Patent GB-585106-A (GB)
Title: Manufacture of sulphuric ester-salts of reduced vat dyestuffs and other quinones
IPC: C09B9/00
Filed: 1944-12-22
Abstract: Water-soluble sulphuric ester salts of leuco compounds of vat dyestuffs, and analogous reduction products of quinones that are not vat dyestuffs, are obtained by reacting these reduction products in aqueous alkaline medium with sulphur trioxide compounds of tertiary amines having a dissociation constant of at least 1 x 10-1 at 25 DEG C. particularly non-aromatic tertiary amines.  The process may be effected in the case of vat dyestuffs by first vatting the dyestuff and then reacting the leuco compound with the sulphur trioxide-tertiary amine compound or in some cases by vatting in the presence of the amine sulphur trioxide compound.  Solvents miscible with water, e.g. lower aliphatic alcohols, acetone, pyridine and water-soluble polyalkylene oxides can also be used with the aqueous esterification medium.  The amine produced by the reaction may be recovered by methods such as by distillation from the reaction mixture, or by stripping or salting out with caustic alkali from the mother liquor after salting out the ester salt.  In examples, the sulphur trioxide compound of N-ethyl morpholine is stirred with an aqueous caustic soda solution of (1) leuco-indigo; (2) leuco - Bz - 2 : Bz - 21 - dimethoxydibenzanthrone; (3) leuco - 5 : 51 : 7 : 71 - tetrabromoindigo-; (4) leuco-3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone; (5) leuco - 6 : 61 - diethoxythioindigo; the sulphur trioxide compound of trimethylamine is stirred with an aqueous caustic soda solution of (6) leuco-Bz-2 : Bz-21-dimethoxydibenzanthrone; (7) leuco-indigo; the sulphur trioxide compound of dimethylcyclohexylamine is stirred with an aqueous caustic soda solution of (8) leuco-Bz-2 : Bz-21-dimethoxydibenzanthrone; (9) leuco-5 : 51-dichloro-7 : 71-dimethylthioindigo; (10 leuco indigo; to an aqueous caustic soda solution of leuco-Bz-2 : Bz-21-dimethoxydibenzanthrone is added the sulphur trioxide compound of (11) triethylamine; (12) triallylamine; (13) indigo is vatted by means of sodium hydrosulphite and caustic soda in the presence of the sulphur trioxide compound of trimethylamine; the sulphur trioxide compound of N-ethyl morpholine is stirred with an aqueous caustic soda solution of (14) leuco-2-acetylaminoanthraquinone; (15) leuco-b -aminoanthraquinone; and (16) with an aqueous caustic potash solution of hydroquinone. Other specified tertiary amines are the tripropylamines, the tributylamines, aralkylamines, such as dimethylbenzylamine and diethylbenzylamine, alicyclic amines such as cyclohexyldiethylamine, cyclopentyldimethylamine, and heterocyclic amines of aliphatic character such as N-methylmorpholine and N-ethylpiperidine.  Other specified leuco compounds are catechol, naphthohydroquinone, anthrahydroquinone, N-acetyl-2-aminoanthrahydroquinone, and the leuco compounds of 7 : 7-dimethyl indigo, 5 : 51-dibromoindigo, hexabromoindigo, halogenated naphthaleneindol-indigo, 2 : 4-dibromoindol-anthraceneindigo, thioindigo, 4 : 41-dimethyl-6 : 61-dichlorothioindigo, 41-methyl-61-chloro-6-ethoxythioindigo, 4 : 5 : 41 : 51-dibenzthioindigo, thionaphthene - indolindigos, thionaphthene - ace - naphthene-indigos, anthraquinone-triazine vat dyestuffs such as the condensation product of 1 mol. of cyanuric chloride with 3 mols. of 1 - aminoanthraquinone, 21 : 51 - dichloro - 4 - benzoylamino - 1 : 9 - anthrapyrimidine, indanthrone, 3 : 3-dichloro-N : N1 - dihydro-1 : 2 : 11 : 21 - anthraquinone azine, flavanthrone, dibenzanthrone, isodibenzanthrone and its halogen derivatives, 3 : 4 : 8 : 9-dibenzpyrene quinone and its halogen derivatives, anthanthrone and its halogen derivatives, pyranthrone and its halogen derivatives, anthrimide carbazoles such as 1 : 11 : 4 : 111 - trianthrimide-2 : 21 : 31 : 211 - dicarbazole, anthraquinone - 1(N) : 2 - naphthacridone, bz - 2 : bz - 4 : 4 - trichloroanthraquinone-1(N) : 2-benzacridone, anthraquinone-2 : 1(N)-6 : 5(N)-dibenzacridone, anthraquinone azoles such as anthraquinone-1 : 2(N) - 5 : 6(N) - di - (phenylthiazole), benzanthrone anthraquinone acridines, perylene tetracarboxylic acid imides such as the dimethylimide, and derivatives of naphthalene tetracarboxylic acids.  Reference is also made to the preparation of salts of the sulphuric esters with organic bases, e.g. quaternary nitrogen bases.  Sulphur-trioxide compounds of tertiary amines, e.g. simple tertiary alkyl amines, unsaturated straight chain amines, alicyclic amines and heterocyclic amines, may be prepared by known methods such as the action of sulphur trioxide or agents capable of generating sulphur trioxide on tertiary amines.