Patent GB-345728-A (GB)
Title: Manufacture of vat-dyestuffs
IPC: C09B5/06
Filed: 1930-01-20
Abstract: Benzanthronepyrazolanthrone derivatives are prepared by treating a Bzl-benzanthronyl-Pyl-pyrazolanthrone in which the 2-positions of the benzanthrone and pyrazolanthrone nuclei are free and which contains a substituted amino-residue and may contain further substituents, with an alkaline condensing agent. The above term "substituted amino-residue" includes nitrogen-containing groups in which one of the valencies of the nitrogen atom is bound to the nucleus of the parent material, whereas the other two valencies may form part of a heterocyclic ring or may be bound to any organic residues (including hydrogen), other than a di-benzanthrone or isodibenzanthrone residue, at least one of such organic residues not being hydrogen.  The products are similar to those of Specifications 344,057 and 344,147 in some cases, but in others they may differ, probably owing to further structural modification of the molecule during condensation. In examples products are obtained by submitting to alkaline condensation the following bodies:-(1) pyrazolanthrone (1 mol.) condensed with 6-Bzl-dibrombenzanthrone (1 mol.), and this 6-monobromo-Bzl - benzanthronyl - Pyl - pyrazolanthrone condensed with (i) 1-aminoanthraquinone (1 mol.) (dyes blue-grey); (ii) 2-aminoanthraquinone (1 mol.) (dyes blue-grey); (iii) 1.4-diaminoanthraquinone (1 mol.) (dyes blue-grey); (iv) 1.2-diaminoanthraquinone (1 mol.) (dyes blue-grey); (v) 1-amino-4-benzoylaminoanthraquinone (1 mol.) (dyes greenish blue-grey); (vi) 1-amino-5-benzoylaminoanthraquinone (1 mol.) (dyes reddish blue-grey); (vii) 1-aminoanthraquinone-2-aldehyde (1 mol.) (dyes neutral grey); (viii) Bzl-aminobenzanthrone (1 mol.) (dyes greenish blue-grey); (ix) the reduced product from molecular proportions of pyrazolanthrone and mononitrated Bzl-bromobenzanthrone (1 mol.) (dyes greenish blue-grey); (x) pyrazolanthrone (1 mol.) (dyes greenish-blue); (xi) carbazole (1 mol.) (dyes blue-grey) : (2) (5)-dimethylaminopyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) (dyes violet-blue): (3) 4-dimethylaminopyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) (dyes greenish blue-grey): (4) 8-chlorpyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (1 mol.) (dyes greenish grey-blue): (5) 5-chlorpyrazolanthrone (Specification 264,503, [Class 2 (iii), Dyes &c.]), (1 mol.) is condensed with Bzl-brombenzanthrone (1 mol. (and the product condensed with 1-aminoanthraquinone (1 mol.) (dyes grey-green): (6) 4-chloropyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (1 mol.) (dyes olive-green): (7) 3-bromopyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (1 mol.) (dyes olive-green): (8) 5-chlorpyrazolanthrone (1 mol.) condensed with 6-Bzl-dibrombenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (2 mols.) (dyes olive-grey): (9) 8-chlorpyrazolanthrone (1 mol.) condensed with 6-Bzl-dibrombenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (2 mols.) (dyes grey); (10) 8-aminopyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (2 mols.) (dyes greenish blue-grey): (11) 8-aminopyrazolanthrone (1 mol.) condensed with Bzl-brombenzanthrone (1 mol.) and benzoylated (dyes greenish-blue): (12) pyrazolanthrone (1 mol.) condensed with Bzl - bromo - 5 - 8 - dichlorbenzanthrone (1 mol.) and the product condensed with 1-aminoanthraquinone (2 mols.) (dyes greenish-grey): (13) dichlorbenzanthronyl-Pyl-pyrazolanthrone (1 mol.) condensed with 1-aminoanthraquinone (2 mols.) (dyes grey). Specifications 316,156, 318,180, and 324,079, [all in Class 2 (iii), Dyes &c.], are also referred to.  Pyrazolanthrone derivatives. 5-Dimethylaminopyrazolanthrone is prepared by acting on 5-chloranthraquinone-1-hydrazine under pressure and at 160-170 DEG C., with alcoholic dimethylamine. 4-Dimethylaminopyrazolanthrone is prepared by reacting 1-chloro-4-dimethylaminoanthraquinone in pyridine solution with hydrazine (see Specification 22128/01, [Class 2, Acids and salts, Organic &c.],).  4-Chlorpyrazolanthrone is obtained from 1.4-dichloranthraquinone and hydrazine in pyridine, and similarly 3-bromopyrazolanthrone from 1.3-dibromanthraquinone. 8-Aminopyrazolanthrone is obtained by reacting hydrazine with 1-chloro-8-aminoanthraquinone. Dichlorobenzanthronyl-Pyl-pyrazolanthrone is prepared by chlorinating Bzl-benzanthronyl - Pyl - pyrazolanthrone in chlorsulphonic acid and in presence of iodine at ordinary temperatures. Bzl-Bromo-5.8-dichlorobenzanthrone is prepared by benzanthronizing 1.4-dichloranthraquinone to 5.8-dichlorbenzanthrone and brominating the latter.