Patent GB-884669-A (GB)
Title: Process for preparing ª--(hydroxyalkyl) hydrazinium salts
Inventor: RUDNER BERNARD
IPC: C08G59/40
Filed: 1959-03-16
Abstract: A polymeric hydrazinium chloride of the possible structure <FORM:0884669/IV (a)/1> is prepared by reacting dimethylhydrazine hydrochloride with vinylcyclohexene dioxide and isolating the ethyl acetate soluble portion of the product.  Other polymeric hydrazinium chlorides are prepared by the acylation of dialcoholic hydrazinium chlorides with dibasic acids or their reactive functional derivatives.  Thus <FORM:0884669/IV (a)/2>ALSO:Beta-hydroxyalkyl-hydrazinium salts are prepared by reacting an oxirane with an acid-addition salt of a basic hydrazine in which at least one nitrogen atom has both its hydrogen atoms replaced by either two carbon atoms of one or two organic radicals singly bonded to the nitrogen atom or one carbon atom of an organic radical doubly bonded to the nitrogen atom.  The reaction is preferably effected in an anhydrous alcoholic solvent (although other solvents, including water, may also be used) at temperatures between 10 DEG C. and 80 DEG C., and the product in each case is probably a mixture of isomers, as illustrated by the equation <FORM:0884669/IV (b)/1> wherein, for example, R1, R2, R3 and R4 can be hydrogen, alkyl, hydroxyalkyl, cycloalkyl, aryl, or aralkyl, or R1 and R2 or R4 together can form a mono- or bi-cyclo carbocyclic ring structure having no more than 7 annular members in a ring; R5 and R6 can be allyl, alkyl, phenylalkylene or hydroxyalky, or R5 and R6 together with the nitrogen atom on which they are both substituents can represent a 5, 6 or 7 membered heterocyclic ring, or when R6 is alkyl R5 can also be a benzene, nitrobenzene or chlorobenzene radical. Suitable oxiranes for use in the process include alkylene and cycloalkene oxides and dioxides which may contain additional double bonds, aryl and aralkyl radicals and hydroxy, halogen, carboxylic and esterified carboxylic, nitro, aroyl and trifluoromethyl atoms or groups. Suitable hydrazines include hydrazine di-, tri- and tetra-substituted by a variety of alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkanoyl groups, substituted semicarbazones, N-amino-pyrrolidine, -morpholine, -piperidine, -piperazines substituted by aryl, alkyl, amino and arayl groups, and -perhydroindoles, 2-methyl-1-phenyl-5-pyrazolidone, cyclohexylidene acetylidene azine, b -methoxy-propionaldehyde azine, and other hydrazones and azines of the formula R5.R6.C=N.NR7R8 and R5R6C=N.N=CR7R8 wherein R7 and R8 can be hydrogen, phenyl, benzyl, acyl, carbamoyl, thiocarbamoyl, mono-or di-nitro-phenyl, halophenyl, sulphophenyl or naphthyl, R5 can be hydrogen or alkyl, and R6 can be alkyl, phenyl, p-tolyl or benzyl, or R5 and R6 together can form a 5 or 6 membered ring.  Specified anions, e.g. X-, include halides, sulphate, phosphate, nitrate, benzene-sulphonate, monomethyl sulphate and monophenyl phosphate. Examples illustrate many of the above features, the preparation of a mixture of <FORM:0884669/IV (b)/2> ; the formation of <FORM:0884669/IV (b)/3> by benzoylation of the corresponding dihydroxyhydrazinium chloride and of the dibenzoate of 1 : 1-bis(2-hydroxyethyl)-1-methyl hydrazinium chloride by a similar method; the formation of a mixture of <FORM:0884669/IV (b)/4> and <FORM:0884669/IV (b)/5> by the reaction of vinylcyclohexene dioxide with dimethyl hydrazine hydrochloride; and the formation of an unresolvable mixture of bisand tris-hydrazinium chlorides one of which has the probable structure <FORM:0884669/IV (b)/6> by the reaction of the glycerol tri-ester of acetoxy-epoxystearic acid with dimethyl hydrazine hydrochloride.  1-Methyl-1-benzyl-hydrazine hydrochloride is prepared from methylhydrazine and benzyl chloride. Dimethylhydrazine hydrochloride is prepared from the free base and concentrated hydrochloric acid, and is identified by conversion to the oxalate.  Diethylhydrazine hydrobromide is prepared similarly.