Patent GB-318180-A (GB)
Title: Improvements in the manufacture and production of nitrogenous vat dyestuffs
IPC: C09B6/00
Filed: 1928-02-24
Abstract: 318,180. Johnson, J. Y., (I. G. Farbenindustrie .4kt.-Ges.). Feb. 24, 1928. Vat dyes are made by condensing isocyclic compounds containing a plurality of negative substituents of identical or different character, such as halogen or nitro groups, simultaneously or successively with a plurality of cyclic nitrogenous compounds each containing at least one reactive hydrogen atom connected to a nitrogen atom, at least one of the components taking part in the reaction being vatable, and at least one containing a system of four or more condensed rings. Alternatively, the dyes may be made by condensing isocyclic compounds containing a plurality of nitrogen atoms, with reactive hydrogen atoms attached to at least two nitrogen atoms, simultaneously or successively with several different cyclic compounds containing negative substituents, at least one of the latter compounds being vatable, and a least one of the components containing a system of four or more condensed rings. The condensation is preferably effected with the aid of acid fixing agents or condensing catalysts or both, in the presence or absence of solvents or diluents, such as nitrobenzene, nitrotoluene, naphthalene, nitronaphthalene and the like. The products for the most part possess better tinctorial properties and are faster than the corresponding products substituted several times by the same nitrogenous bodies. The products from isocyclic compounds of high molecular weight (above about 250) in general dye in deep shades, such as violet, blue, grey or blue black while those from isocyclic compounds of lower molecular weight dye brighter shades, such as yellow, red or blue. Such products dyeing brighter shades are preferably obtained by employing acid amides as nitrogenous components. As isocyclic compounds containing negative groups those derived from benzene naphthalene, anthracene, phenathrene, perylene, pyrene, the various dianthrones connected with each other by one or more ring systems, dibenzanthrone, isodibenzanthrone, dibenzpyrenequinones, and anthranthrone are mentioned. The components need not be brought into reaction in exact stoichiometric proportions. In examples, (1) Dibromopyranthrone (prepared by bromination in chlorsulphonic acid, with a sulphur catalyst), is condensed with alpha-aminoanthraquinone, and aminoviolanthrone (grey to black). (2) Dibrompyranthrone (prepared by bromination with hypobromite in aqueous suspension) is condensed with alpha-aminoanthraquinone and 5-amino-4'-benzoylamino-8-methoxy- 1 : 1 -anthrimidocarbazole (dark brown). (3) Tribrompyranthone is condensed with aminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (1 mol.), or 1 : 5-diaminoanthraquinone (1 mol.) or 1 amino-8-methoxyanthraquinone (1 mol.) ur 1 . amino - 5 -benzoylamino - 8 - methoxyanthraquinone (grey to black). (4) Tetrabrompyranthrone is condensed with (i) alpha-aminoanthraquinone (3 mol.) and 6-aminobenzanthrone (I mol.) (violet grey), (ii) alpha-aminoanthraquinone (2 mol.) and 1-amino-4-methoxyanthraquinone- (2 mol. (grey to black), (iii) a-aminoanthraquinone (2 mol.) and #-aminoanthraquinone (2 mol.) (grey to black), (iv) aminoviolanthrone (1, 2, 2¢, 3 or 3¢ mols.) and alpha-aminoanthraquinone (3, 2, 1¢, 1 or ¢ mol.) (grey to black, redder the less aminoviolanthrone is employed), (v) aminoviolanthrone (1 mol), alpha-aminoanthraquinone (2 mol.) and #- aminoanthraquinone (1 mol.) (grey to black), (vi) dibromaminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (2 mol.) (grey to black), (vii) aminoisoviolanthrone (2 mol.) and alpha-aminoanthraquione (2 mol.) (blue black) (viii) aminoviolanthrone (3 mol.) and aminopyranthrone (1 mol.) (grey to black) and (ix) aminoviolanthrone (3 mol.) and aminoanthanthrone (1 mol.) (grey to black). (grey to black) and ix) aminoviolanthrone (3 mol.) and aminoanthraquinone (1 mol.) (grey to black). (5) Pentabrompyranthrone is condensed with aminoviolanthrone (4 mol.) and alpha-aminoanthraquinone (1 mol.) (grey to black). (6) Pentabrommonochlorpyranthrone is condensed with aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (2 mol.) (grey to black). (7) Dibromanthanthrone is condensed with (i) alpha-aminoanthraquinone and 1 : 5-diaminoanthraquinone (grey), (ii) alpha-aminoanthraquinone and 5-amino-4<1>-1-benzcylamino-8- methoxy-1:1<1>-dianthrimidocarbazole (grey), (iii) aminoviolanthrone and a - aminoanthraquinone (blue-black), (iv) aminoviolanthrone and 1 : 5- diaminoanthraquinone (green-grey), and (v) aminoanthanthrone and aminopyranthrone' (brown). (8) Tetrachloranthanthrone is condensed with alpha-aminoanthraquinone (2 mol.) and 1- amino-5-benzoylamino-8-methoxyanthraquinone (2 mol.) (brown) or with a-aminoanthraquinone (2 mol.) and 5-amino-4<1>-benzoylamino-8-methoxy-1 : 1<1>-dianthrimidocarbazole (2 mol.) (brown). (9) Dibrom-3 : 4 8 : 9-dibenzpyrene-5 : 10-quinone is condensed with (i) alpha-aminoanthraquinone and 1 : 5-diaminoanthraquinone (violet), (ii) 1-amino-8- methoxyanthraquinone and 1-amino-4-benzoylamioanthraquinone (dark blue), (iii) alpha-aminoanthraquinone and 5-amino-4<1>-benzoylamino-1 1<1>-dianthrimidocarbazole (violet), (iv) aminoviolanthrone and alpha-aminoanthraquinone (grey to blueblack), (v) aminoviolanthrone and aminoanthanthrone (green-black), and (vi) dibromaminoviolanthrone alpha - aminoanthraquinone (grey to black). (10) Tetrachlor-3: 4 : 8 : 9-dibenzpyrene- 5 : 10-quinone is condensed with aminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (2 mol.) (green-grey to black). (11) Hexachlor-3 : 4 : 8 : 9 - dibenzpyrene-5 : 10-quinone is condensed with aminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (4 mol.) (green-grey). (12) Dibromperylene-3 : 10-quinone is condensed with aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (1 mol.) (black). (13) Tetrabrom-ms-benzdianthrone is condensed with aminoviolanthrone (1 or 3 mol.) and alpha-aminoanthraquinone (3 or 1 mol.) (violet blue and violet black respectively. (14) Tribrom-ms-naphthdianthrone is condensed with aminoviolanthrone and alpha - aminoanthraquinone (violet black to black). (15) Dichlor-allo-msnaphthdianthrone is condensed with (i) benzamide and m-methoxybenzamide (red), (ii) anthraquinone-2-carboxylic amide and m-methoxybenzamide (brown-red), (iii) anthraquinone-2-carboxylic amide and benzamide, (iv) alpha-aminoanthraquinone and 6-aminobenzanthrone (grey), and (v) aminoviolanthrone (1¢ mol.) and alpha-aminoanthraquinone (¢ mol.) (black). (16) Dibrom-msanthradianthrone is condensed with aminoviolanthrone and alpha-aminoanthraquinone (black). (17) Dibromviolanthrone is condensed with (i) alphaaminoanthraquinone and 1-aminoanthraquinone-2- aldehyde (grey), (ii) alpha-aminoanthraquinone and 5-amino-4<1>-benzoylamino-1 : 1<1>-dianthrimidocarbazole (green to black), (iii) aminoviolanthrone and alpha-aminoanthraquinone (green-blue), (iv) monamino-3 : 4: 8: 9-dibenzpyrene-5: 10-quinone and alpha-aminoanthraquinone (blue-black), (v) aminopyranthrone and 1-amino-5-benzoylaminoanthraquinone (grey to black), and (vi) aminoanthanthrone and alpha-aminoanthraquinone (grey). (18) Tribromviolanthrone is condensed with (1) alphaaminoanthraquinone (2 mol.) and 1 : 5-diaminoanthraquinone (¢ mol.) (grey), (ii) aminoviolanthrone (2 mol.) and 6-aminobenzanthrone (1 mol.) (green-grey), (iii) aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (1 mol.) (greengrey), (iv) aminopyranthrone (2 mol.) and alphaaminoanthraquinone (1 mol.) (grey), and (v) aminoanthanthrone (1 mol.), alpha-aminoanthraquinone (1 mol.), and 5-amino-41-benzoylamino- 1 : 1<1>-dianthrimidocarbazole (1 mol.) (black). (19) Tetrabromviolanthrone is condensed with (i) alphaaminoanthraquinone (3 mol.) and #-aminoanthraquinone (1 mol.) (grey), (ii)) aminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (1 mol.) (green-grey), (iii) aminoviolanthrone (2 mol.) and #-aminoanthraquinone (2 mol.) (blue-black), and (iv) aminoviolanthrone (2 mol.), aniline (1 mol.), and p-toluidine (1 mol.) (green-grey). (20) Tetrabromdichlorviolanthrone is condensed with (i) aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (2 mol.) (blue-grey), and (ii) aminoanthanthrone (1 mol.) and aminopyranthrone (1 mol.) (grey to black). (21) Dibromisoviolanthrone is condensed with (1) alpha-aminoanthraquinone and 1-aminoanthraquinone-2-aldehyde (violet), (ii) alpha-aminoanthraquinone and 5- amino - 4<1>-benzoylamino-1 : 1<1>-dianthrimidocarbazole (dark blue), (iii) aminoviolanthrone and alphaaminoanthraquinone (blue), (iv) amino-3 : 4 : 8 :- 9 - dibenzpyrene - 5: 10 - quinone and alpha-aminoanthraquinone (dark blue), (v) aminopyranthrone and 1-amino-5-benzoylaminoanthraquinone (dark blue), and (vi) aminoanthanthrone and alpha-aminoanthraquinone (dark blue). (22) Tribromisoviolanthrone is condensed with (i) alpha-aminoanthraquinone (2 mol.) and 1 : 5-diaminoanthraquinone (¢ mol.) (blue grey), (ii) aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (1 mol.) (greyblue), (iii) aminoviolanthrone (2 mol.) and 6- aminobenzanthrone (2 mol) (dark blue), (iv) aminopyranthrone (2 mol.) and alpha-aminoanthraquinone (1 mol.) (grey), and (v) aminoanthanthrone (1 mol.), alpha-aminoanthraquinone (1 mol.), and 5 - amino - 41-benzoylamino-1 : 1<1>-dianthrimidocarbazole (1 mol.) (grey to black). (23) Tetrabromisoviolanthrone is condensed with (i) alphaaminoanthraquinone (3 mol.) and #-aminoanthraquinone (1 mol.) (grey), (ii) alpha-aminoanthraquinone (2 mol.) and 5-amino-4<1>-benzoylamino-1 : 1<1>-dianthrimidocarbazole (2 mol.) (grey), and (iii) aminoviolanthrone (2 mol.) and alpha-aminoanthraquinone (2 mol.) (blue-grey). (24) Tetrabromdichlorisoviolanthrone is condensed with aminoviolanthrone (1 mol.) and alpha-aminoanthraquinone (2 mol.) (blue-grey). (25) Dibromphenanthraquinone, is condensed with aminoviolanthrone and alpha-aminoanthraquinon