Patent GB-610117-A (GB)
Title: Manufacture of dyestuffs and intermediates
IPC: C09B9/00
Filed: 1946-03-26
Abstract: Ester derivatives are made from dyestuffs or dyestuff intermediates by treating in presence of a metal and an organic amide as hereinafter defined, with or without diluents, with sulphur trioxide, or with an addition compound of sulphur trioxide and an organic amide or tertiary base, or with any substance known to be capable of forming sulphuric esters from vat dyestuffs in presence of metals or from leuco compounds, or metal salts thereof or complex compounds comprising the metal salts thereof, either alone or in the presence of other substances.  The amides are defined as bodies of the formula R-CO-NR1R2, where R stands for hydrogen or an organic radicle, R1 and R2 stand for hydrocarbon radicles or substituted hydrocarbon radicles which may be the same or different and which may be connected with each other to form together with the nitrogen atom a closed ring, and where one of the radicles R1 and R2 may be connected to R, when R is an organic radicle, to form, together with the carbonyl carbon atom and the nitrogen atom, a closed ring.  Amides specified are dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, tetramethylurea, formyl- and acetyl-piperidide, formylmorpholide, tetramethyladipamide, dimethylbenzamide, dimethylurethane, N - methylacetanilide and N-methylphthalimidine. Diluents specified are inert diluents such as acetone, methylethylketone, acetonitrile, benzonitrile, benzene or nitrobenzene, or tertiary bases such as pyridine or triethylamine. Alternatives to sulphur trioxide are the addition compound of sulphur trioxide and dimethylformamide, chlorsulphonic acid, and methyl and ethyl chlorsulphonates.  Metals specified are iron, nickel, copper, brass and an added substance may be a quaternary ammonium salt such as tetramethylammonium chloride.  In examples, the following combinations of reactants and diluents are reacted together: (1) sulphur trioxide, dimethyl- or diethyl-formamide, 16.17-dimethoxydibenzanthrone, brass powder; (2) dimethylformamide, sulphur trioxide, tetrabromindigo, and brass; (3) methyl chlorosulphonate, acetone, dimethylformamide, 1.4 - dibenzoylaminoanthraquinone, and iron powder; (4) methyl chlorosulphonate, dimethylformamide acetone, anthraquinone, and iron powder; (5) methyl chlorosulphonate, dimethylformamide, acetone, 1 : 11 : 4 : 111-trianthrimidecarbazole, and iron powder; (6) methyl chlorosulphonate, formylpiperidide, acetonitrile (or benzonitrile, acetone or methyl ethyl ketone), anthraquinone, and iron powder; (7) as in (6) but using nickel powder; (8) tetramethyladipamide, acetone, methyl chlorosulphonate, indigo, and iron powder; (9) diethylacetamide, acetonitrile, chlorosulphonic acid, 4.10-dichloranthanthrone, copper powder; (10) dimethylformamide, benzene, chlorsulphonic acid, dimethoxydibenzanthrone, copper powder; (11) N-formylmorpholide, acetone, ethyl chlorosulphonate, 1.4 - di - (m - methanesulphonyl - benzoylamino) - anthraquinone, and iron powder; (12) dimethylformamide, chlorosulphonic acid, thioindigo, copper powder; (13) N-dimethylbenzamide, acetone, methyl chlorosulphonate, 2-chloro-3-acetylaminoanthraquinone, iron powder; (14) tetramethylurea, acetone, methyl chlorosulphonate, 2-chloro-3-acetylaminoanthraquinone, iron powder; (15) chlorsulphonic acid, tetramethylurea, dibenzpyrenequinone, copper powder; (16) methyl chlorosulphonate, dimethylurethane, 16.17 - dimethoxydibenzanthrone, acetonitrile, and copper powder; (17) N-methyl acetanilide, acetonitrile, methyl chlorosulphonate, 4.10-dibromanthanthrone, iron powder; (18) N-methyl-phthalimidine, acetone, methyl chlorosulphonate, 2-chloranthraquinone, iron powder; (19) methyl chlorsulphonate, acetopiperidide, benzonitrile, 4.10 - dibromanthan - throne and iron powder.ALSO:Ester derivatives are made from dyestuffs or dyestuff intermediates by treating in presence of a metal and an organic amide as hereinafter defined, with or without diluents, with sulphur trioxide, or with an addition compound of sulphur trioxide and an organic amide or tertiary base, or with any substance known to be capable of forming sulphuric esters from vat dyestuffs in presence of metals or from leuco compounds, or metal salts thereof or complex compounds comprising the metal salts thereof, either alone or in the presence of other substances.  The amides are defined as bodies of the formula R-CO-NR1R2, where R stands for hydrogen or an organic radicle, R1 and R2 stand for hydrocarbon radicles or substituted hydrocarbon radicles which may be the same or different and which may be connected with each other to form together with the nitrogen atom, a closed ring, and where one of the radicles R1 and R2 may be connected to R, when R is an organic radicle, to form, together with the carbonyl carbon atom and the nitrogen atom, a closed ring.  Amides specified are dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, tetramethylurea, formyl- and acetyl-piperidide, formylmorpholide, tetramethyladipamide, dimethylbenzamide, dimethylurethane, N-methylacetanilide, and N - methylphthalimidine. Diluents specified are inert diluents such as acetone, methylethylketone, acetonitrile, benzonitrile, benzene or nitrobenzene, or tertiary bases such as pyridine or triethylamine. Alternatives to sulphur trioxide are the addition compound of sulphur trioxide and dimethylformamide, chlorsulphonic acid, and methyl and ethyl chlorsulphonates.  Metals specified are iron, nickel, copper, brass and an added substance may be a quaternary ammonium salt such as tetramethylammonium chloride.  In examples, the following combinations of reactants and diluents are reacted together: (1) sulphur trioxide, dimethyl- or diethyl-formamide, 16.17-dimethoxydibenzanthrone, brass powder; (2) dimethylformamide, sulphur trioxide, tetrabromindigo and brass; (3) methyl chlorosulphonate, acetone, dimethylformamide, 1.4 - dibenzoylaminoanthraquinone, and iron powder; (4) methyl chlorosulphonate, dimethylformamide, acetone, anthraquinone, and iron powder; (5) methyl chlorosulphonate, dimethylformamide, acetone, 1 : 11 : 4 : 111-trianthrimidecarbazole, and iron powder; (6) methyl chlorosulphonate, formylpiperidide, p  acetonitrile (or benzonitrile, acetone or methyl ethyl ketone) anthraquinone, and iron powder; (7) as in (6) but using nickel powder; (8) tetramethyladipamide, acetone, methyl chlorosulphonate, indigo, and iron powder; (9) diethylacetamide, acetonitrile, chlorosulphonic acid, 4.10-dichloranthanthrone, copper powder; (10) dimethylformamide, benzene, chlorsulphonic acid, dimethoxydibenzanthrone, copper powder; (11) N-formylmorpholide, acetone, ethyl chlorosulphonate, 1.4 - di - (m - methanesulphonyl - benzoylamino)-anthraquinone, and iron powder; (12) dimethylformamide, chlorosulphonic acid, thioindigo, copper powder; (13) N-dimethylbenzamide, acetone, methyl chlorosulphonate, 2 - chloro - 3 - acetylaminoanthraquinone, iron powder; (14) tetramethylurea, acetone, methyl chlorosulphonate, 2 - chloro - 3 - acetylamino - anthraquinone, iron powder; (15) chlorsulphonic acid, tetramethylurea, dibenzpyrenequinone, copper powder; (16) methyl chlorosulphonate, dimethylurethane, 16.17 - dimethoxydibenz - anthrone, acetonitrile, and copper powder; (17) N - methyl acetanilide, acetonitrile, methyl chlorosulphonate, 4.10 - dibromanthanthrone, iron powder; (18) N-methyl-phthalimidine, acetone, methyl chlorosulphonate, 2-chloranthraquinone, iron powder; (19) methyl chlorsulphonate, acetopiperidide, benzonitrile, 4.10-dibromanthanthrone, and iron powder.