Patent GB-598309-A (GB)
Title: Improvements in the production of organic compounds
IPC: C07C209/48
Filed: 1945-03-15
Abstract: Intermediates for polymers, wetting and emulsifying agents are produced by reacting 1,3-butadiene-4-nitrile or 1 and/or 4-substitution products thereof with a compound containing labile hydrogen attached to carbon having an adjacent activating group, to sulphur, nitrogen or chlorine, or with an alkali metal derivative of a compound containing labile hydrogen attached to sulphur.  Examples of such compounds are nitromethane and other primary or secondary nitroparaffins, aldehydes and ketones, malonic esters, cyanacetic esters, malononitrile, aceto-acetic esters and other b -ketonic esters, aryl-acetonitriles such as benzyl cyanide, aryl acetic esters such as ethyl phenyl-acetate, aryl methane sulphonamides, such as benzyl sulphonamide, fluorene, thiols, including mercaptans and hydrogen sulphide, amines, including hydrazine and its derivatives, amides and ammonia, and hydrogen chloride.  In the case of ester, nitrile, sulphonamide and aryl activating groups, it is preferred to have two such groups attached to one carbon atom.  The main products are those of 1,4-addition.  Substitution products of butadiene nitrile specified as reactants are sorbonitrile, cinnamal acetonitrile, a -cyano-sorbic acid or its esters, cinnamal cyanacetic acid or methyl or ethyl ester, cinnamal malononitrile and cinnamal benzyl cyanide.  Alkaline catalysts such as caustic alkali, sodium carbonate, alkali cyanides, sodium alcoholates, sodium sulphite, quaternary bases, e.g. trimethyl benzyl ammonium hydroxide, are generally used, although acids such as acetic or sulphuric or copper sulphate are, in some cases, of use while, with amines or hydrogen chloride, no catalyst is required. Temperatures are from atmospheric up to 80 DEG  C. or more, while diluents may be present.  With compounds containing two or more labile hydrogen atoms, an excess of, for example, 5-20 moles. may be used if reaction with only 1 mole. of the nitrile is required. The products with nitroparaffins are nitro-nitriles which may be reduced to di- or poly-amines or saponified and reduced to amino-, mono- or poly-carboxylic acids. With ketones, the butadiene nitrile adds first to the carbon adjacent the keto group having the least number of hydrogen atoms and, generally, only when this is saturated does addition to the other adjacent carbon occur. With aldehydes, addition to a mixture of the nitrile and alkaline catalyst may prevent resinification.  Aldehydes with only one hydrogen on the carbon adjacent the aldehyde group, e.g. isobutyraldehyde and diethyl acetaldehyde, give smooth reaction. The keto- or aldehydonitriles produced may be reduced to aminocarbinols, hydrolysed and reduced to hydroxyacids, reduced in presence of ammonia to polyamines or if subsequent to saponification, to amino-acids or treated with hydrogen or ammonium cyanide and reduced, with or without saponification, to yield hydroxy-, amino-hydroxy- and amino-acids, amino-alcohols and polyamines.  Other addition products may similarly be reduced before or after saponification.  Organic thiols, e.g. mercaptans or thiophenols, give thio-ether-nitriles which yield thio-ether-amines or acids.  Hydrogen sulphide gives d ,d 1-thio-dipentenoic nitrile.  Diprimary amines, e.g. ethylene diamine, with 2 moles. of butadiene nitrile, give diamino-dinitriles yielding, on reduction, tetramines convertible to polyamides.  A strong base may sometimes produce simultaneous saponification of the nitrile group.  Thus, butadiene nitrile with ammonium hydroxide and carbonate in presence of caustic soda gives amino-pentenoic acid directly.  In examples: (1) 1,3-butadiene-4-nitrile is added to diethyl malonate and sodium alcoholate in ether and boiled under reflux, the product recovered by fractionation, hydrogenated and hydrolysed to yield pimelic acid; (2) the diethyl ester of ethyl malonic acid similarly gives a -ethyl pimelic acid while the ethyl ester of a -cyanobutyric acid yields the same product.  Other mono-substituted malonic or cyanacetic esters may be used.  Substituted aceto-acetic esters give products which, after reduction and hydrolysis give the dicarboxylic or ketonic acid; (3) butadiene nitrile is added to nitromethane and caustic potash in alcohol at 40 DEG  C., and the product hydrogenated to hexamethylene diamine or saponified prior to hydrogenation yielding e -amino-caproic acid; (4) acetone and butadiene nitrile are reacted, and the product hydrolysed and reduced to give e -acetyl-caproic acid; (5) pentamethylene diamine and the nitrile are reacted, and the product hydrogenated; (6) hydrogen sulphide yields an addition product which, on hydrogenation, gives di-(e -amino-n-amyl)-thio-ether or, on saponification and hydrogenation, gives a thio-dicarboxylic acid. The Provisional Specification comprises also addition of the nitrile to alcohols or phenols, giving unsaturated alkyloxy, aralkyloxy or aryloxy nitriles, which may be reduced to the corresponding amines or saponified and reduced to the carboxylic acids, to water, cellulose or polyvinyl alcohol.  In the presence of a strong base, ethers of cellulose or polyvinyl alcohol are formed which may be saponified giving, for example, carboxy-butenyl cellulose useful as a size or adhesive.  With ammonium hydroxide and carbonate in presence of caustic soda, the nitrile gives the aminopentenoic acid direct.