Methyl 9(10)-formylstearate by selective hydroformylation of oleic oils

A highly selective catalyst system has been discovered for the hydroformylation of methyl oleate into methyl 9(10)-formylstearate in high yields. A rhodium catalyst in the presence of triphenylphosphine is used with oleic esters, acids or triglycerides. Hydroformylation proceeds smoothly at 95-110C with a 1:1 mixture of H₂ and CO at 500 to 2000 psi with or without a solvent, such as toluene. The formylstearate obtained in 90% to 99% conversion from oleate can be either hydrogenated (Raney Ni) or reduced (NaBH₄) to hydroxymethylstearate or oxidized (KMnO₄) to carboxystearate. According to TLC and mass spectrometry, the methylated carboxystearate consists of about equal proportions of the 9 and 10 isomers. Addition of triphenylphosphine inhibits isomerization of the double bond and leads to the formation of a rhodium carbonyl triphenylphosphine complex, which is apparently the active catalyst. Other known methods for hydroformylation (cobalt carbonyl) and carboxylation (Koch’s method) of oleate give a wide distribution of isomers. Presented at the ISF-AOCS Meeting, Chicago, September 1970.     

A bulky phosphite-modified rhodium catalyst for the hydroformylation of unsaturated fatty acid esters

A series of hydroformylation experiments was performed with a high-grade and a technical-grade-derived methyl oleate (MO) and a rhodium catalyst modified by the bulky tris(2-tert-butyl-4-methylphenyl)phosphite. In the hydroformylation of pure methyl oleate, relatively high turnover numbers were obtained (400–500 mol/mol/h) under mild conditions (molar ratio MO/Rh=910, 80–100°C and 20 bar; CO/H₂=1:1, solvent toluene), leading to about 95% conversion in 3 h. Fast isomerization occurs under these conditions to produce the trans oleate. Trans oleate reacts more slowly than cis oleate. At temperatures below 50°C, isomerization does not occur. The use of technical-grade methyl oleate, containing 14% 9,12 diene, methyl linoleate (ML), results in lower reaction rates because dienes form stable π-allylic intermediates, which slowly undergo hydroformylation. More severe conditions were applied to obtain higher rates. The rate varied from 50 to 400 mol/mol/h, depending on conditions (molar ratio MO/Rh=910, T=50–120°C, P = 50–80 bar; CO/H₂=1:1–1:6, solvent, toluene). Several isomers of ML were formed during the reaction. Subsequent hydroformylation of these isomers results in a complicated mixture of products. The product mixture consists predominantly of methyl formylstearate, methyl formyloleate, methyl diformylstearate, and some yet unidentified side products. A comparison of the classic triphenylphosphine-modified catalyst and the bulky phosphite-modified catalyst has shown that the latter is several times more active.     

Hydroformylation with recycled rhodium catalyst and one-step esterification-acetalation: A process for methyl 9(10)-methoxymethylenestearate from oleic acid

Previous studies on hydroformylation of methyl oleate with rhodium and triphenylphosphine or triphenylphosphite have led to a laboratory process for recycling the precious metal catalyst. Another catalyst recycling process has now been studied as the basis for converting commercially available oleic acid into the enol ether of methyl formylstearate. The process involves one-step esterification-acetalation of formylstearic acid made by hydroformylating oleic acid with rhodium and triphenylphosphine. Esterification-acetalation is done in a recycling system with methanol, an acid-exchange resin for catalysis, and molecular sieves to remove water from the reaction mixture. The dimethyl acetal methyl ester formed from formylstearic acid is thermally cracked and distilled in one pot to produce the enol ether, methyl methoxymethylenestearate. The soluble rhodium catalyst in the distillation residue is combined with the insoluble catalyst from filtration and recycled for hydroformylation. The product methoxymethylenestearate is a versatile and stable derivative for various potential industrial applications. Presented at the AOCS meeting, Cincinnati, September 1975.     

New approaches to supramolecular transition metal catalysis

The combination of molecular recognition, phase transfer catalysis and transition metal catalysis in one and the same water–soluble catalyst leads to new perspectives, including increased activity, novel substrate selectivity and the possibility of simple catalyst recovery. For example, Rh–complexes of β–cyclodextrin modified diphosphanes function as supramolecular catalysts in aqueous two–phase hydrogenation and hydroformylation. Metal–containing dendritic compounds constitute another new class of supramolecular catalysts which are easily recycled. This revised version was published online in June 2006 with corrections to the Cover Date.     

Mizellare Zweiphasen-Hydroformylierung von ungesättigten Fettstoffen mit wasserlöslichen Rhodiumcarbonyl/tert. Phosphan-Komplexkatalysatorsystemen

Micellar Two Phase-Hydroformylation of Multiple Unsaturated Fatty Substances with Water Soluble Rhodiumdicarbonyl/tert. Phosphine Catalyst Systems Low- and medium-molecular ω-unsaturated carboxylic acid methyl esters inclusive of the ω-decenoic acid ester can be hydrofomylated successfully according to the two phase method in an aqueous-organic medium using the water soluble rhodium carbonyl/tris(sodium-m-sulfonatophenyl)phosphine complex as catalyst system. Highermolecular unsaturated fatty acid esters, e.g. the triple unsaturated linolenic acid methyl ester or fatty oils like linseed oil can be hydroformylated only according to the micellar two phase technique in course of which surfactant micelles cause a solubilisation of the water insoluble unsaturated fatty substances in the aqueous catalyst phase. The different efficiences of the various types of surfactants for the micellar two phase hydroformylation was investigated and interpreted. Best suitable for the micellar two-phase hydroformylation are cationic surfactants. By means of these surfactants linolenic acid methyl ester could be hydroformylated to the triformyl derivative with a selectivity of 55%. The recovery of the catalyst solution free from losses of rhodium succeeded by simple phase separation in a technically satisfying manner.     

Hydroformylierung mit wasser- und methanollöslichen Rhodiumcarbonyl/Phenyl-sulfonatoalkylphosphan-Katalysatorsystemen – Ein neues Konzept für die Hydroformylierung höhermolekularer Olefine

Hydroformylation with Water- and Methanol-soluble Rhodium Carbonyl/phenyl-sulfonatoalkyl-phosphine Catalyst Systems – A New Concept for the Hydroformylation of Higher Molecular Olefins The heterogenization of the homogeneous hydroformylating catalyst system enables the recovery of the catalyst from the reaction products by a simple phase separation but it is unfavourable that many advantages of the homogeneous catalysis are given up by this procedure. To avoid this drawback we used rhodium carbonyl/tert. phosphine catalyst systems soluble as good in methanol as in water for the homogeneously catalyzed hydroformylation of the olefin in methanolic solution. Only after reaction the product mixture is heterogenized by adding water forming an aqueous phase containing the catalyst system. It was shown by the hydroformylation of n-tetradecene-1 with rhodium carbonyl/phenyl-sulfonatoalkyl-phosphine catalyst systems that this new conception is very useful for the oxo reaction of high-molecular olefins.     

Organometallic Rhodium Complexes Encapsulated in Mesoporous Molecular Sieves

Rh(III) complexes both dimmer [Cp*RhCl]₂(μ-Cl)₂ and monomer ([RhCp*(S)₃]²⁺) were encapsulated into MCM-41 channels. All silica MCM-41 molecular sieve and aminosililated MCM-41 matrix were used for rhodium complexes accommodation. Reactivity of Cp* rhodium complexes encapsulated in meso structure was estimated on the grounds of their susceptibility to interaction with CO molecules resulting in the formation of carbonyl complexes. Formation of Cp*Rh carbonyls was recorded by means of FTIR spectra. It was found that accommodation of Rh(III) complexes in MCM-41 molecular sieves activated the complex and led to the formation of Rh(III)Cp* carbonyls as a result of contact with CO. Contact of rhodium (III) complexes encapsulated in MCM-41 matrix with CO did not result in rhodium (III) reduction, whereas in the presence of amine groups in aminosililated MCM-41 the reduction of Rh(III) to Rh(I) occurred relatively easily and formation of Cp*Rh(CO)₂ complex containing Rh(I) was noted. Encapsulated rhodium complexes showed some activity in methanol carbonylation reaction carried out under heterogeneous conditions. For the most active catalyst the amount of methyl acetate reached about 8 mol.%, however, deactivation of catalyst occurred and after 2 h on stream methyl acetate was not found in the product.     

Rhodium catalyzed hydroformylation of 1-octene in microemulsion: comparison with various catalytic systems

In this work, we describe how addition of alkylpolyglycol ether type nonionic surfactant affects the hydroformylation of 1-octene in the presence of phosphine modified rhodium catalyst. Influence of different process parameters such as ligand excess and amount of surfactant on the reaction rate and selectivity were discussed. Direct comparison of microemulsion systems with classic processes was achieved by performing the reactions under comparable homogeneous and biphasic conditions. Thus, the experiments were carried out using catalysts such as unmodified rhodium carbonyl HRh(CO)₄ and HRh(CO)(PPh₃)₃ in homogeneous system, Rh–TPPTS complex in two-phase system and in association with co-solvent.     

Hydroformylation of methyl oleate with a recycled rhodium catalyst and estimated costs for a batch process

Methyl oleate was hydroformylated to methyl formylstearate at 120 C and 850–900 psig with a 1:1 mol mixture of hydrogen and carbon monoxide. In the presence of triphenylphosphite, an activated rhodium-on-alumina catalyst produced an essentially quantitative conversion in about 40 min. Filtration followed by distillation yielded methyl formylstearate. The solubilized rhodium catalyst was concentrated in the distillation residue. The residue was resupported on the spent support in a gas-fired rotary kiln. The process was repeated 9 times without significant loss of catalyst activity. Assuming the catalyst can be recycled repeatedly to the process without affecting the efficiency of operation, a preliminary estimate based on a hypothetical plant producing 2 million 1b of methyl formylstearate annually places the processing costs, not including cost for methyl oleate, at about 13.7 cents per pound. Presented at the AOCS Meeting, New Orleans, La., April 1973. ARS, USDA.     

水溶性铑-膦络合物催化烯烃氢甲酰化反应--阳离子表面活性剂的加速作用

介绍了以水溶性铑-膦络合物RhCl(CO)(TPPTS)₂作为催化剂前体在水/有机两相体系中催化烯烃氢甲酰化反应研究的进展,阐述了阳离子表面活性剂的加速作用和介稳态胶束-离子对协同作用机理关系.通过两相体系中界面分子组装和选择与烯烃分子链长相匹配的表面活性剂, 设计制备了高区域选择性复合催化剂体系.当采用双长链表面活性剂与铑-膦络合物组成的复合催化体系时,在不搅拌的情况下就显示出极高的催化活性.     

Surface organometallic chemistry on metals. Application to chemicals and fine chemicals

Some applications of surface organometallic chemistry on metals to catalysis are presented, showing the great importance of the modification of a metallic surface by organometallic compounds on its catalytic properties. The selective hydrogenation of α–β unsaturated aldehydes such as citral (Z and E) can be achieved on rhodium–tin catalysts. While rhodium alone is relatively unselective, geraniol (and nerol) can be obtained selectively (> 98%) without a significant loss of activity by use of a rhodium–tin catalyst showing a typical ligand effect of the organotin fragment on the surface. Similarly, in the isomerization of (+) 3-carene into (+) 2-carene or the dehydrogenation of butan–2–ol into methyl ethyl ketone, the selectivity into the desired product is increased by introduction of small amounts of tin which will form adatoms poisoning unselective sites. An alloying effect of tin is also presented in the dehydrogenation reaction of isobutane in isobutene. This revised version was published online in June 2006 with corrections to the Cover Date.     

A new chiral diphosphine ligand and its asymmetric induction in catalytic hydroformylation of olefins

A new chiral ligand, 1,6-anhydro-2,4-bis(diphenylphosphino)pyranose (ABDPP), was prepared from -glucose. The ligand was used to prepare a chiral rhodium catalyst system for asymmetric hydroformylation of olefins. For vinyl acetate, the catalytic hydroformylation gave rather high yield (96%), high enantioselectivity (92% ee), and high regioselectivity (b/n=95/5). But for styrene and norbornene, the results were not so good. The rather high sterioselectivity in the hydroformylation of vinyl acetate is explained in terms of the hydrogen bonding between OH group in the ligand molecule and the carbonyl group of vinyl acetate.     

双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应

研究了采用水溶性铑膦络合催化体系对双环戊二烯的氢甲酰化反应，考查了反应温度、相转移剂ＣＴＡＢ、铑催化剂浓度等对反应的影响。氢甲酰化反应的产物经ＧＣ／ＭＳ鉴定是不饱和的三环癸单醛     

Continuous high temperature preparation of alkylolamides

Lauric diethanolamide was prepared from methyl laurate and diethanolamine in the presence of an alkaline catalyst by a continuous high temperature process. The conventional batch process requires cycle times of 2–6 hr which can lead to undesirable by-products. With a reaction time of about 10 sec, product purity of 91–94% was obtained at 149C for an absolute pressure range of 10–760 mm Hg. When reaction temperature was lowered to 110C, product purity became poorer as the absolute pressure was increased from 30 mm Hg to 760 mm Hg. Two studies for optimum catalyst content of either KOH or sodium methylate showed that maximum product purity of about 97% was obtained at 0.20% catalyst by weight. *** DIRECT SUPPORT *** A03O2184 00003     

Kinetics and mass transfer in hydroformylation—bulk or film reaction?

The kinetics of a gas–liquid reaction, alkene hydroformylation was studied in the presence of a homogeneous catalyst in a pressurised laboratory‐scale semibatch reactor. Hydroformylation of propene to isobutyraldehyde and n‐butyraldehyde was carried out at 70–115°C and 1–15 bar pressure in 2,2,4‐trimethyl‐1,3‐pentanediol monoisobutyrate solvent with rhodium catalyst using the ligands cyclohexyl diphenylphosphine. In order to evaluate the influence of mass transfer, experiments were made using varied stirring rate from 100 to 1000 rpm at 100°C and 10 MPa syngas pressure. Only at higher stirrings rates, the reaction took place in the kinetic regime. A reactor model was developed comprising both complex kinetics and liquid‐phase mass transfer. The model was based on the theory of reactive films. The model is able to predict under which circumstances the hydroformylation process is affected by liquid‐phase diffusion of the reactants. Experimental data and model simulations are presented for the hydroformylation of propene in the presence of a homogeneous rhodium catalyst.     

Preparation of glycol derivatives of partially hydrogenated soybean oil fatty acids and their potential as lubricants

Glycol diesters and mixtures of mono- and diesters have been prepared from methyl esters of partially hydrogenated soybean oil fatty acids and diethylene, dipropylene, neopentyl and triethylene glycols. The catalyst used in these reactions was a mixture of calcium acetate/barium acetate (3∶1, w/w). The reactions were carried out under nitrogen with 0.5% catalyst at temperatures in the range of 190–275°C. Borated esters of mixed mono- and diesters were prepared with 0.33 equivalent of boric acid per 1.0 equivalent hydroxyl group on the ester. Refractive indices, viscosities, and flash and fire points were determined for diesters, mixed mono- and diesters, and mixed diesters and borated esters. The viscosities, flash points and fire points indicate that these esters can be used as a component of lubricating oils. Wear-prevention characteristics of mixed diesters and borated esters indicated that they can be used as antifriction additives in lubricating oils. Lecture presented at the joint meeting of the International Society for Fat Research and the American Oil Chemists' Society in Toronto, May 10, 1992.     

The rhodium-catalyzed deuteration of unsaturated triglycerides

Tripalmitolein, triolein, trilinolein and trilinolenin were deuterated with deuterium gas and Wilkinson’s catalyst [(Ph₃P)₃RhCl(I)]. Recrystallization of the products from acetone yielded highly pure deuterium-labelled triglycerides (TG). The deuterated TG were converted to methyl esters and analyzed by gas chromatography/mass spectroscopy to determine the deuterium distribution. Methyl palmitate-9,10-d₂ (from tripalmitolein) and methyl stearate-9,10-d₂ (from triolein) yielded isotopic distributions of 93–97% d₂, methyl stearate-9,10,12,13-d₄ (from trilinolein) of 74% d₄ and methyl stearate-9,10,12,13,15,16-d₆ (from trilinolenin) of only 58% d₆. Because the deuterium-labelled TG were to be used in human metabolism studies, atomic absorption spectroscopy was used to determine if any residual rhodium was present. No rhodium was detected at 70 ppb (the minimum detection limit).     

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).     

Conversion of methyl 9(10)-formylstearate to carboxymethylstearate

Methyl 9(10)-formylstearate was converted to methyl 9(10)-carboxymethylstearate. The reactions to prepare the intermediates methyl 9(10)-hydroxymethyl-, 9(10)-ace toxymethyl-, 9(10)-methylene-, and 9(10)-formylmethylstearate are described. Methyl 9(10)-hydroxy methylstearate readily loses methanol and forms a trimeric polymer. The acetate of the primary alcohol when pyrolyzed gives 59% yield of methyl 9(10)-methylenestearate. Hydroformylation of the methylene compound followed by permanganate oxidation gave methyl carboxymethylstearate. Evidence is presented to show that pyrolysis of the acetate ester and hydroformylation of the pyrolysis product produce, respectively, only the methylene and formylmethylstearates. Rates of esterification-transes terification of methyl 9(10)-carboxymethyl sterate show that the carboxymethyl group is 2–3 times as active as the carboxyl group in methyl 9(10)-carboxystearate and that the terminal carboxyl group is about 10 times more active towards esterification than the branched carboxymethyl group.     

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.