Patent GB-640158-A (GB)
Title: Methods of making derivatives of n-(cyanoalkyl) dithiocarbamic acids, and the new compounds resulting therefrom
IPC: C07C333/16
Filed: 1947-03-06
Abstract: Resinous products are obtained by treating with carbon disulphide a secondary amine which has an N-(cyano-alkyl) group. The amine is used in excess and the products are apparently polymeric forms of the salts of N-(cyano-alkyl), N-alkyl (or cycloalkyl or aralkyl) amines with N-(cyano-alkyl), N-alkyl (or cycloalkyl or aralkyl) dithiocarbamic acids.  Examples show the production of the N-(2-cyano-ethyl)- N-ethyl, N-benzyl and N-cyclohexyl compounds, and many others are mentioned.  Other salts of the acids which may be formed are those of organic bases and metals (e.g. sodium, zinc). The acids may also be converted into thiuram mono-, di- and polysulphides.ALSO:Dithiocarbamates derived from N-(cyano-alkyl)-dithiocarbamic acids are obtained by treating with carbon disulphide secondary amines containing an N-(cyano-alkyl) group; the products may be oxidized to thiuram disulphides.  The dithiocarbamic acids contain the grouping <FORM:0640158/IV (b)/1> where R is an alkylene group and R1 is an alkyl, cycloalkyl or aralkyl group; R1 may contain hydroxy, chlorine or further cyano groups, and if a diamine is used as starting material, R1 will contain a cyanoalkylamino group which will form an inner salt with the dithiocarbamic acid group.  The acids may be converted into primary, secondary and tertiary amine salts, metallic salts and thiuram mono-, di- and poly-sulphides.  The last-named may be obtained by the action of sulphur chlorides on the dithiocarbamates. The disulphides are produced by oxidation of the dithiocarbamates in aqueous solution.  Examples are given of the preparation of typical compounds: (1) by using an excess of the cyano-alkyl secondary amine to give the salt of this base with the acid; (2) by carrying out the reaction in the presence of a tertiary amine to produce the salt of the latter with the acid; (3) by conversion into sodium and zinc salts; and (4) by oxidation with hydrogen peroxide to yield the thiuram disulphide.  A list is given of many other compounds prepared by the process of the invention, e.g. from N-(cyano-alkyl)-methyl, ethyl, isopropyl, n-butyl, n-amyl, n-dodecyl and cyclohexyl amines. N-(cyano-alkyl) secondary amines can be prepared from primary amines and a ,b -unsaturated aliphatic nitriles or from ammonia and two molecules of the nitriles.  Thus acrylonitrile with ethylamine, benzylamine, cyclohexylamine and ethylene diamine yields N-(2-cyanoethyl)- N-ethyl amine, N-(2-cyano-ethyl) - N - benzyl amine, cyclohexylaminopropionitrile and N : N1 - di - (2 - cyano - ethyl) - ethylene diamine respectively.  N - (cyano - methyl) - N - n - butyl amine is produced from n-butylamine, sodium cyanide and formaldehyde.  The Specification as open to inspection under Sect. 91 refers to R1 as a substituted alkyl group in general and states that the alkyl chain may be interrupted by nitrogen, oxygen, sulphur or other elements.  It also states that thiuram mono-sulphides may be obtained by the removal of one atom of sulphur from the disulphides either simultaneously with their formation or subsequently.  This subject-matter does not appear in the Specification as accepted.