M-Nitrobenzonitrile

Fig. 3 Electrochemical and homogeneous standard free energies of activation for self-exchange in the reduction of aromatic hydrocarbons in A./V-dimethylformamide as a function of their equivalent hard sphere radius, a. 1, Benzonitrile 2, 4-cyanopyridine 3, o-toluonitrile 4, m-toluonitrile 5, p-toluonitrile 6, phthalonitrile 7, terephthalonitrile 8, nitrobenzene 9, m-dinitrobenzene 10, p-dinitrobenzene 11, m-nitrobenzonitrile 12, dibenzofuran 13, dibenzothiophene 14, p-naphthoquinone IS, anthracene 16, perylene 17, naphthalene 18, frn/w-stilbene. Solid lines denote theoretical predictions. (Adapted from Kojima and Bard, 1975.)...

Three hundred milliliters of concentrated sulfuric acid is added to 110 g. of powdered potassium nitrate, and the mixture is cooled to 10° in an ice-salt bath. Benzonitrile (100 g., 0.97 mole) is added dropwise with stirring. The addition requires about 3 hours, and the temperature of the mixture is held below 20° during the entire operation and for an additional hour. The thick reaction mixture is added with stirring to 2 1. of an ice-water mixture. The precipitated solid is collected by filtration and washed with water. The solid is stirred with dilute ammonia water, and the resulting mixture is filtered and washed until the ammoniacal filtrate is only slightly yellow. The product is recrystallized from dilute ethanol or acetic acid to give 88 g. (61%) of m-nitrobenzonitrile melting at 115-116°. 

Obtained by reaction of m-nitrobenzonitrile with resorcinol in the presence of zinc chloride and hydrochloric acid in ethyl ether, followed by hydrolysis of the resulting ketimine hydrochloride in boding water (73%) [215], for 30 min [1261], (11%) [1262] (Hoesch reaction). 

The kinetics and mechanism of the phosphorus-catalysed dimerization of acrylonitrile to give 1,4-dicyanobut-l-ene and 2,4-dicyanobut-l-ene have been studied.114 The reactions of aryhminodimagnesium (138) with //-substituted p-cyanobenzophenones, l-cyano-9-fluorenenone, o-, m-, and p-dicyanobcnzcnes, and o-, m-, and p-nitrobenzonitriles have been examined.115 The effect of pressure on the reaction of 3 -methyl- l-(4-tolyl)triazene (139) and benzoic acid in chloroform and acetonitrile has been studied.116 The effect of acids on the rate of urethane formation from alcohols and isocyanates in the presence of alkyltin carboxylates has been examined.117 A Hammett a value has been reported for the amidine group N=CHNMe2 and used for the prediction of the basicity of sites in bifunctional amidines.118... 

In the nitrobenzonitriles, such resonant structures will be mutually suppressed and consequently no large deviations from the additivity rule occur, such as exist when the two groups are of opposite charge so that the resonance is augmented by additional valence bond structures. The dipole moment of />-nitrobenzonitrile is zero, of o-nitrobenzonitrile, 6 19, D and m-nitro-benzonitrile, 3-78, D. Similar behaviour is observed with the di-substituted halogen derivatives of benzene and with the phenylenediamines. 

Chloro-6-nitrobenzonitrile, 519 5a-Chloro,6 -nitrocholestanyl acetate, 750 l-Chloro-4-(o-nitrophenyl>2-butene, 743 l-Chloro-2-nitroso-l,2-didesoxyglucose,751 iy -7-Chloronorcamphorquinone, 994 l-Chloro-3-pentanone, 388, 389 m-Chloroperbenzoic acid, 135-139,1192 p-Chlorophenol, 65 a-Chloro-a-phenylacetanilide, 1078... 

C. Nese, M.N. Schuchmann, S. Steenken and C. von Sonntag, Oxidation vs. fragmentation in radiosensitization. Reactions of a-alkoxyalkyl radicals with 4-nitrobenzonitrile and oxygen. A pulse radiolysis and product analysis study, J. Chem. Soc., Perkin Trans. 2, (1995) 1037. 

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