Patent GB-337374-A (GB)
Title: Improvements in the manufacture and production of derivatives of the acridone series
IPC: C09B1/34
Filed: 1929-04-26
Abstract: 337,374. Johnson, J. Y., (I. G. Farbenindustrie Akt.-Ges.). April 26, 1929. Samples furnished. Halogenated acridone derivatives.-Compounds having a condensed ring system of at least five rings comprising the acridone ring system, at least two further carbocyclic rings being connected to the said condensed ring system, and at least two ketonic groups being contained in the compounds in addition to that in the acridone ring, are treated with chlorine or bromine or both these halogens, or agents supplying these halogens, preferably in the presence of diluting media and/or halogenating catalysts. The said two further carbocyclic rings may be connected to the condensed five-ring system by direct linkages, or indirectly through a heterocyclic ring system, or they may also be condensed therewith. As suitable diluents for the process may be used high boiling organic solvents such as nitrobenzene, nitronaphthalene, di- and trichlorbenzene, or inorganic solvents such as sulphuric acid, oleum, chlorsulphonc acid, phosphoric acid, perchloric acid or other oxygen acids. As catalysts may be used metals, non-metals and compounds thereof, for example, iron, copper, manganese, antimony, iodine, selenium, phosphorus and sulphur; these may be used singly or severally. The number and orientation of the halogen atoms entering the molecule and the dyeing properties of the products may be influenced by the kind and amount of catalyst employed; thus treatment of 1.2 ; 5.6- diphthaloylacridone in trichlorbenzene with chlorine in presence of (i) 5-10 per cent of iodine and (ii) a similar amount of sulphur, yields two different dichloro derivatives dyeing different shades of red. Halogenating temperatures depend on the substance under treatment and the diluent employed, being higher when organic diluents are used than with inorganic diluents. Both halogens may be introduced by simultaneous or successive treatment with chlorine and bromine in the same or different solvents. The products may be purified by way of their oxonium sulphates, by recrystallization from, or boiling with, high boiling solvents, or by oxidation of the aqueous pastes. In examples, (1) 1.2 : 5-6-diphthaloylacridone is treated in chlorsulphonic acid in presence of iron and iodine (or instead, sulphur, antimony, manganese, phosphorus or selenium) with bromine; the product contains bromine and chlorine; oleum, monohydrate, sulphuric acid, or nitrobenzene may be used as diluent in place of chlorsulphonic acid, and chlorinated products also obtained by these means : treatment in oleum and in presence of iodine with theoretical amounts of bromine yields mono-, di- and tribromo derivatives, and other derivatives may be obtained with other catalysts or in the absence of any catalyst; chlorination in trichlorbenzene in presence of iodine yields a monochloro derivative; alternatively sulphuryl chloride without any catalyst may be used. These products dye orange-red shades, the monohalogen derivatives being stated to be particularly valuable. (2) The product obtained by condensation of 2 mols. of 1-chloranthraquinone-2-carboxylic acid and 1 mol. benzidine followed by ring closure by means of sulphuric acid, is brominated in chlorsulphonic acid in presence of sulphur (or other metal or non-metal catalyst), or in nitrobenzene in presence of iodine and iron, to give a tribromo derivative; it is chlorinated by heating the product in chlorsulphonic acid contaning sulphur, or by the introduction of further chlorine into the chlorsulphonic acid solution, or by treatment in a mixture of chlorsulphonic acid and monohydrate in presence of iron chloride with chlorine, or by treatment in nitrobenzene or trichlorbenzene with a chlorinating agent, with or without a little iodine or dimethylaniline, or by treatment with sulphuryl chloride containing a little dimethylaniline. (3) The product obtained by condensing 1 mol. of dibromo-3-4--8-9-dibenzopyrene-5-10-quinone (obtained by brominating the quinone in chlorsulphonic acid in presence of 10 per cent iodine at 60-80‹ C.) with 2 mols. of 1-aminoanthraquinone-2-aldehyde so that ring closure results, is brominated in chlorsulphonic acid in presence of iodine. (4) The product from 1 mol. of the dibromo derivative of (3) and 2 mols. anthranilic acid (with ring closure) is brominated in nitrobenzene in presence of iodine and iron. (5) The ring-closed product from 1 mol. of 1-aminoanthraquinone-2-aldehyde and 1 mol. of monobromo-3-4-8-9-dibenzopyrene-5-10-quinone (prepared by treating the quinone in oleum with 1-2 atomic proportions of bromine) is treated in trichlorbenzene in presence of iodine with chlorine or sulphuryl chloride, or in nitrobenzene in presence of iodine and iron with bromine. (6) The ring-closed product from the monobromo derivative (1 mol.) of (5) and anthranilic acid methyl ester (1 mol.) is brominated as in (4). (7) The ring-closed product from -aminoanthraquinone-2-aldehyde (1 mol.) and monobromo-4-5- 8-9-dibenzopyrene-3-10-quinone (1 mol.) (prepared by brominating the quinone in nitrobenzene in presence of iodine) is brominated as in (4). (8) Products obtained by condensing 1-aminoanthraquinone-2-aldehyde with dibromanthanthrone (prepared by brominating in dilute oleum), or with halogen benzanthrones followed by ring closure, or diphthaloylacridones generally, may be brominated in chlorsulphonic acid in presence of iodine. A number of structural formulae illustrating tyes of compounds which may be halogenated are given, and these include the ring- closed condensation product (i) from 1 mol. of 7-bromperylene-1-6-quinone (prepared by brominating perylene-1-6-quinone in aqueous suspension) and 1 mol. of anthranilic acid ester; (ii) from a # - halogen-3-4-8-9-dibenzopyrene - 5 - 10- quinone (prepared by condensing benzanthrone with m-halogenbenzoylchloride and treating the product with aluminium chloride) and anthranilic acid (molar proportions); (iii) from alpha-anthramine and 1-chloranthraquinone-2-carboxylic acid (molar proportions); (iv) from a #-#<1>-dibromo-3-4-8-9- dibenzopyrene-5-10-quinone (1 mol.) (prepared as described in (3) ) and 1 mol. each of anthranilic acid ester and 1-aminoanthraquinone-2-carboxylic acid ester; (v) from 1-chloranthraquinone-2-carboxylic acid, 1-aminoanthraquinone and 4-4'- chloraminodiphenyl (Specification 28361/12, [Class 120 (iii), Yarns &c.]). These halogenated products dye in fast clear brown to orange shades. Specifications 894/11 and 325,550 also are referred to.