A highly selective catalytic, one-step synthesis converts oleic acid into 9(10)-carboxystearic acid in high yields (85-99%). Hydrocarboxylation with water and carbon monoxide under pressure (3000-4000 psi)

Hydroformylation of methyl linoleate and linolenate with a rhodium-triphenylphosphine catalyst yields 1,4diformyl esters as major products and 1,3-diformyl esters as minor products. Unsaturated and saturated monoformyl esters are also produced from both substrates and triformyl esters from methyl linolenate. Conjugated methyl linoleate produces mainly monoformyl esters, whereas methyl c/s-9,c/s-l 5-octadecadienoate produces diformyl esters. The mechanism postulated for dihydroformylation involves cyclic unsaturated acyl-rhodium-triphenylphosphine complexes controlling the position of the second formyl group. These intermediates are also implicated in double-bond hydrogenation and isomerization which accompany dihydroformylation. The polyformyl ester products formed contrast with the monoformyl ester products obtained when cobalt carbonyl catalysts are used.

Soybean, safflower and linseed oils and their methyl esters were effectively hydroformylated with a rhodium and triphenylphosphine catalyst system. The product from safflower methyl esters, hydroformylated at 100 C and 1000 psi synthesis gas (H2 + CO), proved to be a mixture of formylstearate, formyloleate and diformylstearate. At 150 C and 15 00 psi synthesis gas the formyloleate was hydrogenated and the product formed was a mixture of mono‐ and diformylstearates. The unsaturated monoformyl fraction (100 C) was tentatively identified as a mixture consisting mainly of methyl 9(10)‐formyl‐cis‐12‐and methyl 12(13)‐formyl‐cis‐9‐octadecenoates. The saturated monoformyl fraction (150 C) was a more complex isomeric mixture of methyl formylstearate. The diformyl fractions from hydroformylated safflower and linseed esters were identified as mixtures consisting mainly of 9,12‐(10,13)‐ and 10,12‐(11,13)‐diformyloctadecanoates. When hydroformlyation of polyunsaturated fats was interrupted,cis‐unsaturated formyl oils resulted.

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Hydroxymethylstearates were made by hydroformylation or oxo reaction of mono-and polyunsaturated fats and esters with either rhodium-triphenylphosphine or cobalt carbonyl catalysts. Rhodium-oxo products were hydrogenated with nickel catalyst, whereas, cobalt-oxo products were heated directly under hydrogen pressure. Hydroxymethyl fatty alcohols also were prepared by a two-step copper-chromite hydrogenation of hydroformylated linseed fatty esters. Of these hydroxymethyl compounds, 39 were converted to their acetates and other acyloxy derivatives and then evaluated as primary plasticizers for polyvinylchloride. For compounds with good compatibility, methyl 9(10)-acetoxymet hylstearate and 9(10)-acetoxymethyloctadecyl acetate gave the lowest flex temperature (-47 C). An unusual combination of good compatibility and low flex temperature was obtained with 2-methoxyethyl 9(10)-acetoxymethylstearate. Addition of more than one acetoxymethyl group in the fatty acid molecule, made possible by rhodium hydroformylation, imparted good compatibility and outstanding permanence (low migration and volatility) but raised flex temperature. Butyl diacetoxymethylstearate, methyl triacetoxymethylstearate, and polyacetoxymethyloctadecyl acetate from linseed esters displayed good compatibility, strength, and volatility characteristics. As glycerides, acetoxymethytated safflower and linseed oils produced good compatibility and outstanding permanence, better than esters commonly used as commercial plasticizers. Z > © ~q > Z r~ o0 < © L~ t,~

Studies with a palladium chloride-triphenylphosphine catalyst have been extended to the carboxylation of polyunsaturated fats. Linseed, soybean, and safflower oils, acids, and esters were carboxylated catalytically with water-carbon monoxide (4000 psig) at 120-160 C with or without acetone as a solvent. Main products were monocarboxy, 1,3-and 1,4dicarboxy and tricarboxy acids. Minor products were carbomethoxy esters and disubstituted 2-cyclopentenone. Optimum reaction conditions were determined for the carboxylation of linseed oil and methyl esters by statistically designed experiments. Yields of total carboxy and tricarboxy acids were maximized at low triphenylphosphine and water levels, low temperatures, and high palladium-chloride concentrations. Carboxylated soybean esters were separated by ether extraction of the palladium catalyst from sodium carbonate or hydroxide carboxylate salts. This salt extraction permits catalyst recycling.

Methyl mono‐, di‐, and tricarboxystearates were prepared by either a two‐step hydroformylation‐oxidation reaction or direct hydrocarboxylation of unsaturated vegetable oil methyl esters. Procedures were developed for preparing alkyl dicarbomethoxy‐, dicarboethoxy‐, and dicarbobutoxystearates. These triesters, along with some di‐ and tetraesters from mono‐ and tricarboxystearic acids, were evaluated as primary plasticizers for polyvinyl chloride (PVC). Except for butyl carbobutoxystearate, the esters were compatible at the 32% level and had properties equal or superior to those of dioctyl phthalate. Methyl and butyl diesters of carboxystearic acid had undesirable migration and volatility properties. The migration and volatility properties of some tri‐ and tetraalkyl esters were equal to or better than the controls. Of the various esters tested, methyl dicarbomethoxystearate containing 13–49% methyl tricarbomethoxystearate was an efficient plasticizer for PVC at the 32% level.

IN the pieceding investigation (this vol., p. 793), a n account has been given of the hydrolysis of indican by means of acids, and the present paper deals with the still more important question of the behaviour of the glucoside with its specific enzyme, indimulsin. With the exception of some preliminary experinierits by Gaunt, Thomas, and Bloxam