Patent GB-510904-A (GB)
Title: Improvements in the manufacture and production of unsaturated nitrogenous condensation products
Filed: 1938-03-14
Abstract: 510,904. Unsaturated amino compounds. JOHNSON, G. W. (I.G. Farbenindustrie Akt.-Ges.). March 14, 1938, No. 7876. [Class 2(iii)] Amino compounds having triple unsaturated carbon linkages are prepared by treating in the liquid phase at temperatures not exceeding 120‹C. dimethyolurea, or methylolamino or substituted methylolamino compounds obtained by condensation of aldehydes and ketones with primary or secondary amino compounds, with acetylene in the presence of heavy metals of the first and second groups of the periodic systems or their compounds, for example copper chloride' or cuprous bromide, copper acetate, copper formate or acetylene-copper compounds. The catalysts may be applied to carriers such as kieselguhr. Specified methylolamino compounds are methylol-isobutylamine and tertiary basic compounds prepared by the condensation of aldehydes or ketones with secondary amines or heterocyclic secondary bases such as dimethylamine, diethylamine, dibutylamine, ' diisobutylamine, diethanolamine, N-alkylanilines, N-alkylnaphthylamine, dicyclohexylamine, piperidine and morpholine. When starting from the condensation products of ketones with primary or secondary amines, it is preferred to effect the reaction in the presence of basic compounds such as ammonia or amines, alkali alcoholates or salts of alkali or alkaline earth metals with weak acids, and when starting from the condensation products of aldehydes with primary or secondary amines it is preferred to use a weakly acid medium. The process may be carried out in the presence or absence of solvents, often at normal temperatures and under ordinary or increased pressure. Both hydrogen atoms of the acetylene may be replaced. The products may be polymerised into resinous products either directly or after conversion of the triple linkage to a double linkage. They are also initial materials for the preparation of solvents, pharmaceutical agents and dyestuffs. Products still containing an hydrogen atom in the acetylene radicle yield, with alcohols, vinyl ethers which are convertible into carbonyl compounds by the splitting off of the alcohol radicle and rearrangement. In the examples, (1) the condensation product of formaldehyde and dimethylamine is treated with a mixture of nitrogen and acetylene in the presence of acetic acid and copper acetate ; N-dimethyl-propargylamine is formed, together with a small amount of tetramethyldiaminodimethylacetylene; if isobutylamine is used as the initial material, N-isobutylpropargylamine is obtained; (2) the condensation product of dimethylamine and butyraldehyde is treated with acetylene and nitrogen in the presence of formic acid and copper chloride, yielding alpha-propyl-N- dimethyl-propargylamine ; small amounts of the disubstituted acetylene are also produced ; (3) the condensation product of butylamine and formaldehyde is treated with acetylene and nitrogen in the presence of acetic acid and cuprous chloride, yielding propargyl-(di-normalbutyl)-amine together with a small amount of tetra-normal-butyl-diamino-dimethylacetylene ; (4) the condensation product of dimethylamine and acetaldehyde is treated with nitrogen and acetylene in the presence of formic acid and cuprous chloride, yielding alpha-methyl-N- dimethyl-propargylamine together with small amounts of the disubstituted acetylene ; (5) the condensation product of dimethylamine and benzaldehyde is treated with nitrogen and acetylene in the presence of acetic acid and cuprous chloride, yielding alpha-phenyl-N- dimethyl-propargylamine and a small amount of the disubstituted acetylene ; (6) the condensation product of diethylamine and formaldehyde is treated with nitrogen and acetylene in the presence of acetic acid, cuprous chloride and keiselguhr, yielding N-diethyl-propargylamine ; (7) the condensation product of acetone and dimethylamine is treated with acetylene and nitrogen in the presence of sodium alcoholate and cuprous chloride, yielding N-dimethylalpha-dimethyl-propargylamine ; (8) the condensation product of dimethylamine and formaldehyde is treated with nitrogen and acetylene in the presence of cuprous chloride, silver nitrate, keiselguhr and acetic acid, yielding dimethyl-propargylamine ; (9) dimethylolurea is treated with nitrogen and acetylene in the presence of methanol and cuprous chloride, yielding N-hydroxymethyl-N<1>-omega-propineurea which polymerises to an elastic resin soluble in ethylene glycol monomethyl ether or monoethyl ether. A sample has been furnished under Sect. 2(5) of a product prepared by treating the condensation product of diethanolamine and formaldehyde with acetylene and nitrogen in the presence of glacial acetic acid and copper acetylide. The constitution of the product is probably #<HO CH2 ><CH2># N-CH2-C#CH. The Provisional Specification states that the reaction products of aldehydes or ketones with ammonia or acid amides or with methylamine ethylamine, butylamine, benzylamine or diamines may be used as starting materials.