Patent GB-326148-A (GB)
Abstract: 326,148. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). Dec. 4, 1928. Benzanthrone dyes.-Vat dyes, which apparently contain acridine or acridone rings, are made by condensing mono- or di-halogenated derivatives of benzanthrone or its nuclear substitution products, or of 2 : 2<1>- or Bz1: Bz1<1>-dibenzanthronyl, or of Bz1: Bz1<1> - dibenzanthronylsulphide, with 1-aminoanthraquinone-2-aldehyde or an azomethane derived therefrom, such as 1- aminoanthraquinone - 2 - aldehyde - anil, or with anthraquinone 1 : 2-isoxazole, or by condensing the coresponding mono- and di-amino derivatives of benzanthrone, &c. with 1-chloranthraquinone- 2-aldehyde. The condensation is carried out at raised temperatures, preferably in the presence of an organic diluent at the boiling point, and advantageously with the addition of an acidbinding agent and a catalyst. In examples, (1) Bz-1-brombenzanthrone is condensed with 1- aminoanthraquinone-2-aldehyde in nitrobenzene with the addition of cuprous chloride and potash, yielding a product which dyes cotton in fast brown shades which become violetish on standing; similar dyestuffs are obtained from 1-aminoanthraquinone-2-aldehyde-anil and anthraquinone-1 : 2- isoxazole, (2) 8-chlorbenzanthrone is condensed with 1-aminoanthraquinone-2-aldehyde in nitrobenzene in the presence of sodium acetate and copper oxide; the product, which is probably 2<1> : 1<1> - anthraquinone-7 : 8-benzanthroneacridone dyes in reddish-brown shades, while from 2-chlorbenzanthrone a yellowish-brown product is obtained, (3) 6-chlorbenzanthrone is similarly condensed with 1 - aminoanthraquinone-2-aldehyde; the product dyes in brown shades, (4) 2 : 6-dichlorbenzanthrone is condensed with 1-aminoanthra.quinone-2-aldehyde (2 mols.) in nitrobenzene or naphthalene with addition of copper oxide and sodium acetate, the product (which may also be obtained from 2 : 6-dibrombenzanthrone) dyes in brown shades, (5) 6 : Bz-1-dibrombenzanthrone is condensed with 1-aminoanthraquinone- 2-aldehyde (2 mols.) in nitrobenzene in the presence of potash and copper acetate, yielding a dianthraquinone-benzanthrone-acridine dyeing in yellowish-brown shades; a similar product i s obtained from Bz1-brom-6-chlorbenzanthrone, or by using the aldehyde-anil instead of the aldehyde a dyestuff dyeing brownish-violet shades is obtained, (6) Bz1-brom-6-nitrobenzanthrone is condensed with 1-aminoanthraquinone-2-aldehyde in nitrobenzene in the presence of potash and cuprous chloride yielding a product, dyeing dark shades, which may be purified by vatting and reprecipitating, whereby the nitro group is reduced to the amino group; a similar dyestuff is obtained by using Bz1 - brom - 6 - benzenesulphamino - benzanthrone and saponifying the product, (7) 6-aminobenzanthrone is condensed with 1-chloranthraquinone-2-aldehyde in nitrobenzene with addition of copper oxide and sodium acetate; the product is identical with that of example (3), (8) 2 : 6- diaminobenzantbrone is similarly condensed with 1-chloranthraquinone-2-aldehyde (2 mols.), yielding the product of example 4, (9) dibrom-2 : 2'- dibenzanthronyl is condensed with 1-aminoanthraquinone-2-aldehyde, yielding a product which dyes cotton in brown shades; the corresponding dyestuff from anthraquinone-1 : 2-isoxazole dyes in somewhat more olive brown shades, (10) dibrom- Bz1- : Bz1<1>-dibenzanthronyl is condensed with 1- aminoantbraquinone - 2 - aldehyde and with the corresponding aldehyde-anil; the products dye in brownish-olive and brownish-grey shades, and (11) 6 : 6<1>-dibromo-Bz1 : Bz1<1>-dibenzanthronyl is condensed with 1-aminoanthraquinone-2-aldehyde; the product dyes yellowish-brown shades. Dibenzanthronyl derivatives.-Amino derivatives of Bz1 : Bz1<1>-dibenzanthronyl are made by treating the corresponding halogen derivatives with acylamides, particularly arylsulphamides, and saponifying the products. Dibrom-2 : 2<1>-dibenzanthronyl is made by brominating in chlorsulphonic acid, and dibrom-Bz1 : Bz1<1>-dibenzanthronyl by introducing Bz1 : Bz1<1> - dibenzanthronyl into an excess of bromine. 6 : 6<1> - Dibrom-Bz1 : Bz1<1>-dibenzanthronyl sulphide is obtained by treating 6 : Bz1-dibrom-benzanthrone with potassium xanthogenate in nitrobenzene. Bz1-brom - 6 - nitrobenzanthrone is made by nitrating Bz1-brombenzanthrone in nitrobenzene. 2 : 6-Diaminobenzanthrone is made by treating the corresponding halogen compound with an acid amide, particularly an arylsulphamide, and saponifying the product.