α-Halogenation of Secondary Nitriles^1,2

Comparison of the Bromureide Sedative-Hypnotic Drugs, Bromvaletone (Bromisoval) and Carbromal, and Their Chloro Analogues in Mice

“…140-141 "C) were prepared by treating the corresponding acyl chloride with urea (Spielman et al, 1948). The 2-chloro acyl chlorides were prepared by chlorination of the acyl chlorides with sulphuryl chloride and iodine (Kharasch & Brown, 1940;Stevens & Coffield, 1951).…”

Hofmann Degradation

“…1 It is the conversion of carboxylic amides into primary amines with one less carbon atom via the isocyanate intermediate by means of basic hypohalite treatment. 5 This reaction is often used as a method for cuting a single carbon atom out of a chain. 2,3y,3z In this reaction, heat is needed; and in some cases, cyanate is also formed.…”

α-Bromination of primary nitriles

“…Recent work in this laboratory has shown that secondary nitriles could be halogenated in the «-position by the phosphorus pentahalides to give good yields of pure «-halo nitriles (1). This paper represents a continuation of that work and an investigation of the halogenation of primary nitriles (primary alkyl cyanides) to determine whether or not the -halo nitriles or a derivative could be isolated in good yield.…”

“…To show that the method of preparation was not responsible for the instability of the «-bromo primary nitriles, the «-bromobutyronitrile and a-bromovaleronitrile were prepared from the pure crystalline amides by dehydration using phosphorus pentoxide. «-Bromocapronitrile was prepared from the pure amide 1 Abstracted from a thesis submitted by Mr. William Holland to the Graduate School of Wayne University in partial fulfillment of the requirements for the degree of Master of using thionyl chloride as a dehydrating agent. The bromo nitriles from each of these preparations exhibited the same instability as material from the bromination reaction, even when fractionated at 30°under reduced pressure.…”