Patent GB-585798-A (GB)
Title: Manufacture of anthraquinone derivatives
IPC: C09B6/00
Filed: 1943-04-19
Abstract: Aminoanthraquinone derivatives, which are dyes or intermediates therefor, are obtained by reaction of a derivative of the general formula <FORM:0585798/IV/1> wherein "acyl" is the residue of a carboxylic acid and X represents H or any substituent, with an amine carrying a reactive H in an amino group or with two such amines, the amine or amines being used in such proportion that 1 mol. of the anthraquinone derivative reacts with 2 mols. of the same or 1 mol. of each of the different amines.  The products may be subjected to further treatment with a carbazolising agent and/or with an agent capable of introducing a substituent.  The Acyl residue may be that of a carboxylic acid of the aliphatic, hydroaromatic, aromatic or heterocyclic series, e.g. of acetic, cinnamic, benzoic, p-chlorobenzoic or nicotinic acid.  Specified amines are aminopyrenes, 1-aminoanthraquinone and its 4- or 5-benzoylamino and 5 - benzoylamino - 8 - methoxy derivatives, aminodibenzanthrones, 4 - amino - anthraquinone-2 : 1(N)-acridone, and halogen, alkyl or sulphonic acid substitution products of such amines.  Examples (1) to (7) relate to the reaction of (1) 1 : 4-dichloro-5-benzoylaminoanthraquinone (1 mol) with 1-aminoanthraquinone (2 mols.) in boiling naphthalene or nitrobenzene in presence of sodium carbonate and cuprous chloride; (2) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with 1-amino-4- or 5-benzoylaminoanthraquinone (2 mols.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride; (3) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with 1-amino-8-benzoylamino-anthraquinone or 1-amino-5-benzoylamino-8-methoxy-anthraquinone (2 mols.) in boiling nitrobenzene in presence of sodium carbonate and cuprous chloride; (4) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with 4-aminoanthraquinone-2 : 1(N)-acridone (2 mols.) in boiling nitrobenzene in presence of sodium carbonate and cuprous chloride; the product gives grey vat dyeings on cotton; (5) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with 3-aminopyrene (2 mols.) in boiling nitro benzene in presence of sodium carbonate and cuprous chloride; the product gives yellow-olive vat dyeings on cotton; (6) 1 : 4-dichloro-5-nicotinylamino-anthraquinone (1 mol.) with 1-aminoanthraquinone (2 mols.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride; (7) 1 : 4-dichloro-5-p-chlorobenzoylamino-anthraquinone (1 mol.) with 1-aminoanthraquinone (2 mols.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride; (7) 1 : 4-dichloro-5-p-chlorobenzoylamino-anthraquinone (1 mol.) with 1-aminoanthraquinone (2 mols.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride.  Example (8) relates to the treatment of the trianthrimide product of (1), (2), (6) and (7) with anhydrous aluminium chloride in boiling pyridine; the products give various brown vat dyeings on cotton.  Examples (9) to (12) relate to the reaction of (9) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with p-toluidine (2 mols.) in presence of potassium acetate and cuprous chloride; the product may be sulphonated to obtain a water-soluble dyestuff dyeing wool green; (10) 1 : 4 - dichloro - 5 - benzoylaminoanthraquinone (1 mol.) with 2-aminonaphthalene (2 mols.) in presence of potassium acetate and cuprous chloride; the product may be sulphonated to obtain a water-soluble dyestuff dyeing wool green; (11) 1 : 4-dichloro-5-benzoylamino-anthraquinone (1 mol.) with anthranilic acid (2 mols.) in alcohol at 150-155 DEG  C. under pressure in presence of potassium acetate and cuprous chloride; (12) 1 : 4-dichloro-5-benzoylaminoanthraquinone (1 mol.) with b -aminoethanol (2 mols.) in presence of potassium acetate and cuprous chloride.  Example (13) relates to the treatment of the trianthrimide product of (1) with a fused mixture of anhydrous aluminium chloride and common salt at 125-130 DEG  C.; the product gives brown vat dyeings on cotton.  Example (14) relates to the treatment of the trianthrimide product of (1) with titanium tetrachloride in pyridine at 125-135 DEG  C.  Example (15) relates to the reaction of 1 : 4-dichloro-5-benzoylaminoanthraquinone (1 mol.) with 1-aminoanthraquinone (1 mol.) and 1-amino-4- or 5-benzoylamino-anthraquinone (1 mol.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride.  Example (16) relates to the treatment of the trianthrimides of (15) with aluminium chloride in pyridine at 130-135 DEG  C.; the products give brown vat dyeings on cotton.  Examples (17) and (18) relate to the treatment of the trianthrimide products of (3) and (4) respectively with aluminium chloride in boiling pyridine; the products give red-brown and olive-green vat dyeings respectively on cotton.  Examples (19) to (21) relate to the reaction of 1 : 4-dichloro-5 : 8-dibenzoylamino-anthraquinone, 1 : 4-dichloro - 5 - acetylamino - anthraquinone and 1 : 4-dichloro-5-cinnamyl-amino-anthraquinone respectively (1 mol.) with 1-aminoanthraquinone (2 mols.) in boiling naphthalene in presence of sodium carbonate and cuprous chloride and treatment of the products with aluminium chloride in pyridine as in (8); the products give grey-brown, olive-black-brown and reddish black-brown vat dyeings respectively on cotton.  Examples are also given of the process of the vat dyeing of cotton with the product of Example (8).