834. GRAF, R. (Ferbwerke vormals Meister Lucius & Brüning). [Nitiles.] German Patent 848,947. Sept. 11, 1952 (Cl. 21 o-11). Chem. Abs., vol. 47, 1953. p. 5425.

Patent Abstracts

834. GRAF, R. (Ferbwerke vormals Meister Lucius & Brüning). [Nitiles.] German Patent 848,947. Sept. 11, 1952 (Cl. 21 o-11). Chem. Abs., vol. 47, 1953. p. 5425.

Saturated aliphatic or cycloaliphatic hydrocarbons with CNCl in the presence of organic peroxides at moderately elevated temperature. 50º-60º C., give nitriles useful as intermediates in the preparation of amines by hydrogenation or saturated aliphatic or cycloaliphatic carboxylic acids by saponification. Suitable initial materials are BuH, hexane, heptane (I), dodecane, cetane, iso-BuH. 2-BuCHEt. cyclohexane (II), and its alkyl derivatives: moreover hydrocarbon mixtures as they are produced by the hydrogenation of petroleum fractions or by the CO hydrogenation: diAc₂O₂ or Bz₂O₂ or peroxides of the general formula RSO₂O₂. Ac produced by treating saturated hydrocarbons with SO₂ and O₂ in the presence of Ac₂O, are suitable catalysts. Adding cyclohexysulfonyl acetayl peroxide (III) 40 to (II) 400 and CNCl 63 with stirring at 30º, rasing the temperature (with intensive reflux-cooling) within 6 hr. to 50º, extracting the (II) layer repeatedly with H₂O, and removing the excess (II) by distillation, gives hexahydrobenzonitrile 50 parts by weight, b10 65º . Similarly are prepared: A mixture of isomeric cyanoheptanes, b₂₃ 84º-95º, from (I), (II), and CNCl: a mixture of isomeric cyanoisooctanes, colorless oil, b₂₅ 70º-105º, N content 10.4%, from isooctane (obtained by hydrogenation of dimerized isobutylene) (II), H₂O, and CNCl.