Patent GB-770928-A (GB)
Title: N-aralkyl-n-hydrocarbyloxyalkyl-halogenated alkanoamides
IPC: C07C233/16
Filed: 1955-01-26
Abstract: The invention comprises compounds of the formula: <FORM:0770928/IV(b)/1> where Ar is a phenyl, naphthyl, biphenylyl, furyl, pyridyl or thienyl radical (which may have substituents as specified below), X is an alkylene radical having one to four carbon atoms, Y is an alkylene radical having 2 to 6 carbon atoms and having its two free valence bonds on different carbon atoms and Ac is a halogenated alkanoyl radical having 1 to 4 carbon atoms.  The radical Ar can have from 1 to 3 substituents such as halo, lower alkoxy, methylenedioxy, ethylenedioxy, lower alkyl, lower alkylmercapto, lower alkylsulphonyl, nitro and di-(lower alkyl) amino ("lower" meaning a radical with 1 to 6 carbon atoms). Such compounds are obtained by reacting a secondary aminoether of the formula Ar-X-NH-Y-O-R with an acylating agent having the formula Ac-halogen or (Ac)2O or, for the chlorformamide, with phosgene.  Lists are given of many specific groups which Ar, X, Y, R and Ac may represent. Included for Ac are various chloro-, bromo-, iodo- and fluoro-acyl groups.  The intermediate amines of the above formula can be prepared by reacting Ar-X- halogen with an aminoether R-O-Y-NH2, or by reacting an aldehyde ArCHO with an aminoether R-O-Y-NH2 and hydrogenating the resulting anil ArCH = N-Y-O-R.  A third method is to react the amine Ar-X-NH2 with a halide of the formula R-O-Y-halogen (e.g. in the preparation of N-(2-cyclopropoxyethyl 3,4-dibromophenethylamine).  In examples: (1) (a) 2,4-dichlorobenzylamine and 2 - ethoxyethyl chloride are reacted to form N - (2 - ethoxyethyl) - 2,4 - dichlorobenzylamine.  A table is given of similarly prepared compounds having substituents in the phenyl residue selected from 2,3- or 3,4-dichloro-, 4-butoxy, 4-isopropyl and methylene dioxy groups and groups at R selected from methyl ethyl, butyl and phenyl groups.  Also listed are N - (2 - ethoxyethyl) - 1 - naphthylmethylamine, N - (2 - ethoxyethyl) - 1 - biphenylmethylamine, N - (2 - ethoxyethyl) - 1 - furylmethylamine, N - (2 - ethoxyethyl) - 2 - pyridylmethylamine, N - (2 - ethoxyethyl) - 2 - thienylmethylamine, N - (2 - ethoxyethyl) - 4 - n-hexylbenzylamine, N - (2 - hexoxyethyl) - 2,4-di - iodobenzyl amine, N - (6 - methoxyhexyl)-1 - (3,4 - dibromophenyl) ethylamine, N - (2-cyclohexoxyethyl) - 4 - nitrophenethylamine, N - [2 - (1 - propenoxy) - ethyl] - 4 - (3,4,5-triethoxyphenyl) butylamine, N - [2 - (cyclopentyl) - methoxy) ethyl] - 4 - n - hexoxybenzylamine and N - [2 - (2 - phenethoxy)-ethyl] - 4 - n - butylsulphonylbenzyl amine. (b) N - (2 - ethoxyethyl) - 2,4 - dichlorobenzylamine is reacted with dichloroacetyl chloride or dichloroacetic anhydride to give N-(2,4-dichlorobenzyl) - N - (2 - ethoxyethyl) - dichloracetamide. The N - (4 - isopropylbenzyl derivative is similarly obtained.  A table is given of similarly prepared compounds of the first formula above where Ar is selected from phenyl or phenyl having 2,4- or 3,4-dichloro-, p-butoxy, and 3,4-methylenedioxy substituents, R is variously methyl, ethyl, butyl or phenyl and Ac is selected from mono-, di- and trichloracetyl groups.  Also listed are similar compounds in which Ar represents variously the other unsubstituted groups listed above for this radical or is a dibromo, di-iodo, n-hexyl, nitro, triethoxy, hexoxy-, or butylsulphonyl substituted phenyl group, -Y-O-R is selected from ethoxyethyl, hexoxyethyl, cyclohexoxyethyl, propenoxyethyl, cyclopentylmethoxyethyl and phenethoxyethyl, and Ac is selected from dichloroacetyl, dibromoacetyl, bromochloroacetyl, di-iodoacetyl, difluoroacetyl, 2,2-dichloropropionyl, 2,2-di-iodopropionyl, 3-chloropropionyl, 2,2,3 - trichloropropionyl, 2,2 - dichlorobutyryl, and 3,4- or 2,4-dibromobutyryl radicals.  (2) (a) N - (3 - ethoxypropyl) - 3,4 - dichlorobenzylamine is prepared for reacting 3, 4-dichlorobenzyl chloride with 3-ethoxypropylamine.  A table is given of similarly obtained N-(3-alkoxypropyl)-benzylamines in which the benzyl residue has substituents selected from 2,4-or 3,4-dichloro and 4-nitro groups and the alkoxy group is selected from methoxy, ethoxy, isopropoxy or butoxy groups; (b) N-(3-ethoxypropyl) - 3,4 - dichlorobenzylamine and dichloracetyl chloride are reacted to give N-(3-ethoxypropyl) - N - (3,4 - dichlorobenzyl) - dichloracetamide.  A table lists similarly prepared di- and trichloracetyl derivatives, containing as the groups Ar and R radicals selected from those specified in Example (2) (a); (3) (a) 4 - n - butoxybenzaldehyde and 3 - n - butoxypropylamine are reacted to give the anil which, without isolation, is catalytically hydrogenated to N - (3 - n - butoxy - propyl) - 4 - n - butoxybenzylamine.  N - (3 - methoxy - propyl) - 4 - n-butoxybenzylamine is prepared similarly; (b) N - (3 - n - butoxypropyl) - N - (4 - n - butoxybenzyl) - dichloracetamide and the corresponding 3-methoxypropyl derivative respectively are obtained by treating the amines obtained in Example (3) (a) as in Example (1) (b).  (4) (a) 2 - phenoxyethyl chloride 3,4 - dichlorobenzylamine are reacted to give N-(2-phenoxyethyl) - 3,4 - dichlorobenzylamine. Similarly obtained are N-(2-phenoxyethyl)-4-n-butylmercaptobenzylamine, N - [2 - (4 - methylphenoxy ethyl] - 4 - di - n - butylaminobenzylamine and N - [2 - (4 - n - hexylphenoxy) ethyl] - 3,4 - dichlorobenzylamine; (b) N-(2-phenoxyethyl)-3,4-dichlorobenzylamine and dichloracetyl chloride are reacted to give N-(3,4-dichlorobenzyl)-N - (2 - phenoxyethyl) - dichloracetamide.  Similarly obtained are 4-(4-n-butylmercaptobenzyl) - N - (2 - phenoxyethyl) - 2,3,4 - trichlorobutanamide, N - (4 - di - n - butylaminobenzyl) - N - [2 - (4 - methylphenoxy) ethyl]-2,2,3 - trichlorobutanamide and N - (3,4 - dichlorobenzyl) - N - [2 - (4 - n - hexylphenoxy) ethyl] dichloroacetamide.