acid radical, in which latter case dyestuffs capable of being chromed are formed. In examples, (1) 2-(p-diphenyl)-amino-5-anilino- 3:6-dichloro-1.4-benzoquinone is heated in nitrobenzene with 1.4-dinitrophenol and ptoluenesulphochloride, followed by sulphonation (red tints on vegetable and viscose artificial staple fibres) (2) 2-(N-ethyl-carbazolyl-31- amino)-5-anilino-3.6-dibromo-1.4-benzoquinone is heated in nitrobenzene, followed by sulphonation (red-violet tints on animal, vegetable and viscose artificial staple fibres) ; (3) 2-(#-anthramino)-5-(p-diphenyl)-amino - 3.6 - dichloro - 1.4- benzoquinone is heated in trichlorbenzene or alpha-chlornaphthalene with p-toluenesulphochloride, followed by sulphonation (grey tints) (4) 2-(alpha-naphthylamino)-5 - anilino-1.4 - benzoquinone is heated in nitrobenzene with m-nitrobenzene sulphochloride, followed by sulphonation : (5) 2-(#-naphthylamino)-5-(N-ethyl-carbazolyl-3<1>-amino)-3.6-dichloro-1.4-benzoquinone is heated in o-dichlorbenzene withp-toluenesulphochloride, followed by sulphonation (reddishblue) ; (6) (#-naphthylamino)-anilino-chlorotoluquinone (obtainable according to example 4 of Specification 509,893) is heated in nitrobenzene with ferric chloride, followed by sulphonation (red-violet) ; (7) 2-(#-anthraquinonylamino) - 5 - (p - diphenyl)-amino-3.6-dichlor-1.4-benzoquinone is heated with sulphuric acid to give a sulphonic acid (red-violet tints on vegetable and viscose artificial staple fibres), or if weaker sulphuric acid is used, a red-violet vat-dye free from sulphonic groups : (8) 2-(p-sulphoanilino)-5-(p-diphetiyl)-amino-3.6 - dichloro- 1.4-benzoquinone is heated with sulphuric acid (red tints on animal, vegetable and viscose artificial staple fibres) ; (9) 2-(4<1>-hydroxy-5<1>- carboxyanilino)-5-(N-ethyl-carbazolyl-3<1>-amino) - 3.6-dichloro-1.4-benzoquinone is heated with sulphuric acid (navy-blue tints on chromed cotton) ; a sulphonic group may be present in the salicylic radical ; (10) 2-(p<1>-aminoanilino)- 5 - (p-diphenyl) - amino - 3.6-dichloro-1.4-benzoquinone is heated with sulphuric acid (reddishblue tints on vegetable and viscose artificial staple fibres) ; the product may be diozotized on the fibre and coupled with a naphthol, redder shades being thereby obtained ; the product obtainable from two mols. 2-methoxy-5-(pdiphenyl)-amino-3.6-dichloro-1.4-benzoquinone and one mol. of (11) p-phenylenediamine and (12) benzidine (see examples 13 and 14 of Specification 509,893) is heated in, sulphuric acid, using manganese dioxide in the latter case (blue tints on vegetable and viscose artificial staple fibres) ; (13) 2-methoxy-5-(#-naphthylamino)-3.6-dichloro-1.4-benzoquinone is reacted with 3-amino-N-ethyl-carbazole in nitrobenzene to give the same product as (5) above ; (14) 2-anilino-3.5.6-trichloro-1.4-benzoquinone is heated with #-anthramine in nitrobenzene in presence of p-toluene sulphochloride, followed by sulphonation ; (15) 2-butoxy-5-(N-ethylcarbazolyl - 3<1> - amino) - 3.6 - dichloro-1.4-benzoquinone is heated with 3-aminopyrene in trichlorbenzene in presence of sodium acetate and alcohol at 90-100‹C., after which the temperature is raised, m-nitrobenzene sulphochloride added, and the product sulphonated (blue tints) ; (16) 2-(N-ethyl-carbazolyl-3<1>- amino)- or 2-(2<1>naphthylamino)-5-(6<11>-hydroxy- 7<11>-carboxynaphthyl-2<11>- amino) - 3.6 - dichloro- 1.4-benzoquinone is heated in nitrobenzene with p-toluene-sulphochloride, followed by sulphonation (blue tints) ; (17) 2-(pyrenyl-3'-amino)-5- (4<11>-hydroxy-3<11>-carboxy-anilido)-3.6 - dichloro- 1.4-benzoquinone is heated in sulphuric acid (blue-grey tints, grey on mordanted fibres). Specification 509,891 also is referred to.