Patent GB-994508-A (GB)
Title: N-cyanoimino compounds and their preparation
IPC: G03C1/73
Filed: 1963-10-30
Abstract: Cyanamide is obtained by hydrolysis of 1 - N - cyanoiminocyclopentane, and is converted into its silver salt, which is also obtained by treating 1-N-cyanoiminocyclopentane or 2-N-cyanoiminohexane with aqueous silver nitrate solution.ALSO:The invention comprises organic compounds containing at least one = NCN group which is (i) bonded by two single bonds to two vicinal carbon atoms, or (ii) bonded by a double bond to a single carbon atom which is itself directly attached to at least one other carbon atom; and their production by reacting an ethylenically unsaturated compound (including steroids) with cyanogen azide at - 25 DEG  to + 75 DEG  C. The reaction is represented generally by the equation <FORM:0994508/C2/1> <FORM:0994508/C2/2> where each R is hydrogen, halogen, nitro, hydroxy, cyano, alkoxy, aryloxy, alkylthio, acyl, acyloxy, carboxy, carbamoyl, N-hydrocarbylcarbamoyl, hydrocarbyloxycarbonyl, hydrocarbyl, or a hydrocarbyl group substituted by one or more substituents as defined; or any pair of R's may form an alkylene or oxygen interrupted alkylene group of 2-10 carbon atoms.  Other types of product have the formula R4 = NCN, where R4 is a cyclopentylidene, bicycloheptylidene or C5-12 alkylidene radical, or a divalent steroidal radical, such as one of the estrene, androstene, pregnene, cholene, cholestene, ergostene or stigmastene class.  The product may also contain silicon or be a polymer (see Division C3).  Many starting materials and examples are given, including cases where ring expansion or contraction occurs. The following reactions are carried out in determinations of structure: 3-cyano azatricyclo[3.2.1.02.4] octane is reduced with LiAlH4 to 3 - azatricyclo[3.2.1.02.4]octane, which with phenyl isothiocyanate gives the corresponding 3 - thiocarboxanilide. Hydrolysis of 1-N-cyanoiminocyclopentane produces cyclopentanone and urea, the former identified as its 2,4-dinitrophenylhydrazone. The action of aqueous AgNO3 solution on 2-N-cyanoiminohexane produces 2-hexanone, identified as its semicarbazide.ALSO:The invention comprises organic compounds containing one or more = N-CN groups bonded by a double bond to a single carbon atom (said atom being directly attached to at least one other carbon atom) or by two single bonds to two vicinal carbon atoms; and their production by reacting an ethylenically unsaturated compound with cyanogen azide at -25 DEG to + 75 DEG  C. Polymeric products may be obtained.  The ethylenic starting material may contain an alkylsilyl group attached to a double bonded carbon atom; or may be a polymer, e.g. a polybutadiene or polychloroprene, an ethylene/propylene/butadiene, ethylene/propylene/hexadiene or isobutylene/butadiene copolymer, or natural rubber.  In particular examples, (A) polymeric products are obtained when reacting cyanogen azide with (VIII) propylene; (XI) butene-1; and (XVI) 3-methyl-butene-1; and by heating 1-N-cyano iminocyclohexane (Example I); (B) cyanogen azide reacts with trimethylivinylsilane to give a mixture of 1-trimethylsilyl-1-cyano iminoethane and 1-cyano-2-trimethylsilylaziridine (Example XXX); and (C) cyanogen azide is reacted with (XXV) cis polybutadiene and (XXVI) 50% trans, 40% cis and 10% 1,2-vinyl polybutadiene to obtain polymers containing cyanoimino and/or N-cyanoaziridine groups. It is stated that polymers modified in this way may be hydrolysed to obtain products with carbonyl groups, which may be reacted with aldehydes or oximes; oximated products may be reduced to polymers containing amine groups. Oxidation of polymers containing carbonyl groups gives products containing carboxylic acid groups.