GB1015024A - New salts and quaternary salts of basic esters of substituted hexahydro benzilic acids, and a method of preparing same - Google Patents

Abstract

The invention comprises acid-addition salts and quaternary salts of the Formula I <FORM:1015024/C2/1> wherein R1 is a hydrogen or halogen atom or an ethyl, methoxy or methylmercapto group, X is a straight or branched chain alkylene group having 2 to 5 carbon atoms, R3 and R4 are alkyl groups having 1 to 4 carbon atoms, which may be linked direct or by way of a nitrogen or oxygen atom to form, together with the adjacent nitrogen atom, a residue of a secondary saturated heterocyclic amine having 4 to 7 carbon atoms, R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and A is an anion of an inorganic or organic acid. The compounds are prepared by (a) reacting a compound of the Formula II <FORM:1015024/C2/2> wherein M is an alkali metal atom, with a compound of the Formula III Y-X-NR3R4 wherein Y is a halogen atom or a residue of an aliphatic or aromatic thio acid, and then converting the thus obtained base either to an acid-addition salt by neutralization with an inorganic or organic acid, or to a quaternary salt by addition of a reactive alkyl ester, or (b) reacting a compound of the Formula II, wherein M is an alkyl group of 1 to 4 carbon atoms, with an excess of a compound of Formula III, wherein Y is a hydroxyl group, in the presence of the corresponding alkali metal amino alcoholate, and then converting the base thus obtained either to an acid-addition salt by neutralization with an organic or inorganic acid, or to a quaternary salt by addition of a reactive alkyl ester. Hexahydrobenzilic acids and esters.-o- and p-Fluoro-, o- and p-chloro-, p-bromo-, p-iodo-, p-ethyl-, p-methoxy-, 3,4-dimethoxy- and p-methylmercapto-hexahydrobenzilic acids are prepared by reacting the corresponding substituted phenylglyoxylic acid ethyl ester with cyclohexyl magnesium bromide, decomposing the resulting complex, and saponifying the hexahydrobenzilic acid ethyl ester so obtained. m-Fluoro-, o- and m-chloro- and m-methoxyhexahydrobenzilic acids are prepared by reacting cyclohexylglyoxylic acid ethyl ester with the corresponding substituted phenyl magnesium bromide, decomposing the complex obtained, and saponifying the resulting hexahydrobenzilic acid ethyl ester. Glyoxylic acids and esters.-o-Fluoro-, o- and p-chloro-, p-bromo- and p-methoxy-glyoxylic acid ethyl esters are prepared by oxidizing the corresponding substituted mandelic acid with KMnO4 and esterifying the resulting glyoxylic acid with ethanol. p-Fluoro-, p-chloro-, p-bromo-, p-iodo- and p-methylmercapto-glyoxylic acid ethyl esters are prepared by Friedel-Crafts reaction of ethoxalyl chloride with the corresponding substituted benzene in the presence of AlCl3 and CS2, and esterifying the resulting glyoxylic acid with ethanol. Cyclohexyl glyoxylic acid ethyl ester is prepared by esterifying the free acid with ethanol in the presence of sulphuric acid.