Patent GB-542577-A (GB)
Title: Manufacture of condensation products
IPC: C09B1/32
Filed: 1940-04-15
Abstract: 542,577. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. April 15, 1940, Nos. 6773 and 6774. Convention dates, April 15,1939 and March 16,1940. [Class 2 (iii)] Vat dyes are obtained by treating with acid condensing agents compounds of the general formula R-(NHR<SP>1</SP>)n, where R is the radicle of a compound not capable of being vatted which contains at least one heterocyclic oxygen or sulphur atom and at least one aromatic ring of 6 carbon atoms, R<SP>1</SP> is the residue of a compound capable of being vatted, and n is a whole number. The compounds of this general formula, which are often themselves vat dyes, may be made by re-acting a compound of the formula R-(halogen )n with an amine of the formula R<SP>1</SP>-NH 2 , or by reacting an amine R-(NH 2 )n with a compound of the formula R<SP>1</SP>-halogen. Compounds containing the radicle R include diphenylene oxides, sulphides and sulphones, xanthones, and compounds of the type of dinaphthylenethiophene. Vattable compounds containing the radicle R' include simple anthraquinones and anthraquinones having a ring fused on in 1 and 9 positions, such as anthapyridones, pyrazoleanthrones, thiazoleanthrones and anthrapyrimidines. The parent materials of the general formula may be obtained by heating the components together in a solvent or diluent, e.g. nitrobenzene, naphthalene or amyl alcohol, advantageously in the presence of an acid-binding agent and of a copper catalyst. As acid condensing agents those suitable for effecting ring closure, particularly carbazole ring closure, are suitable ; concentrated sulphuric acid of chlorsulphonic acid, and aluminium chloride, with or without the addition of common salt or sulphurous acid, are specified. The products are preferably treated with oxidizing agents such as air, nitrous acid, perboric acid or hypochlorous acid. The process may in some cases be carried out in stages ; thus a product containing a replaceable substituent such as halogen may be again caused to react with an amine and, if desired, again treated with an acid condensing agent. In many cases the tinctorial properties of the products can be improved by halogenation. In examples the products obtained by condensing 2 : 7 -, 2 : 6 - or 3 : 6 - dibromodiphenylene oxide, dibromodinaphthylenethiophene, dibromo-2 : 3-benzodiphenyleneoxide, dibromothianthrene, dibromodiphenylene sulphide, dibromodiphenylenesulphone, 2 : 7-dibromoxanthane, 3 : 6-dichloroxanthone (Example 1 of Specification 505,371) or dibromonaphthoxanthone with 1-aminoanthraquinone or 1- amino-4 (or 5)-benzoylaminoanthraquinone are treated with concentrated sulphuric acid or with an aluminium chloride-sodium chloride mixture ; the products dye cotton from the. hydrosulphite vat in various shades, chiefly brown, violet and olive. In a further example the product obtained by treating with aluminium chloride the product from 3 : 6-dibromodiphenylene oxide and 1-aminoanthraquinone is brominated. Bromine compounds. 2 : 6- and 2 : 7-Dibromodiphenylene oxides are made from the corresponding diamino compounds by the Sandmeyer reaction. 3 : 6-Dibromodiphenylene oxide is made by brominating diphenylene oxide in carbon tetrachloride, with addition of some iodine and ferric chloride. Dibromodinaphthylenethiophene is made by brominating dinaphthylenethiophene in nitrobenzene. Dibromo-2 : 3-benzodiphenylene oxide is made by brominating 2 : 3-benzodiphenylene oxide in carbon tetrachloride with addition of iodine and ferric chloride. Dibromothianthrene is made by brominating thianthrene in nitrobenzene. Dibromodiphenylene sulphide is made by bromination in carbon tetrachloride ; the corresponding sulphone is obtained by oxidation with chromic acid. Dibromonaphthoxanthone is made by suspending 6-bromo-2- oxy-3-naphthoic acid in α-chloronaphthalene and heating with acetic anhydride. The Specification as open to inspection under Sect. 91 comprises also the use as parent materials of compounds of the general formula R-(NHR<SP>1</SP>)n, in which R may be the radicle of any non-vattable aromatic compound whose ring system is interrupted by at least one hetero atom or by at least one carbon atom which does not enter into the aromatic conjugation of double linkages. Such compounds include carbazoles, acridones, quinolines, phenanthridones, fluorenes, x- and #-truxenes, and fluorenones. In further examples, the products obtained by condensing 2-bromofluorene, 2 : 7 - dibromofluorenone, 3 : 6 - dibromocarbazole, 3 : 6 - dibromo - 9 - ethylcarbazole (made by bromination in carbon disulphide), 3 : 6 - dibromo - 9 - benzoylcarbazole, tribromo-α-truxene (made by brominating α-truxene in nitrobenzene), dibromoacridone (made by brominating acridone in nitrobenzene), the compound obtained from 2-amino- 6-bromonaphthalene by. the Skraup reaction, dibromo-#-naphthindenone (made by bromination in nitrobenzene), mono- or di-bromophenanthridone (made by brominating phenanthridone in glacial acetic acid or nitrobenzene) and 2 : 6-dibromonaphthindenone with #- aminoanthraquinone or 1-amino-4 or 5-benzoylaminoanthraquinone are treated with acid condensing agents. This subject-matter does not appear in the Specification as accepted.