Patent GB-513846-A (GB)
Title: Manufacture of polynuclear compounds
IPC: C07D209/86
Filed: 1938-03-15
Abstract: 513,846. Polynuclear compounds. CARPMAEL, A. (I.G. Farbenindustrie Akt.-Ges.). March 15, 1938, Nos. 8038/38, 13823/38, 35881/38, 6746/39 and 7950/39. [Class 2 (iii)] An aromatic or heterocyclic compound not substituted by an amino or a hydroxyl group is treated with an aromatic or heterocyclic diazo compound which has been converted into a water-insoluble or sparingly soluble form; the azo group is thus eliminated, and the nuclei of the two components are linked together. The production of the diazo compound in a waterinsoluble or sparingly soluble form may be effected by forming a suitable salt or double salt of the diazo compound or by combining the diazo compound with a soluble primary or secondary amine to form a diazoamino compound. When the diazo compound is taken as a salt or double salt, the reaction is preferably effected in the presence of a condensing agent, e.g., a halide of aluminium or iron. When the diazo compound is taken as a diazoamino compound, the latter is decomposed by an acid (or a reagent which yields an acid), immediately before the reaction. In a modification, the reaction is effected by producing the diazo compound from the corresponding amine in the presence of the other reaction component. In the examples, (1) the double salt from diazotized 2-toluidine and zinc chloride is warmed with benzene in the presence of aluminium chloride, whereby 2-methyldiphenyl is obtained ; similarly, 4-toluidine and benzene yield 4-methyldiphenyl, 2-aminonaphthalene and benzene yield 2-phenylnaphthalene, pseudocumidine and benzene yield 2:4:5-trimethyldiphenyl, 4- benzoylaminoaniline and benzene yield 4- benzoylaminodiphenyl (identical with the product obtained by benzoylating 4-aminodiphenyl), 2:5-dichloraniline and benzene yield 2:5-dichlorodiphenyl, and 2:5-dichloraniline and chlorobenzene yield 2:5:4<1>-trichlorodiphenyl; (2) the double salt from diazotized 3:4-dichloraniline and zinc chloride is boiled with benzene in the presence of ferric or aluminium chloride or antimony trichloride or stannic chloride, whereby 3:4-dichlorodiphenyl is obtained; similarly, 4-methoxyaniline and m-xylene yield 2:4-dimethyl-4<1>-methoxydiphenyl; (3) the diazo compound from 5-chloro-2-aminotoluene is converted into its salt with anisolesulphonic acid, and the salt is boiled with benzene in the presence of aluminium chloride, whereby 2-methyl-4-chlorodiphenyl is obtained ; similarly, m-nitraniline and benzene yield 3-nitrodiphenyl ; (4) 1-aminoanthraquinone in sulphuric acid solution is diazotized by addition of sodium nitrite or nitrosylsulphuric acid, and the sparingly soluble diazonium sulphate is isolated and heated with benzene in the presence of aluminium chloride, whereby 1-phenylanthraquinone is obtained ; similarly, Bz1-aminobenzanthrone and benzene yield Bz1-phenylbenzanthrone, and Bz1-aminobenzanthrone and m-xylene yield Bzl-(2<1>:4<1>-dimethylphenyl) benzanthrone; (5) dry 1-diazonaphthalene-4- sulphonic acid is heated with benzene in the presence of aluminium chloride ; a mixture of 1-phenylnaphthalene-4-sulphonic acid and 1- chloronaphthalene-4-sulphonic acid is obtained, and is separated by converting it, by way of the sulphochlorides, into a mixture of sulphonamides, from which 1-phenylnaphthalene-4- sulphonamide is separated by virtue of its low solubility; the product yields 1-phenyl-4- naphthol when treated with caustic alkali; similarly, 2-diazonaphthalene-6-sulphonic acid may be converted into 2-phenylnaphthalene- 6-sulphonamide, which yields 2-phenyl-6- naphthol when treated with caustic alkali; correspondingly substituted products are obtained by using chlorobenzene or m-xylene in place of benzene ; (6) the diazoamino compound from diazotized 3:4-dichloraniline and dimethylamine is heated with nitrobenzene, and hydrogen chloride is passed through the mixture ; a nitrodichlorodiphenyl is obtained ; if aniline is used instead of 3:4-dichloraniline, 2-nitrodiphenyl and a subordinate proportion of 4-nitrodiphenyl are obtained ; (7) the diazoamino compound from diazotized aniline and 'dimethylamine is treated as in example 6 with benzophenone, whereby 4-benzoyldiphenyl is obtained ; if phthalic anhydride is used in place of benzophenone, a mixture of diphenyl-2:3- and - 3:4-dicarboxylic acid anhydrides is obtained, and may be separated by vacuum distillation; similarly, the diazoamino compound from diazotized 3:4-dichloraniline and dimethylamine' yields by reaction with benzaldehyde a dichlorodiphenyl aldehyde, the phenylhydrazone of which is described ; (8) the diazoamino compound from diazotized 1:2-dimethyl-4-aminobenzene and dimethylamine is treated with benzene as in example 6 to yield 3:4-dimethyldiphenyl; similarly, 1:3-dimethyl-4-aminobenzene and benzene yield 2:4-dimethyldiphenyl 3-aminocarbazole and benzene yield 3-phenylcarbazole, 4-aminodiphenyl and o-dichlorobenzene yield 3:4-dichloro-4<1>-phenyldiphenyl, 2-amino-4:5-dichlorotoluene and benzene yield 2-methyl-4:5-dichlorodiphenyl, 1-methoxy-2- amino-4:5-dichlorobenzene and benzene yield 2-methoxy-4:5-dichlorodiphenyl, and 1-phenoxy- 2-amino-4:5-dichlorobenzene and benzene yield 2-phenoxy-4:5-dichlorodiphenyl; (9) the diazoamino compound from diazotized 4-chloro-2- aminotoluene and sarcosine is treated with benzene in the presence of aluminium chloride to yield 2-methyl-5-chlorodiphenyl; (10) the diazoamino compound from 3:4-dichloraniline and dimethylamine is warmed with benzene in the presence of aluminium chloride or formic acid, whereby 3:4-dichlorodiphenyl is obtained ; if diphenyl is used in place of benzene, a mixture of 3:4-dichloro-2<1>- and -4<1>-phenyldiphenyl results ; (11) the diazo compound from 3-nitro- 4-aminoanisole, in the form of its salt with anisolesulphonic acid, is boiled with benzene to yield 2-nitro-4-methoxydiphenyl; similarly, the diazo compound from 2-amino-4-chloro-5-nitroanisole, in the form of its cobaltous chloride double salt, yields 2-methoxy-4-nitro-5-chlorodiphenyl by reaction with benzene ; (12) the diazo amino compound from diazotized 2:3- dichloraniline and diethylamine is boiled with benzene in the presence of aluminium chloride to yield 2:3-dichlorodiphenyl; similarly, 2:4:5- trichloraniline and benzene yield 2:4:5-trichlorodiphenyl; (13) the diazoamino compound from diazotized 4-aminophthalic acid diethyl ester and dimethylamine is treated with benzene, and hydrogen chloride is passed into the mixture ; diphenyl-3:4-dicarboxylic acid diethyl ester is obtained; similarly, anthranilic acid methyl ester and naphthalene yield o-(alpha-naphthyl) benzoic acid methyl ester ; (14) the diazoamino compound from diazotized 3-amino-N-ethylcarbazole and dimethylamine is treated with benzene as in example 13 to yield 3-phenyl-N- ethylcarbazole; (15) a mixture of 1-aminoanthraquinone and benzene is treated with nitrous gases, optionally while removing water by azeotropic distillation ; 1-phenylanthraquinone is obtained ; the same product is obtained by treating the initial mixture with sodium nitrite and acetic, formic or phosphoric acid or an acid-reacting salt such as sodium bisulphate or zinc sulphate; similarly, 1:5- diaminoanthraquinone and 1-amino-5-chloranthraquinone yield, by reaction with benzene, 1:5-diphenyl- and 1-phenyl-5-chloro-anthraquinone respectively; (16) a mixture of 3- amino-N'-ethylcarbazole and benzene is treated as in example 15 to yield 3-phenyl-N-ethylcarbazole ; (17) a mixture of 3:4-dichloraniline and nitrobenzene is treated as in example 15 to yield 4-nitro-3<1>-4<1>-dichlorodiphenyl; similarly, aniline and benzene yield diphenyl; (18) a mixture of 1-aminoanthraquinone and nitrobenzene is treated as in example 15 to yield a mixture of 1-(o- and p-nitrophenyl) anthraquinone ; (19) a mixture of 1-amino-5-benzoylaminoanthraquinone and benzene is treated as in example 15 to yield 1-phenyl-5-benzoylaminoanthraquinone, which yields 1-phenyl-5- aminoanthraquinone by saponification; 1- amino-4-benzoylaminoanthraquinone similarly yields 1-phenyl-4-benzoylaminoanthraquinone ; (20) a mixture of aniline and benzene is treated as in example 15 to yield diphenyl ; similarly, p-toluidine and benzene yield 4-methyl'diphenyl, p-chloraniline and benzene yield 4-chlorodiphenyl and p-nitraniline and benzene yield 4-nitrodiphenyl. Reference is made also to the reaction of the diazo compounds with benzoic acid esters and also with thiophene, pyridine and quinoline and their derivatives containing halogen atoms or nitro, aldehyde, keto, carboxylic acid ester or carboxylic anhydride groups. The first and third Provisional Specifications state generally that the diazo compound and (or) the aromatic or heterocyclic compound with which it is condensed may contain as substituents a halogen atom, a trifluoromethyl, nitro, sulphone or sulphoxide group, or a carboxylic or sulphonic group or a group derived therefrom, such as an ester, amide, nitrile, aldehyde or ketonic group ; the aromatic or heterocyclic compound may also be substituted by an alkyl, alkoxy or aryloxy group. Diphenylene oxide and phenylthiazole are mentioned in the first Provisional Specification as suitable heterocyclic compounds.