GB820095A - Beta-alkoxycarbonyl compounds and process for manufacture of same - Google Patents

Abstract

Solid polyvinyl chloride resins may be plasticized with phthalic acid esters of alcohols of formula <FORM:0820095/IV (a)/1> where R1, R2 and R3 are hydrogen or C1-4 alkyl, R4 is C1-8 alkyl, and R5 is an alkyl or cycloalkyl radical having 2-10 carbon atoms, or a hydrogenated aryl or furyl group.ALSO:The invention comprises compounds of the formula <FORM:0820095/IV (a)/1> where R1, R2 and R3 are hydrogen atoms or an alkyl group containing 1-4 carbon atoms, R4 is an alkyl group containing 1-8 carbon atoms, and R5 is an aryl, furyl, alkenyl, cycloalkenyl, alkadienyl or cycloalkadienyl radical containing a gamma-delta double bond, said alkenyl radical having 2-10 carbon atoms and said alkadienyl, cycloalkadienyl and cycloalkenyl radicals having 5-10 carbon atoms. These compounds may be prepared by reacting no more than one mol. of a compound <FORM:0820095/IV (a)/2> with at least one mol. of a compound R5CHO under substantially anhydrous conditions in the presence of a Friedel-Crafts metallic halide catalyst (including BF3), sulphoacetic acid, concentrated sulphuric acid, or a catalyst composed of a boron compound containing a B-O linkage and oxalic acid, an o-hydroxy aromatic acid, or an alpha-hydroxy acid. This last catalyst may be prepared in situ or separate from the reactants, by grinding the organic carboxylic acid with the oxy-boron compound, or by adding the ingredients simultaneously to the aldehyde reactant. Specified ingredients are pyro-, meta- and ortho-boric acids and trimethyl, triethyl and tributyl borate on the one hand, and oxalic, glycolic, lactic, malic, citric, tartronic, tartaric, mucic, salicylic and mandelic acids on the other, preferably in equimolar proportions. The catalyst may be used in amounts of 0.02-2% of the reactants. The preferred ratio of reactants is 2.5-5 mols. of aldehyde per mol. of ether reactant; preferred temperatures are 10-120 DEG C. Examples describe the preparation of (1)-(8) and (19)-(23) 3-ethoxy-4-hexenol; (9) 3-methoxy-4-hexenol; (10) 3 - butoxy - 4 - hexenol; (11) 3 - ethoxy-2 - ethyl - 4 - hexenol; (12) 2,2 - dimethyl - 3-methoxy - 4 - hexenol; (13) 3 - ethoxy - 2-ethyl - 4 - octenol; (14) 3 - ethoxy - 3 - phenylpropanol; (15) 3 - ethoxy - 2 - ethyl - 3-phenylpropanol; (16) 4 - ethoxy - 5 - heptene-2 - one; (17) 3 - ethoxy - 2 - ethyl - 4,6 - octadienol; and (18) 3 - ethoxy - 2 - ethyl - 3-furylpropanol. Comprehensive lists are given of suitable reactants, and many other compounds which may be prepared are specified. The compounds of the invention may be hydrogenated with Raney nickel catalyst at 50-150 DEG C. and 500-3000 p.s.i.g. to produce the corresponding saturated alcohols, which may be esterified with phthalic acid; the phthalate esters are useful as plasticizers (see Group IV (a)). Also 3-methoxy-, 3-ethoxy- and 3-butoxy-4-hexenol may be hydrolytically dealcoholated in the presence of 50 per cent acetic acid to sorbaldehyde, which can be oxidized with silver oxide to sorbic acid.