GB788541A - 3, 4-epoxycyclohexanecarboxylic acids and esters thereof - Google Patents

Abstract

The invention comprises 3,4-epoxycyclohexane carboxylic acids and their esters having the general formula <FORM:0788541/IV (b)/1> in which R1, R2, R3, R4, R5 an R6 are either hydrogen atoms or alkyl groups, and when n is 1, M is a hydrogen atom or an aliphatic group, and when n is 2, M is a residue of an aliphatic polyhydric halogenated alcohol, or an aliphatic polyhydric ether alcohol, or a thiodiglycol. The novel compounds may be prepared by epoxidizing a 3,4-cyclohexenyl-carboxylic acid or ester thereof either by using acetaldehyde monoperacetate in accordance with the method described in Specification 735,974, or by reaction with peracetic acid at 20-50 DEG C. in an inert organic solvent. The starting materials are derived by the reaction of butadiene or homologues thereof with a ,b -unsaturated aliphatic acids, such as: crotonic acid and 2-methyl-1,3-pentadiene, 2-methyl-3-ethylacrylic acid and 2,3-dimethyl butadiene, acrylic acid and isoprene, crotonic acid and 2,4-dimethyl-1,3-butadiene, crotonic acid and 1,3-pentadiene, 3-ethylacrylic acid and isoprene, acrylic acid and 2,4-hexadiene, 2-methyl-3-ethyl-acrylic acid and isoprene, acrylic acid and butadiene, crotonic acid and butadiene. The alcohols used to esterify the acids so-formed may be any suitable substituted or unsubstituted, saturated or unsaturated, aliphatic mono- or polyhydric alcohols, ether alcohols, or halogenated alcohols, or thiodiglycols, such as methanol, ethanol, butanol, hexanol, allyl alcohol, ethylene glycol, diethylene glycol, 2-ethyl - 1,3 - hexanediol, 3 - methyl - 1,5 - pen-tanediol, 2 - methoxymethyl - 2,4 - dimethyl - 1,5-pentanediol, triethylene glycol, 1,5-pentanediol, or 1,1,1-trimethylol propane. The products obtained by peracetic acid epoxidation may be recovered by mixing with ethyl benzene and distilling at a temperature up to 90 DEG C. under reduced pressure. Examples describe the preparation using peracetic acid in acetone solution of (1) diethylene glycol bis-(3,4-epoxycyclohexanecarboxylate); (2) 2-ethyl-1,3-hexanediol bis (3,4-epoxycyclohexanecarboxylate); (3) 1,6-hexanediol bis-(3,4-epoxycyclohexanecarboxylate); (4) diethylene glycol bis-(6-methyl - 3,4 - epoxycyclohexanecarboxylate); (5) 3 - methyl - 1,5 - pentanediol - bis - (3,4 - epoxycyclohexanecarboxylate); (6) 2-methoxymethyl - 2,4 - dimethyl - 1,5 - pentanediol bis-(3,4 - epoxycyclohexanecarboxylate); (7) triethylene glycol bis-(3,4-epoxycyclohexanecarboxylate); (8) 1,5-pentanediol bis-(3,4-epoxycyclohexanecarboxylate); (9) ethylene glycol bis - (3,4 - epoxycyclohexanecarboxylate); (10) allyl 3,4 - epoxycyclohexanecarboxylate; (11) ethyl 3,4 - epoxycyclohexanecarboxylate; (12) vinyl 3,4 - epoxycyclohexanecarboxylate; (13) 3,4 - epoxy - 6 - methyl - cyclohexanecarboxylic acid. The products are useful as modifiers, plasticisers and stabilizers for synthetic resins and as intermediates in the preparation of synthetic lubricants, tanning agents and biological preparations.