Patent GB-675266-A (GB)
Title: Improvements in or relating to a process of preparing new tertiary amines and the tertiary amines resulting from said process
IPC: C07D409/12
Filed: 1947-09-30
Abstract: A tertiary amine of the formula <FORM:0675266/IV (b)/1> [where R1 is phenyl, pyridyl or picolinyl, R2 is hydrogen or alkyl of 1-3 carbon atoms, R3 is alkyl of 1-3 carbon atoms, R4 is hydrogen, methyl, ethyl, chlorine or bromine, and R5 and R6 are hydrogen or methyl] is prepared by heating a 2-thenyl chloride or bromide with a solution of an ethylenediamine of the general formula NHR1.CH2.CH2.NR2R3, where R1, R2 and R3 are as above defined, or with a sodium derivative thereof, or where R2 and R3 are methyl groups, the hydrochloride of the ethylene diamine may be employed. In some cases, heating the reaction components is not necessary and a mere admixture is sufficient.  Exemplary of the thenyl halides are 2-chloromethyl - 5 - chlorothiophene and 5 - bromothiophene, and 2-bromomethyl-5-chlorothiophene and 5-bromothiophene.  It is preferred that R2 and R3 are methyl or ethyl, R5 and R6 are hydrogen, and R4 is chlorine or bromine.  When R2 and R3 are ethyl, n-propyl or isopropyl, the reaction is effected by heating the 2-thenyl halide in benzene solution with the diamine.  When R2 and R3 are methyl, the monohydrochloride of the N-R1-N1,N1-dimethylethylenediamine is first prepared by refluxing the diamine with ammonium chloride in benzene, and then heated with the 2-thenyl halide.  Salts, e.g. monohydrochloride, sulphates and phosphates, of the product are prepared by the usual methods.  N-phenyl-N1-alkyl and N-phenyl-N1-N1-dialkyl-ethylenediamines are prepared by heating 2 mols. of aniline with 0.2 mol. of the appropriate alkyl-b -chloroethylamine hydrochloride.  The corresponding N-pyridyl and N-picolinyl diamines are prepared by heating the amino-pyridine or picoline with sodamide and the appropriate alkyl-b -chloroethylamine hydrochloride in, e.g., toluene.  In the examples: (1) aniline and N,N - dimethyl - b  - chloroethylamine hydrochloride are heated to give N-phenyl-N1,N1-dimethylethylenediamine, which, after reaction with ammonium chloride, is refluxed with 2-thenyl chloride to give N-phenyl-N-(2-thenyl)-N1,N1-dimethylethylenediamine; the hydrochloride is also prepared; (2) 2-thenyl chloride is reacted with N-phenyl-N1,N1-diethylethylenediamine to give N-phenyl-N-(2-thenyl)-N1,N1-diethylethylenediamine; (3) 2-aminopyridine is treated with sodamide and then with N : N-dimethyl-beta-chlorethylamine and the product with 2-thenyl chloride to form N-(2-pyridyl)-N-(2-thenyl)-N : N1-dimethyl-ethylenediamine; (4) as in example (3) using 3-aminopyridine in place of 2-aminopyridine; (5) as in example (3) using 4-aminopyridine in place of 2-aminopyridine; (6) as in example (3) using 2-methyl-3-aminopyridine in place of 2-aminopyridine; (7) as in example (3) using 3-methyl-2-aminopyridine in place of 2-aminopyridine; (8) 2-amino-pyridine is treated with sodamide and then with N-methyl - N - ethyl - betachloroethylamine hydrochloride and the product refluxed with thenyl chloride to form N-(2-pyridyl)-N-(2-thenyl) -N1-methyl-N1-ethyl-ethylenediamine; (9) aniline and N : N-dimethyl-beta-chloroethylamine are refluxed, treated with caustic soda to form N - phenyl - N1 : N1 - dimethylethylene diamine which is refluxed with ammonium chloride and 2-chloromethyl-5-chloro-thiophene added to form N-phenyl-N-(5-chloro-2-thenyl)-N : N1-dimethylethylenediamine.  This may be converted to its monohydrochloride.  (10) 2-Aminopyridine is treated with sodamide and then with N : N-dimethyl-beta-chloroethylamine and the product refluxed with sodium hydride and 2-chloromethyl-5-chloro-thiophene added to form N-(2-pyridyl)-N-(5-chloro-2-thenyl)-N1 : N1-dimethylethylenediamine. Specification 606,181 is referred to.