Catalytic carboxylation of fats. Carboxy acids and esters from monounsaturates

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) is catalyzed with a mixture of palladium chloride and triphenylphosphine at 120–150 C with or without acetone or acetic acid solvents. Palladium supported on carbon is also an effective hydrocarboxylation catalyst in the presence of triphenylphosphine and HCl. Methyl 9(10)-carbomethoxystearate was prepared by catalytic carbomethoxylation of methyl oleate with methanol and carbon monoxide but in lower yields. The carboxystearic acids and esters consisted of the 9 and 10 isomers (87–94%) in approximately equal proportions. This catalytic carboxylation procedure is a more efficient route to carboxystearic acid and ester than the two-step hydroformylation-oxidation process reported previously. Carboxylated acids, methyl esters and triglycerides of potential industrial importance have been prepared. Presented at the AOCS Meeting, Ottawa, September 1972.     

Acyl esters from oxo-derived hydroxymethylstearates as plasticizers for polyvinyl chloride

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)-acetoxymethylstearate 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, acetoxymethylated safflower and linseed oils produced good compatibility and outstanding permanence, better than esters commonly used as commercial plasticizers.     

Hydroformylation of unsaturated fatty acids

When hydroformylation of unsaturated fatty materials is done with rhodium-triphenyl phosphine (or phosphite) catalysts, a number of advantages become apparent compared to cobalt carbonyl-catalyzed reactions. With rhodium, the reaction can be carried out (a) at pressures as low as 200 psi, (b) at each double bond location in a polyunsaturated fatty acid, and (c) in high yield and conversion. Solubilized catalyst can be recovered from distillation residue and readsorbed on spent catalyst support by thermal treatment in a rotary kiln. The reconstituted catalyst is more active than the original catalyst and can be recycled indefinitely at a relatively low cost. Recently developed supports for “homogeneous” catalysis may make catalyst recovery even more effective. Acetalation, oxidation with air to polycarboxylic acids and catalytic hydrogenation to hydroxymethyl compounds can be done easily and in high yield on mono-, di- and triformyl derivatives alike. Other reactions investigated for monoformyl fatty esters include reductive amination to form aminomethyl derivatives and Tollen’s condensation with formaldehyde to form geminal,bis-hydroxymethyl compounds. although the Northern Center has carried out some basic investigations on the hydroformylation reaction and on the chemistry of the hydroformylated products, there is a great deal more that can be done with regard to synthesis of new compounds and development of new applications.     

Fatty methyl ester hydrogenation to fatty alcohol part II: Process issues

Fatty alcohols are produced by hydrogenating fatty methyl esters in slurry phase in the presence of copper chromite catalyst at temperatures of 250–300°C and hydrogen pressures of 2000–3000 psi. The fatty methyl ester, catalyst, and hydrogen are fed to the reactor cocurrently. The product slurry is passed through gas-liquid separators and then through a continuous filtration system for removal of the catalyst. A portion of the used catalyst in crude alcohol is recycled to the hydrogenator. The overall efficiency of the process depends upon the intrinsic activity, life, and filterability of the catalyst. The fatty alcohol producer therefore requires a catalyst with high activity, long life, and good separation properties. The main goal of the present laboratory investigation was to develop a superior copper chromite catalyst for the slurry-phase process. Two copper chromite catalysts, prepared by different procedures, were tested for methyl ester hydrogenolysis activity, reusability, and filtration characteristics. The reaction was carried out in a batch autoclave at 280°C and 2000–3000 psi hydrogen pressure. The reaction rates were calculated by assuming a kinetic mechanism that was first-order in methyl ester concentration. The catalyst with the narrower particle size distribution was 30% more active, filtered faster, and maintained activity for several more uses than the catalyst with the broader particle size distribution. X-ray photoelectron spectroscopy data showed higher surface copper concentrations for the former catalyst.     

Chemical reactions of fatty acids with special reference to the carboxyl group

Unsaturated fatty acids contain unsaturated centres and the carboxyl group both of which can be modified to give a range of interesting and useful compounds. The former have been discussed in detail in two recent references [8, 9] and therefore this paper will be concerned with the reactions of the carboxyl group and its derivatives. Attention is directed to the lactones, alcohols and their ethoxylates and sulfates, to the preparation of cleavable surfactants (acetals, ketals, ortho esters and ester quats), Guerbet alcohols and acids, alkyl polyglycosides and to amines and other nitrogencontaining compounds.     

Rigid urethane foams from hydroxymethylated castor oil,safflower oil,oleic safflower oil,and polyol esters of castor acids

Castor, safflower, and oleic safflower oil derivatives with enhanced reactivity and hydroxyl group content were prepared by hydroformylation with a rhodium-triphenylphosphine catalyst, followed by hydrogenation. Rigid urethane foams prepared from these hydroxymethylated derivatives had excellent compressive strengths, closed cell contents, and dimensional stability. Best properties were obtained from hydroxymethylated polyol esters of castor acids.     

Reactions of carbon monoxide with unsaturated fatty acids and derivatives: A review

The important reactions of carbon monoxide with unsaturated fatty derivatives that are reviewed in this paper include hydroformylation (the oxo reaction), Koch carboxylation and Reppe carbonylation. With oleic acid as a substrate, the products are C₁₉ bifunctional compounds e.g., formyl- or carboxy-stearic acid. Double bond isomerization before carbon monoxide addition is characteristic of these catalytic reactions; additionally, rearrangement to introduce methyl branching occurs in the Koch carboxylation. Isomerization does not occur when a rhodium-triphenylphosphine catalyst replaces cobalt in the oxo reaction. Properties of the C₁₉ dicarboxylic acids differ and depend upon method of preparation: Many areas of application have been reported for C₁₉ compounds-lubricants, plasticizers, polyurethanes, epoxy resins, leather and other coatings, unsaturated polyester resins and transparent polyamide plastics. Presented at the AOCS Meeting, Los Angeles, April 1972. N. Market. Nutr. Res. Div., ARS, USDA.     

Some factors affecting hydrogenation of milk fat

Hydrogenation of milk fat with palladium and nickel as catalysts was studied at various temperatures, pressures, and concentrations of catalyst. Samples were removed from the laboratory hydrogenator at intervals during the reaction, and changes in refractive index, iodine value, Wiley mp, and percentages of fatty acids andtrans-isomers were determined. Palladium was several times more active as a catalyst than nickel. Milk fat with an iodine value of 35 and mp of 34 C was hydrogenated with 0.05% palladium to an iodine value of 6 and a mp of 46 C in 30 min at 66 C and 53 psi of hydrogen. Kinetic data for each catalyst yielded two slopes, indicating that a change in reaction rate occurred.     

Zur Hydrocarboxymethylierung von ungesättigten Fettsäureestern

On the Hydrocarboxymethylation of Unsaturated Fatty Acid Esters The hydrocarboxymethylation of technical oleic acid and eruca acid methyl ester was tested in the presence of the catalyst system cobalt/4-picoline. It was known for non terminal olefins that the formation of unbranched carboxylic acid derivatives is facilitated with the cobalt/picoline system. So up to 75% of the unbranched product is obtained during the hydrocarboxymethylation of μ-olefins. It was shown in the case of the unsaturated fatty acid methyl esters that here, too, by precise control of the reaction temperature, promoter/catalyst ratio and CO pressure the hydrocarboxymethylation can be carried out in such a way that up to 60% of the α, ω-dicarboxylic acid dimethyl esters are obtained.     

Metal-Catalyzed Alkene Functionalization Reactions Towards Production of Detergent and Surfactant Feedstocks

Metal complexes have been used as catalysts in alkene transformation reactions to produce alcohols, esters, and organic acids as potential raw materials for the manufacture of detergents, perfumes, and other fine chemicals. Herein, we report the use of palladium(II) and ruthenium complexes as efficient catalyst precursors for the methoxycarbonylation, hydrogenolysis, and ethoxylation reactions of higher alkenes. The palladium catalysts showed high chemoselectivity (>98 %) and regioselectivities of about 40 % towards the formation of esters and branched isomers, respectively. Subsequent hydrogenolysis of the esters to the corresponding alcohols was achieved using ruthenium catalysts. Reactions of the esters and alcohols with ethylene oxide using calcinated aluminum oxide catalysts produced the corresponding alcohol and methyl ester ethoxylates, respectively. The identity of the phosphine derivatives, catalyst loading, reaction time, temperature, and pressure were found to influence the catalytic activity and regioselectivity of the complexes.     

Aspects of carbon dioxide utilization

Carbon dioxide reacts with hydrogen, alcohols, acetals, epoxides, amines, carbon–carbon unsaturated compounds, etc. in supercritical carbon dioxide or in other solvents in the presence of metal compounds as catalysts. The products of these reactions are formic acid, formic acid esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, polycarbonate (bisphenol-based engineering polymer), aliphatic polycarbonates, etc. Especially, the productions of formic acid, formic acid methyl ester and dimethylformamide with a ruthenium catalyst; dimethyl carbonate and urethanes with a dialkyltin catalyst; 2-pyrone with a nickel-phosphine catalyst; diphenyl carbonate with a lead phenoxide catalyst; the alternating copolymerization of carbon dioxide and epoxides with a zinc catalyst has attracted attentions as the industrial utilizations of carbon dioxide. The further development of these production processes is expected.     

Hydrocarboxylation of Styrene in Aqueous Media with Pd-guanidinumphosphine Systems

Hydrosoluble palladium complexes with guanidinumphosphine ligands are active catalyst precursors for the hydrocarboxylation of styrene forming the corresponding carboxylic acids using water as a solvent. The aryl guanidinum derivative is much more stable than the alkyl derivative studied and provided high selectivity in the acids with conversions up to 96%.     

Catalytic carboxylation of fats: Carboxy acids from polyunsaturates

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 1,4-dicarboxy 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. Presented at the AOCS Spring Meeting, Mexico City, April 1974. Biometrician, North Central Region, USDA. ARS, USDA.     

Preparation of meadowfoam dimer acids and dimer esters,and their use as lubricants

Meadowfoam dimer acids have been prepared in a thermal clay-catalyzed reaction. Reaction conditions have been optimized, and yields of 44% were obtained with 2% water and 6–8% of an acid-washed montmorillonite clay, based on the meadowfoam fatty acids. Purity of the distilled dimer acids was 79–89% with most of the remaining 11–22% being residual mono- and tribasic acids. Dimethyl, di-(2-ethylhexyl), and di-n-butyl meadowfoam dimer ester derivatives were also prepared. Color, viscosity, and wear-preventive characteristics of the meadowfoam dimer acids and dimer ester derivatives were compared to those of commercial dimer acids and dimer esters. The viscosity of the meadowfoam dimer acids is similar to that of Empol® 1010, which is also derived from a highly monounsaturated fatty acid source. Viscosities of the meadowfoam dimer esters were also comparable to those of commercial dimer esters. Wear prevention characteristics, as determined by the four-ball test method, of the meadowfoam dimer acids and dimer esters were similar to those of the commercial products. In one case, the di-n-butyl esters, the meadowfoam derivative showed a significantly smaller wear scar than that shown by the di-n-butyl derivative of Unidyme® 14.     

Hydrogenolysis of saturated,oleic and ricinoleic acids to the corresponding alcohols

Fatty acids are hydrogenolysed to correspond-ing alcohols in 90% yield at 220-250C at pres-sures of 3500-4000 psi. For saturated acids the catalyst is one per cent of copper and for oleic and ricinoleic acids 2% of copper and one per cent of cadmium, all present as their soaps. Only 10% of the unsaturation is lost. The main side product is the acid-alcohol ester. In hydrogenoly-sis of ricinoleic acid, the alcohol obtained con-tains 15% of ester and 10% of lower alcohols such as undecenyl.     

Chemo-enzymatic synthesis of disaccharide fatty acid esters

A novel enzymatic method for the synthesis of disaccharide fatty acid esters was developed with immobilizedMucor miehei lipase (Lipozyme IM-60; Novo Nordisk, Bagsvaerd, Denmark) as a catalyst. A range of lactose and maltose monoesters was prepared in overall yields of 48–77% from the corresponding sugar acetals and fatty acids.     

Hydroformylierung einfach und mehrfach ungesättigter Fettstoffe mit heterogenisierten Cobaltcarbonyl- und R

Hydroformylation of mono and multiple unsaturated fatty substances with heterogenized cobaltcarbonyl and rhodiumcarbonyl catalysts. Heterogenized cobalt and rhodiumcarbonyl catalyst systems can be used for the hydroformylation of mono and polyunsatured fatty substances in a technically simple and satisfying manner to useful chemical intermediates. The used solid tert. phosphane complex ligands have a silicate matrix and therefore they are also suitable for the cobalt catalyzed hydroformylation which is best performed at temperatures of 160–180^oC. The cobalt catalyzed reaction gives with polyunsaturated fatty substances almost only products with monofunctionalized fatty acid chains. Whereas, the rhodium catalyzed reaction gives with linolic acid compounds inhomogeneous mixtures of mono- and diformyl derivatives of these fatty substances. The heterogenized rhodium carbonyl catalyst systems therefore seem to be more suitable for the hydroformylation of monounsaturated compounds. This is also true for rhodiumcarbonylsupported aqueous phase-catalysts which give likewise mixtures of mono and diformyl derivatives in the hydroformylation of polyunsaturated fatty substances. In batch process after the complete conversion of the olefin and reduction of the CO/H₂-pressure the loss of catalyst metal from the support is negligible and in most cases below the detection limit (<1 ppm).     

Selektivhydrierung von Fettstoffen mit metallorganischen Mischkatalysatoren nach Ziegler-Sloan-Lapporte II: Hydrierung von Fettsäureestern zu Fettalkoholen

Selective Hydrogenation of Fats and Derivatives using Ziegler-Type Organometallic Catalysts II: Hydrogenation of Fatty Acid Esters to the Primary Alcohols The reaction of cobalt- or nickelcompounds with triethylaluminium lead to homogeneous metallorganic catalysts from Ziegler-type, which were applicated in the hydrogenation of fatty acid esters as homogeneous analogous of the heterogeneous Adkins-catalyst. The fatty acid esters could be hydrogenated, under milder conditions (Temperature = 70–190°C, Pressure = 10–90 bar), with good conversions till 100% and yields over 80 mol% to the corresponding primary alcohols. But the needed amounts of catalyst were high. It could be secured that the excess of triethylaluminium in the catalyst complex (AlEt³/transition metall = 7.5) didn't participate to the hydrogenation of the fatty acid ester to the primary alcohol, but only to the formation of insignificant amounts of alkylated derivatives of the fatty acid ester.     

Die unterschiedliche Bedeutung der Fettsäuren in ihrer fungistatischen Wirkung

Significance of Fatty Acids in Their Fungistatic Action The fungistatic action of saturated and unsaturated fatty acids, halogenated fatty acids and esters as well as sulfurcontaining derivatives is reviewed. Fungistatic agents, known since a long time, are propionic acid, caprylic acid and its salts as well as undecylenic acid and its salts. The recently known fatty acid derivatives having fungistatic action are morpholine and piperidine compounds of long chain fatty acids and the new class of aminimides of fatty acids with 14–16 C atoms.     

Hydrogenation of cyclopropenoid fatty acids occurring in cottonseed oil

The hydrogenation of cyclopropenoid acids and their relative reactivities during hydrogenation as compared to linoleic and oleic acids were examined. Pure methyl sterculate and purifiedSterculia foetida oil and its methyl esters, which have a cyclopropene content more than 60 times that of cottonseed oil, were used for the hydrogenation experiments. Nickel, palladium and platinum catalysts were used. The effect of temperature and type of catalyst were demonstrated in a series of hydrogenation experiments of safflower andS. foetida oil mixtures, and methyl oleate and methyl dihydrosterculate mixtures. Partial hydrogenation of methyl sterculate formed as many as twenty compounds in addition to the cyclopropenoid derivatives. Most of these compounds were monounsaturated. The cyclopropene group hydrogenated very readily compared to the 9,12-diene system in linoleate. The cyclopropane group obtained by hydrogenating the cyclopropenoid acids group was quite resistant to further attack by hydrogen and nickel catalyst had little effect. With palladium catalyst, a temperature of 180 C was necessary for the reaction to go to completion. Platinum in acetic acid was a good system for hydrogenolysis of the cyclopropane group at 80 C. Retired.