Patent GB-344117-A (GB)
Title: Manufacture of anthraquinone derivatives
IPC: C09B1/26
Filed: 1929-12-27
Abstract: The products of the general formula <FORM:0344117/III/1> wherein x in one case stands for an amino group and in the other case for an NHR1, group, R1 stands for alkyl or hydrogen, and R2 for an aromatic or hydroaromatic residue, colour varnishes, such as "Zapon" varnishes, in blue to blue-green tints.  In an example, 4-5 parts of 1.4.5-triamino-8-p-anisidinoanthraquinone are dissolved in 1000 parts of finished nitrocellulose lacquer; the liquid gives a transparent green-blue coat on metal, glass, leather, wood, cellulose, silk, &c. The following products also dye "Zapon" varnishes blue to green: 1.5.8-triaminoanthraquinones containing in 4-position a p-toluido-, o-anisidino-, hexahydroanilido-, p-chloranilido-, p-cresidino-methylether, a  - and b  - naphthylamino-, aminonaphthol ether-, and aminodiphenyl residue.ALSO:Aminoanthraquinone derivatives are prepared by treating with a reducing agent a compound of the general formula: <FORM:0344117/IV/1> wherein x in one case stands for a nitro-group and in the other case for an NHR1-group, R, stands for hydrogen or alkyl, and R2 for an aromatic or hydroaromatic residue, and, if desired, subjecting the product to sulphonation, alkylation, or acidylation, or to two or more of these operations in succession (which operations may be carried out in any order).  The products dye cellulose derivatives, such as acetyl or alkyl cellulose, and animal fibres and colour varnishes, such as "Zapon" varnishes, in blue to blue-green tints.  The subsequent alkylation may be effected by means of alkyl esters of the aromatic sulphonic acids, alkyl halides, alkylene halides, alkylene chlorhydrins and alkylene oxides and acidulation with acetic anhydride or benzoyl chloride.  The products obtained by a subsequent methylation or ethylation are stated to be particularly valuable.  In examples, (1) 1,5-diamino - 4,8 - dinitroanthraquinone, 1,8 - diamino-4,5-dinitroanthraquinone, or a technical mixture of both is condensed with aniline and the nitrodiaminoanilidoanthraquinone reduced with alcoholic sodium sulphide to 1,5,8 - triamino - 4 - anilidoanthraquinone which dyes acetate silk blue: (2) a nitro group in 1,5 - diamino - 4,8 - dinitroanthraquinone is replaced by condensing with p-anisidine and the product reduced to 1,5,8-triamino-4-p-anisidinoanthraquinone; it dyes acetate silk green-blue.  Similar condensation products are obtained by replacing a nitro group by p-toluidine, o-anisidine, hexahydroaniline, p-chloraniline, p-cresidine-methyl ether, a - and b -naphthylamine, aminonaphthol ethers, aminodiphenyl and similar substances, followed by reduction; these products dye "Zapon" varnishes blue to green: (3) 1,5-8 triamino-4-anilidoanthraquinone is treated with dimethylsulphate in nitrobenzene and dyes acetate silk blue-green shades; a similar dyestuff is obtained by treating in alcohol with ethylene oxide, and other alkylating agents such as propyl, butyl, amyl or alkyl chlorides may also be used.  Treatment of the same product in nitrobenzene with acetic anhydride yields a dyestuff giving blue shades on acetate silk: (4) 1,5,8 - triamino - 4 - p - toluidoanthraquinone is treated with monohydrate giving a product dyeing wool green tints; a similar product results from sulphonating the 4-anilidoanthraquinone.  A further example describes the use of 1,5,8 - triamino - 4 - p - anisidinoanthraquinone in a nitro-cellulose lacquer suitable for coating a transparent blue-green on metal, glass, leather, wood, celluloid, silk, &c.  Specification 293,006, [Class 2 (iii), Dyes &c.], is referred to.