Patent GB-1499056-A (GB)
Title: Alkyl polyamines having a cyclic substituent methods of preparing such compounds and their use as antimicrobials
IPC: C09D17/00
Filed: 1976-04-22
Abstract: 1499056 Dicycloalkylalkyl polyamines MERCK & CO Inc 22 April 1976 [28 April 1975] 16374/76 Heading C2C [Also in Divisions C5 and E1] The invention comprises compounds of the formula wherein A is cyclohexyl or cyclohexenyl which may be substituted by (C 1 -C 6 ) alkyl, each n is 0 or 1, R 1  is (C 1 -C 4 ) alkylene, Z is where Q is 1,4-piperidinediyl or -piperazinediyl; Q<SP>1</SP> is 1,4-cyclohexylene, R 2  is or (C 1 -C 4 )alkylene, R 3  is H, (C 1 -C 4 )alkyl, (C 2 -C 4 )aminoalkyl, (C 1 -C 4 )hydroxyalkyl or (C 2 -C 4 )dihydroxyalkyl, R 4  is or (C 1 -C 4 )alkylene, R 5  is H, H 2 N-CH 2 CH 2 -, H 2 N-CH 2 CH 2 CH 2 -, (C 1 -C 4 )monohydroxyalkyl, or (C 2 -C 4 )dihydroxyalkyl, R 6  is H, (C 1 -C 4 ) monohydroxyalkyl or (C 2 -C 4 )dihydroxyalkyl, R 7  and R 8  are direct links (C 1 -C 4 )- alkylene or -CH 2 CHOHCH 2 - radicals, and R 9  is aminoethyl, aminopropyl or aminohydroxypropyl; and acid addition salts thereof. They may be obtained by chemical or catalytic reduction of a Schiffs' base of the formula They are useful as antimicrobial agents and algae inhibitors. Antimicrobial compositions comprise compounds of the above formula together with a carrier. Ketones of the formula are obtained by acylative decarboxylation of acids of the formula at elevated temperature in the presence of transition metals or oxides thereof, alkaline earth metal oxides, polyphosphoric acid or BF 3 . Ketones of the above formula may also be obtained by a Grignard reaction of with a nitrile of the formula The acids of the above formula may be obtained by reacting an appropriate cyclohexene with an excess of refluxing aliphatic carboxylic acid anhydride in the presence of a free radicalforming catalyst. N - (3 - Aminopropyl) - 1,4 - cyclohexanebis- (methylamine) is obtained by reaction of acrylonitrile with 1,4-cyclohexane-bis(methylamine) followed by hydrogenation over a sponge Ni catalyst. N - (3 - Aminopropyl) - 1,4 - cyclohexane bis(2 - ethylamine); N,N<SP>1</SP> - bis - (3- aminopropyl) - 1,4 - bis(2 - aminoethyl)cyclohexane, and N - (3 - aminopropyl) - N<SP>1</SP> - (2- hydroxyethyl) - 1,4 - cyclohexanebis(methylamine) are obtained in a similar manner. N - (2 - Aminoethyl) - 1,4 - bis - (2 - aminoethyl) - cyclohexane is obtained by reacting 1,4-bis-(2-aminoethyl)cyclohexane with ethyleneimine. N - (2 - Hydroxyethyl) - 1,4 - bis - cyclohexanebis(methylamine is obtained by reacting 1,4- cyclohexanebis(methylamine) with ethylene oxide. N - (3 - Amino - 2 - hydroxypropyl) - 1,4 - cyclohexanebis(methylamine) and N - (2,3 - dihydroxypropyl) - 1,4 - cyclohexanebis(methylamine) are obtained by reacting 1,4 - cyclohexanebis- (methylamine) with epichlorohydrin and reacting propylene chlorohydrin obtained with NH 3  gas or aqueous methanolic NaOH respectively. N,N - Bis - (3 - hydroxypropyl) - 1,4 - cyclohexanebis(methylamine) is obtained by reacting 1 - bromomethyl - 4 - cyanocyclohexane with di - (3 - hydroxypropyl)amine and hydrogenating the resulting product over a sponge Ni catalyst. N,N - Di - (2,3 - dihydroxypropyl)trimethylenediamine is obtained by reacting bis-(2,3-dihydroxypropyl)amine with acrylonitrile and hydrogenating the resulting product as described above. The final product may be reacted with glycidol to form N,N,N<SP>1</SP>-tri-(2,3- dihydroxypropyl)trimethylenediamine, which may in turn be reacted with acrylonitrile and the intermediate hydrogenated as above to give 5,9,9 - tri - (2,3 - dihydroxypropyl) - 1,5,9 - triazanonane.