Y-Bromobutyronitrile

A mixture of 1 kg. of methanol, 65 g. (1.0 mole) of potassium cyanide, and 404 g. (2.0 moles) of trimethylene bromide is heated to reflux on a steam bath for 7-8 hours. The precipitated potassium bromide is filtered off, and the methanol is distilled from the filtrate. Fractional distillation of the residual oil gives 175 g. (0.87 mole) of unreacted trimethylene bromide, b.p. 70-72°/20 mm., and 70 g. (42% based on unrecovered trimethylene bromide) of y-bromobutyronitrile, b.p. 100-102°/20 mm. 

Hydrogen chloride gas is passed rapidly into a mixture of 1 g. of aluminum chloride, 3 ml. of water, and 720 g. (10 moles) of tetra-hydrofuran [Org. Syntheses Coll. Vol. 2, 566 (1943)]. The mixture is heated during this operation until a temperature of 105° is reached, and then the heating is discontinued and the mixture is allowed to come gradually to room temperature. The resulting material is 

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The submitter reports that an equivalent number of moles of Y-bromobutyronitrile or a mixture of 7-chloro- and 7-bromo-butyronitrile may be substituted for 7-chlorobutyronitrile. If the bromo compound is used the reaction mixture should be refluxed six hours and it is necessary to filter off the sodium bromide just before the final vacuum distillation. 

Trialkylammonium salts of the N-unsubstituted tetrazoles 231 are equally applicable as substrates in reactions both with haloalkyls and unsaturated compounds. These reactions, as already mentioned, lead mainly to formation of Nz-isomers. For instance, the reaction of 5-phenyltetrazole triethylammonium salt 231 (generated in situ from 5-phenyltetrazole and triethylamine) in acetonitrile with y-bromobutyronitrile (alkylation) or with acrylonitrile (Michael s method) afforded the corresponding Nz-substituted derivatives 254 and 255 in acceptable yields (Scheme 26) <2002CHE986>. 

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