Patent GB-190122128-A (GB)
Title: Improvements in the Manufacture and Production of New Derivatives of the Anthraquinone Series.
Inventor: NEWTON HENRY EDWARD
Filed: 1901-11-02
Granted: 1902-10-02
Abstract: 22,128. Newton, H. E., [Farbenfabriken vorm. F. Bayer & Co.]. Nov. 2. Alkylated amidoanthraquinones; dyes, artificial. -Relates to the production of alkylated amidoanthraquinones. Consists in two general methods, viz. (a) in treating with primary and secondary amines of the aliphatic series, or with piperidine, piperazine, or the like, such anthraquinone derivatives as contain in the alpha-position negative substituents, such as chlorine or bromine atoms, nitro- or hydroxylgroups, or the like, whereby the negative groups are replaced by the amine radicle employed ; and (b) in alkylating amines of the anthraquinone series by the known methods, or by a new process consisting in using formaldehyde and a strong acid. The alkylated amidcanthraquinones thus produced yield blue to green shades, and, as they are more basic than the corresponding unalkylated amido compounds, they dye level shades. Examples of the first method are given in which alpha-mononitro-, alpha-monochloro-, or alpha-monobromoanthraquinone is converted into alpha-monomethylamidoalpha-dimethylamido-, and alpha-piperidoanthraquinone by means of monomethylamine, dimethylamine and piperidine, respectively alpha1 alpha3- dinitro-, alpha1 alpha3-dichloro, or alpha1 alpha3-dibromo-anthraquinone is converted into alpha1 alpha3-nitromethylamido- and alpha1 as-dimethyldiamidoanthraquinone by means of monomethylamine ; the corresponding alpha1 alpha4-derivatives of anthraquinone are similarly produced ; analogous alpha1 alpha3- and alpha1 alpha4-derivatives of anthraquinone are produced by using ethylamine, benzylamine, dimethylamine, piperidine, or the like ; alpha1 alpha2- dimethylamido-oxyanthraquinone, which has both basic and acid properties, is produced from quinizarin and dimethylamine ; a, alpha3-dichloroalpha2 a,- dinitroanthraquinone is converted into alpha1 alpha3-tetramethyldiamido alpha2 alpha4-dinitroanthraquinone by means of dimethylamine; similar compounds are produced by substituting in the preceding process alpha1 alpha4-dichloroalpha2 alpha3-dinitroanthraquinone, alpha1 alpha2- chloronitroanthraquinone, or the corresponding bromo compounds, on the one hand, and monomethylamine, monoethylamine, &c. on the other ; alkylated diamido - anthraquinones containing different alkylated amido groups, such as alpha1 alpha3- methylamido benzylamido anthraquinone, are produced from anthraquinone derivatives which contain one or more alkylated amido groups and one or more negative substituents, by means of amines containing other alkyls than those present in the initial compounds ; anthraquinone derivatives containing alkylated or similar amido groups and alphylated amido groups, such as alpha1 alpha3-amidopiperidoanthraquinone, are produced from anthraquinone derivatives containing negative substituents and alphylamido groups by means of primary or secondary amines or the like, or from anthraquinone derivatives containing negative substituents and alkylamido groups by means of primary aromatic amines. The second method is illustrated by examples in which alpha-monoamidoanthraquinone alpha1 a4- and alpha1 alpha3-diamidoanthraquinones, the dibromoalpha-amidoanthraquinone of Specification No. 19,531, A.D. 1899, the condensation product of dibromoalpha-amidoanthraquinone and p-toluidine described in Specification No. 19,531, A.D. 1899, and the sulphonic acid thereof, are alkylated to a greater or less extent by means of dimethyl sulphate ; and in which alpha-amidoanthraquinone is alkylated by means of hydrobromic acid and methyl alcohol. An example is also given in which a solution of alpha-monoamidoanthraquinone in concentrated sulphuric acid is mixed at 20‹-30‹ C. with formaldehyde, the mixture is subsequently heated to 55‹-60‹ C., and filtered when cool, and alpha-monomethylamidoanthraquinone is precipitated from the filtrate by addition of water. Symmetrical alpha1 alpha3- and alpha<1> alpha4-dimethyl-diamidoanthraquinones may be produced in a similar manner.