Patent GB-436414-A (GB)
Title: Improvements in the manufacture and production of tertiary amines of high molecular weight
IPC: C07C215/08
Filed: 1934-09-14
Abstract: Tertiary amines are obtained by the reaction of secondary amines (or reagents which form them under the reaction conditions) with alcohols or their carboxylic esters, or with aldehydes or ketones, at a raised temperature in the presence of a hydrogenation catalyst, at least one of the reagents containing a radicle of at least eight carbon atoms; the reaction is effected in the presence of hydrogen when aldehydes or ketones are treated, in the presence or absence of hydrogen when alcohols are treated, and in the absence of hydrogen when esters are treated.  Specified alcohols, esters, aldehydes and ketones are methyl, ethyl, butyl, octyl, undecyl, dodecyl, octodecyl, and oleyl alcohols, montanol, octadecanediol, cyclohexanol (which may be formed in situ from phenol and hydrogen), phenylethyl alcohol, and alcohols obtainable by oxidizing paraffin wax or mineral oils; esters of these alcohols with acetic, propionic, butyric, lauric, oleic, oxalic, succinic, benzoic, or naphthoic acid; butyraldehyde, oenanthaldehyde, paraformaldehyde, cyclohexanone, and undecyl methyl ketone; the use of furfural is disclaimed.  Specified secondary amines are dimethylamine, diethylamine, diethanolamine, butylethanolamine, cyclohexylethylamine, butyldodecylamine, propyloleylamine, didodecylamine, and methyldodecylamine; the use of secondary amines containing heterocyclic nitrogen is disclaimed; as reagents which yield secondary amines under the reaction conditions, reference is made to mixtures of primary amines with aldehydes or ketones. Hydrogenation catalysts selected from groups 1, 2, 6, 7 and 8 of the periodic system may be used, but the use of noble-metal catalysts is disclaimed; copper, zinc, manganese, cobalt, chromium, molybdenum or tungsten, or mixtures of these or their compounds, are suitable. The catalysts may be mixed with activating substances, e.g. aluminium oxide, and may be distributed on carrier substances, e.g. bleaching earths, silica gel, bauxite, magnesium oxide, kieselguhr or pumice. Specified catalysts contain the following elements or compounds thereof: cobalt and aluminium; copper and manganese precipitated on bleaching earth; zinc, manganese, chromium and aluminium; nickel and chromium; copper, aluminium and barium.  When an alcohol and a secondary amine are reacted in the absence of hydrogen, the catalyst should be in the reduced state or the mixture should include, at least at the beginning of the process, a reducing agent such as hydrogen or gases containing hydrogen, or methanol.  The reaction may be effected in the liquid or gaseous phase, preferably under pressure, and either continuously or discontinuously.  Inert substances such as nitrogen or hydrocarbons may be present in the reaction mixture. In the examples, (1) dodecyl alcohol and diethylamine are heated in hydrogen to 250 DEG  C. under 220 atm. pressure in the presence of a catalyst prepared by treating a solution of the nitrates of copper, aluminium, and barium with sodium bicarbonate, and washing and drying the precipitate; diethyldodecylamine is obtained; (2) dodecyl alcohol and diethylamine are heated in hydrogen to 230 DEG  C. under 40 atm. pressure in the presence of reduced basic cobalt carbonate; diethyldodecylamine is obtained; (3) dodecyl acetate and diethylamine are heated to 250 DEG C. in the presence of the reduction product of the catalyst used in example 1; diethyldodecylamine is again obtained; (4) octadecanediol and diethylamine are heated in hydrogen to 230 DEG  C. under 45 atm. pressure in the presence of reduced basic cobalt carbonate; N-diethylaminooctadecanol and N : N<1> - tetraethyldiaminooctadecane are obtained; (5) undecyl methyl ketone and dimethylamine are heated to 270 DEG  C. under a hydrogen pressure of 200 atm. with a catalyst comprising copper and manganese oxides supported on bleaching earth; N-dimethyl-2-aminotridecane is obtained; (6) paraformaldehyde and methyldodecylamine are heated to 270 DEG  C. under a hydrogen pressure of 200 atm. with a catalyst prepared by heating basic zinc chromate; dimethyldodecylamine is obtained; (7) paraformaldehyde and dodecylamine are heated to 150 DEG  C. under a hydrogen pressure of 150 atm. with a catalyst comprising reduced nickel on bleaching earth; dimethyldodecylamine is again obtained; (8) methyl alcohol and methyldodecylamine are heated to 270 DEG  C. under a hydrogen pressure of 200 atm. with a tungsten sulphide catalyst prepared according to Specification 379,335; dimethyldodecylamine is again obtained.  Specifications 265,960, 306,414, 334,193, 334,579, [all in Class 2 (iii)], 365,214, 384,314, 409,732, and 412,914 also are referred to.  The Specification as open to inspection under Sect. 91 states that the reaction may be applied to esters of alcohols with weak acids, and refers to the treatment of esters of boric acid.  It states also that the treatment of the esters may be effected in the presence of hydrogen, and refers to the presence of hydrogen in the process of example 3 above.  Piperidine is stated to be a suitable secondary amine, and pyridines, quinolines and pyrroles are mentioned as substances from which secondary amines are obtainable under the reaction conditions.  This subject-matter does not appear in the Specification as accepted.