Patent GB-340524-A (GB)
Title: Process for the manufacture and production of vat dyestuffs of the 1.2-benzanthraquinone series
IPC: C09B3/58
Filed: 1929-07-29
Abstract: 1.2-Benzanthraquinone dyes.-a -Anthraquinonyl-Bz4-amino-1.2-benzanthraquinones having a free Bz3- or 3-position are treated with acid or alkaline condensing agents whereby dyestuffs furnishing quite different shades are obtained according as to whether the above starting materials are further substituted or not, and according to the condensing agent employed. The products fall into two groups (to which structural formul  are assigned), the one group dyeing yellow to red shades, and the other blue to green.  The treatment of starting materials containing an acylamino group with acid condensing agents generally results in blue to green dyestuffs. Acid condensing agents specified are concentrated or fuming sulphuric acid, chlorsulphonic acid, metal chlorides such as aluminium, ferric or zinc chlorides, or mixtures of these, or mixtures such as sodium-aluminium-chloride; alkaline condensing agents are alkali metal hydroxides (to which phenols or alcohols are advantageously added), alcohol and arylides.  Similar vat-dyestuffs to those of the latter group (i.e. blue to green dyestuffs) are prepared by treating a  - anthraquinonyl-3-amino-1.2-benzanthraquinones containing at least one acylamino group with acid condensing agents.  The acylamino group in the resulting condensation products may be saponified and the hydrogen atoms of the amino group replaced by other radicles, or the amino group itself replaced by other radicles by Sandmeyer's reaction, if desired.  In some cases substituents may also enter the molecule by acting with acid condensing agents such as aluminium or iron chloride, chlorosulphonic or sulphuric acid, on the above starting materials.  In examples, (1) the condensation product of Bz4-brom-1.2-benzanthraquinone (obtained by brominating 1.2-benzanthraquinone in glacial acetic acid) with 1-aminoanthraquinone is heated with sulphuric acid at 130 DEG , or with sodium-aluminium-chloride at 150 DEG , or with zinc chloride at 200 DEG , to give a product dyeing yellow shades; similar dyestuffs are obtained from the product of Bz4-bromo-1.2-benzanthraquinone and 1-amino-2-methylanthraquinone; a brown-olive dyeing product is, however, obtained by heating with potassium pyrosulphate at 360 DEG : (2) the starting material of (1) is heated with a mixture of aluminium chloride and pyridine at 220-230 DEG , or with potash and m-cresol at 230-240 DEG  C., to give a product dyeing blue-green shades: (3) the condensation product from Bz4-bromo-1.2-benzanthraquinone (1 mol.) and 1.5-diaminoanthraquinone (1 mol.) is heated with sulphuric acid at 130 DEG  to give a product dyeing red shades, and with potash and m-cresol at 210-220 DEG  to give a product dyeing bluish-grey shades: (4) the condensation product from Bz4-bromo-1.2-benzanthraquinone (2 mols.) and 1.5-diaminoanthraquinone (1 mol.) is heated with potash and m-cresol at 210-220 DEG  to give a product dyeing red shades: (5) the condensation product of Bz4-bromo-1.2-benzanthraquinone (1 mol.) and 1-amino-4-(or 5-)-benzoylaminoanthraquinone (1 mol.) is treated with chlorosulphonic acid, preferably with the addition of pyridine or other tertiary base, at room temperature to give a product dyeing green shades: (6) the condensation product from 3-chloro-1.2-benzanthraquinone and 1 - amino - 4 - benzoylaminoanthraquinone is heated with aluminium chloride and pyridine at 170 DEG ; the product dyes blue shades; by using iron chloride as condensing agent a product containing chlorine and dyeing similar shades is obtained: (7) the condensation product from 3-chloro-1.2-benzanthraquinone and 1-amino-5-benzoylaminoanthraquinone is heated with chlorosulphonic acid at 50-55 DEG ; the product dyes blue shades, and may be saponified by heating with sulphuric acid to give an amino derivative dyeing reddish-blue shades.  This amino derivative may be further transformed into other dyestuffs by replacing the hydrogen atoms attached to the amino group by substituents according to the usual methods, or by diazotizing and replacing the diazo group by hydrogen (to give a blue-green dyestuff), or by other substituents.