Patent GB-744675-A (GB)
Title: Improvements in or relating to new cyanoaminonitriles and process for their manufacture
IPC: C07C255/24
Filed: 1953-02-27
Abstract: The invention comprises as new compounds cyanoaminonitriles of the formula: R.N(CN).C.(R1)(R2)(CN) in which R is an alkyl group of 1 to 8 carbon atoms having at least one hydrogen atom on the carbon atom adjacent the nitrogen atom, R1 is hydrogen or methyl and R2 is an alkyl group of 1 to 8 carbon atoms.  The compounds may be obtained by reacting an aminonitrile having the formula R.NH.C(R1)(R2)(CN) under alkaline conditions in the presence of an inert solvent with a cyanogen halide.  The aminonitrile may be obtained by reacting a primary amine RNH2 with a carbonyl compound R1.CO.R2 and hydrogen cyanide.  Suitable primary amines are methyl-, ethyl-, propyl-, isopropyl-, n-butyl-, isobutyl-, sec.-butyl-, and 2-ethylhexyl amines.  Suitable carbonyl compounds are those in which R1 is hydrogen or methyl and R2 is methyl, ethyl, propyl or other alkyl radical up to octyl, e.g. acetaldehyde, propionaldehyde, nonyl aldehyde, acetone, and methyl ethyl ketone.  The aminonitrile may also be formed by first forming a cyanohydrin HO.C(R1)(R2)(CN) and then reacting the latter with the primary amine RNH2.  In preparing the cyanoamino-nitrile the alkalinity of the reaction medium should be maintained by the addition of sufficient basic substance to combine with the acid formed during the reaction. Suitable basic substances are sodium and potassium hydroxides or carbonates and lime.  The reaction is carried out in an inert solvent such as benzene at room temperature or slightly above room temperature, e.g. up to 50 DEG  C.  In examples: (1) the aminonitrile CH3.NH.CH(CN(CH3) is prepared by reacting methylamine with acetaldehyde and hydrogen cyanide in benzene and is then converted to the cyanoaminonitrile CH3.N(CN).CH(CN)(CH3) by adding cyanogen chloride to a solution of the aminonitrile in benzene, then adding anhydrous potassium carbonate in water, and finally an additional amount of cyanogen chloride; (2) methyl ethyl ketone containing a small amount of piperidine is reacted with anhydrous hydrogen cyanide to form the cyanohydrin which is then reacted with methylamine to form the aminonitrile, the latter is then dissolved in benzene, a solution of cyanogen chloride in benzene added and then a solution of anhydrous potassium carbonate in water, the product being the cyanoaminonitrile CH3.N(CN).C.(CH3)(C2H5)(CN); (3) n-butylamine is reacted with lactonitrile to yield the aminonitrile n-C4H9.NH.CH(CH3)(CN) which is then reacted with cyanogen chloride in benzene solution by a procedure similar to that of (2) to yield the corresponding cyanoaminonitrile, n-C4H9.N(CN).CH(CH3)(CN); (4) gaseous methylamine is added to acetone cyanohydrin and the reaction mixture stripped at room temperature to yield the crude aminonitrile which is then reacted with cyanogen chloride in the presence of benzene, anhydrous potassium carbonate and water to yield the cyanoaminonitrile, CH3.N(CN).C(CH3)2(CN); (5) acetone cyanohydrin is reacted with n-butylamine to yield the aminonitrile which is then converted into the cyanoaminonitrile, C4H9.N(CN).C(CH3)2CN, by reacting with cyanogen chloride in benzene solution followed by the addition of a solution of anhydrous potassium carbonate in water; (6) 3,5,5-trimethylhexaldehyde cyanohydrin in benzene is reacted with methylamine to yield the aminonitrile which is then reacted with cyanogen chloride by a procedure as in (2) to yield the cyanoaminonitrile CH3.N(CN).CH(C8H17)(CN); (7) 2-ethylhexylamine is reacted with acetone cyanohydrin to yield the aminonitrile which is then reacted with cyanogen chloride in the presence of benzene, anhydrous potassium carbonate, and water to yield the cyanoaminonitrile C8H17N(CN).C(CH3)2CN.  The cyanoamino nitriles may be combined with dicyanodiamide to form a bis-(aminotriazine) as disclosed in Specification 744,676 and the latter may be combined with formaldehyde or formaldehyde and an alcohol as in Specification 744,674, [Group IV (a)], to yield resinous condensation products.