Patent GB-420969-A (GB)
Title: Improvements in the manufacture and production of condensation products of the aromatic series
IPC: C07C255/32
Filed: 1933-03-06
Abstract: Compounds of the formul  <FORM:0420969/IV/1> and/or <FORM:0420969/IV/2> (wherein X is a benzene nucleus to which further aromatic or nitrogen-containing heterocyclic nuclei may be condensed, and Z represents a cyano group or a hydrocarbon radicle which may be substituted) are prepared by reacting, in the presence of a strongly alkaline condensing agent, a compound containing the group X, a nitro group and in para-position thereto a hydrogen or halogen atom, with a compound Z--CH2--CN, if necessary in the presence of oxygen.  One of the two hydrogen atoms of the methylene group in the second reactant is thereby eliminated, together with the atom in the para-position of the first reactant, to effect a coupling of the two.  If halogen is present in the para-position, hydrogen halide is split off; when hydrogen stands in the para-position, an oxidation is necessary either by means of added oxygen or at the expense of the nitro group, in which latter case hydroxylamines are formed.  The presence of air in other cases is desirable.  Condensing agents mentioned are alkali metal hydroxides and alcoholates, sodamide and sodium sulphide.  The products are useful as dyestuffs or intermediates.  Examples are given of the interaction of (1) 4-chlornitrobenzene and benzyl cyanide to give 4-nitrophenylacetonitrile; (2) nitrobenzene and benzyl cyanide to form a mixture of 4-nitrophenylacetonitrile and the corresponding hydroxylamine compound; (3) nitrobenzene and benzyl cyanide to give 4-hydroxylaminodiphenylacetonitrile; (4) 3-nitrobenzoic acid and benzyl cyanide in the presence of air to produce a nitrodiphenylacetonitrile-carboxylic acid which readily isomerizes; the use of 2-chlor-5-nitrobenzoic acid gives rise to the same product; (5) 3<1>-nitro-2-benzoylbenzoic acid and benzyl cyanide, while passing air through, to give a product which isomerizes; instead of benzyl cyanide, malonic nitrile may be used and in place of 3<1>-nitro-2-benzoylbenzoic acid, the 4<1>-chlor and 4<1>-methyl derivatives may be employed; (6) 3<1>-nitro-2-benzoylbenzoic acid or its 4<1>-methyl derivatives and acetonitrile in the presence of air; (7) 2-chlornitrobenzene and benzyl cyanide, while passing air through, giving a chlornitrodiphenylacetonitrile; (8) m-nitraniline and benzyl cyanide, in the presence of air, to give a product which dyes acetate artificial silk orange shades; (9) m-nitrotoluene with benzyl cyanide, in the presence of air; (10) 8-nitroquinoline and benzyl cyanide, while passing air through; (11) a -nitroanthraquinone and benzyl cyanide, in the presence of air; (12) o-nitroanisole and benzyl cyanide, in the presence of air, to give a hydroxylamino - methoxy - diphenylacetonitrile in admixture with the corresponding nitro compound; (13) m-nitrobenzaldehyde and benzyl cyanide, while passing air through; (14) 1-nitronaphthalene and malonic nitrile, while passing air through, to give a mixture of nitro and hydroxylamino compounds; 1-chlor-4-nitronaphthalene may be similarly condensed with benzyl cyanide.  The probable formul  of the foregoing products are given.  The Provisional Specification describes the reactants as (1) aromatic nitro and nitroso compounds containing a halogen or hydrogen atom or alkoxy group in the ortho- and/or para-position to the nitro or nitroso group, and (2) compounds containing reactive methylene groups, such as acetoacetic ester, acetonitrile, acetophenone, benzyl cyanide, succinimide and tetrahydronaphtholones.  It includes additional examples describing the interaction of (1) 4-chlornitrobenzene and succinimide: (2) 2-chlornitrobenzene and acetic acid ethyl ester to give products, of which one is a dinitrodichlordiphenylacetic acid; (3) 2-nitrobenzoic acid and acetophenone, while passing air through, to form a nitrodesoxybenzoin-carboxylic acid; (4) 2 : 5-dichlornitrosobenzene (obtained by oxidizing 2 : 5-dichloraniline with permonosulphuric acid) and acetonitrile or benzyl cyanide, in the presence of air; (5) 4-nitroanisole and benzyl cyanide to give the nitrodiphenylacetonitrile of (1).