Patent GB-642409-A (GB)
Title: Improvements in or relating to the preparation of guanamines
Filed: 1947-05-06
Abstract: Guanamines of the formula <FORM:0642409/IV (b)/1> where R1 is an aliphatic or aryl radical and R2 is hydrogen or an aliphatic or aryl radical, are prepared by reacting a compound <FORM:0642409/IV (b)/2> with a nitrile R1CN in the presence of a strongly basic alkali metal compound, the reaction mixture being dissolved in a hydroxylated solvent such as water, alcohols, glycols, and glycol mono-ethers. The use of excess nitrile is thereby unnecessary and nitriles of more than 8 carbon atoms can be made to react.  Alkali metals, their hydroxides, alkoxides, oxides, cyanamides, dicyandiamides, and anilides, especially of potassium, may be used as catalysts generally in amounts of 1/20 -\ba1/10 mol. per mol. of nitrile.  Temperatures may be from room to 200, preferably 100-150 DEG  C.  Solvents boiling above 100, preferably 100-150 DEG  C. are suitable.  Times may be 1/4 -1 hour, or more.  Comparative figures are given for reaction of succinonitrile and dicyandiamide using alkali metal or alkali metal hydroxide, or the known catalyst piperidine, and methanol, butanol or glycol monoethyl ether as solvent or excess of nitrile. Benzyl and benzo nitriles are also specified.  In examples: (1) acetoguanamine is prepared by heating dicyandiamide and acetonitrile with potassium hydroxide in monomethyl or ethyl ether of glycol, butanol, methanol or isopropanol; (2) octanonitrile similarly yields octanoguanamine, glycol monoethyl ether being the solvent; (3) potassium dicyandiamide is used as catalyst with the same solvent in preparing oleoguanamine from oleonitrile; (4) d -cyanovaleroguanamine is made from adiponitrile, the cyandiamide, and sodium in the same solvent; (5) sebaconitrile similarly gives #q-cyanononyloguanamine; (6) with additional dicyandiamide and potassium hydroxide in glycol monobutyl ether this is converted to sebacoguanamine; (7) b -sulphopropionoguanamine is prepared from the sodium salt of b -sulphopropiononitrile and dicyandiamide, sodium hydroxide or sodium being the catalyst, and water, ethylene glycol or its monoethyl ether the solvent; (8) phenylacetoguanamine is prepared from phenylacetonitrile and dicyandiamide, using potassium dicyandiamide or hydroxide and ethylene or diethylene glycol mono-ethers; (9) trichloroacetoguanamine is obtained using trichloracetonitrile; (10) b  - aminopropiononitrile obtained from acrylonitrile, ammonia and methanol is converted to the acetamido derivative with acetic anhydride and reacted with dicyandiamide to yield b -acetamidopropionaguanamine; (11) b  - N - butylaminopropiononitrile, from a crylonitrile and n-butylamine is reacted to give the corresponding guanamine or first converted with acetic anhydride to the acetamido derivative and reacted to give b -N-butylacetamidopropionoguanamine; (12) b  - N - phenylaminopropiononitrile, from acrylonitrile and aniline, reacts to yield b -N-phenylaminopropionoguanamine; (13) phenylglycinonitrile, prepared from formaldehyde, aniline, sodium cyanide, and sodium bisulphite, reacts to give phenylaminoacetoguanamine or, after converting to the acetamido derivative to give N-phenylacetamidoacetoguanamine; (14) benzonitrile gives benzoguanamine; (15) 1-phenyl dicyandiamide prepared from potassium dicyanimide and aniline, yields with acetonitrile 4-N-phenyl-acetoguanamine; (16) using succinonitrile, 4 - N - phenyl - b  - cyanopropionoguanamine is produced; (17) 1-dodecyldicyandiamide, prepared similarly, is converted to 4-N-dodecyl-b -cyanopropionoguanamine; (18) o - cyanobenzoguanamine is obtained from o-phthalonitrile and dicyandiamide; (19) b -cyanopropionoguanamine is obtained using succinonitrile.