Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds

The two catalyst systems rhodium-triphenylphosphine and palladium chloride-triphenylphosphine were investigated for the respective hydroformylation and hydrocarboxylation of oleic acid or ester to produce C-19 bifunctional compounds. Compared to conventional cobalt carbonyl for making formylstearate, rhodium-triphenylphosphine permits lower pressures (1000–2000 psi vs. 3000–4000 psi), higher conversions (95% vs. 80%), and no loss of functionality (vs. 15% hydrogenation with cobalt). Although palladium chloride-triphenylphosphine for hydrocarboxylation introduces the carboxyl function directly into the fatty acid chain, CO pressures of 3000–4000 psi and corrosion-resistant equipment are necessary. When applied to polyunsaturated fatty acids, both rhodium and palladium catalyst systems have the outstanding advantage of introducing functionality at each double bond position to produce polyformyl- and polycarboxystearates. Selected formyl derivatives were converted in excellent yield to acetals, to acids and their esters, to hydroxymethyl compounds and their esters, and also to aminomethyl compounds that could be condensed to polyamides. Several of the esters and acetals were effective primary plasticizers for poly(vinyl chloride) that had outstanding low volatility characteristics. Other applications for these new and highly versatile derivatives included rigid urethane foams, urethane-modified coatings, ester lubricants, and a shrink-resist treatment for wool.     

Hydrozirconation for unsaturated fatty acid derivatives

In the hydrozirconation reaction, developed by Schwartz and coworkers,bis(π-cyclopentadienyl) zirconium hydridochloride Cp₂-Zr(H)Cl, is added to the double bond of an olefin. The organozirconium intermediate can be functionalized by reaction with a variety of electrophiles such as oxygen, halogens, acetyl chloride and carbon monoxide. Furthermore, the double bond can be reformed by treatment with a hydride acceptor such as triphenylmethyl tetrafluoroborate. When a short-chain internal olefin is hydrozirconated, the initially formed alkylzirconium intermediate is rapidly isomerized to a compound in which the zirconium moiety is bound to the sterically least hindered position, which most often is the terminal position. The isomerization occurs rapidly at room temperature in contrast to the corresponding organoboron or aluminum compounds, which slowly positionally rearrange only at elevated temperatures. Because of the facile isomerization of internal alkylzirconium compounds to the terminal ones, we investigated application of the reaction to unsaturated fatty acids such as oleic and erucic acids. However, reactions on long-chain alkenes (such as oleic acid) are frequently much slower than those conducted on shorter-chain alkenes, and attention must be given to optimizing the reaction conditions if good yields are to be obtained. It would also be necessary to find an easily removable protecting group for the carboxylic function, as Cp₂Zr(H)Cl reduces carboxylic acids to alcohols. We found that the 4,4-dimethyl-2oxazoline function is a suitable protecting. group, and therefore synthesized the oxazolines from oleic acid and erucic acid. Hydrozirconation of the 4,4-dimethyl-2-oxazoline of oleic acid followed by oxidation witht-butyl hydroperoxide and conversion to methyl esters, gave methyl 3-hydroxy and methyl 18-hydroxy stearate in 13% and 17% yield, respectively. The relatively low yield is due to competing hydrogenation, the mechanism of which is discussed. Recent results indicate that the carboxyl group can be protected ast-butyl esters in the hydrozirconation and that oleyl alcohol derivatives can also be used. To understand the isomerization pattern in hydrozirconation, the reaction with α,β- and β,γ-unsaturated fatty acid oxazolines is discussed. Possibilities of making the hydrozirconation reaction catalytic by binding of the hydrozirconation reagent to a solid support as well as the synthetic potential in combining hydrozirconation with the olefin metathesis reaction are briefly reviewed.     

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.     

Oxidation of unsaturated fatty acid derivatives and vegetable oils

The present review reports the current literature of the last 10 years on selective oxidation reactions of fatty acid derivatives and vegetable oils. The work is structured in divisions including epoxidation, radical oxidations, Wacker‐type oxidation, dihydroxylation and C=C double bond cleavage.     

Sulfur dichlonde diadducts of unsaturated fatty derivatives. II reactions with nucleophiles

The chloro groups in the bis-9(10)-[alkyl-10 (9)-chlorooetadecanoate]-sulfides described previously (9) underwent reaction with water, alcohols, ammonia, amines, cyanides, cyanates, thiocyanates, and azides. The rates of these reactions were such that the chloro groups were completely replaced before significant attack on the ester group occurred. Without exception, the products of these reactions were the open-chain disubstituted-sulfide diesters, e.g. bis-9(10)-[ethyl-10 (9)-aminooctadecanoate]-sulfide, and no evidence was found for cyclic,e.g. thiomorpholine, structures. The sulfur dichloride diadducts fromcis-2-butene andtrans- 2- butene were also subjected to hydrolysis and ammonolysis and again, only the open-chain sulfides, e.g. bis-2-[3-amino-butyl]-sulfide, were formed. The diol-sulfides from m-olefins differed from the diol-sulfides oftrans- olefins in both physical and special properties. A similar difference was noted in the diamino-sulfides. Several of the fatty products were oxidized to the corresponding disubstituted sulfone diesters.     

Rhodium‐catalyzed hydroformylation of unsaturated fatty esters in aqueous media assisted by activated carbon

Concerns about the environmental impact of chemical transformations prompted chemists to develop clean chemical processes using water as a solvent. Although appropriate for small partially water‐soluble molecules, these processes do not allow for the transformation of hydrophobic substrates due to the mass transfer limitation between the aqueous and the organic phase. In this context, we show that activated carbons can be used as mass transfer additives to promote the rhodium‐catalyzed hydroformylation of methyl oleate and other unsaturated olefins. Due to its mesoporous and hydrophobic character, the Nuchar®WV‐B activated carbon proved to be especially effective as mass transfer promoter. Actually, a significant increase in the conversion was observed. Additionally, more than 90% aldehydes were formed during the course of the reaction. When compared to other mass transfer promoters such as co‐solvents or cyclodextrins, Nuchar®WV‐B was by far the most efficient. Thus, the use of activated carbons appeared to be a suitable solution for the aqueous rhodium‐catalyzed hydroformylation of hydrophobic bio‐sourced substrates. Practical applications: The easiness with which the FAME hydroformylation could be implemented in water using activated carbons as mass transfer promoters is a major advantage in a context of an industrial–environmental approach. This finding is of importance as the obtained oxo‐products can be used in many industrial areas such as surfactants, polymers, or lubricants.     

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.     

Nylon-9 from unsaturated fatty derivatives: Preparation and characterization

Methyl azelaaldehydate, soy nitriles, and oleonitrile were compared as starting materials for making nylon-9. Less difficulty was encountered in purifying intermediates from oleonitrile than from the other two. All 3 routes involved hydrolysis of methyl 9-aminononanoate to 9-aminononanoic acid. Self catalyzed hydrolysis of the amino ester in water produced low yields of monomer owing to oligomer formation, but hydrolysis in the presence of barium hydroxide was more successful. Polymerization of the amino acid proceeded smoothly with 9-acetamidononanoic acid used to control mol wt. Strength and moisture absorbing properties were determined for nylon-9, as well as for nylon-6/9, -9/11, and -9/12 copolymers. Nylon-9 has attractive properties, offering tensile yield and flexural strengths approaching those of nylon-6, while having low water absorption closely approaching that of nylon-11 and -12. The cost of producing 10,000,000 lb/year of nylon-9 from purchased oleonitrile was estimated to be $0.99/Ib at 100% yield and $2.18/Ib at 35.5% yield. Further process development is needed before yields in a commercial plant can be forecast.     

Alkyl-and arylsulfanyl-substituted unsaturated carbonyl compounds

A method for the synthesis of captodative sulfanyl enals, enones and enoates via nucleophilic vinylic substitution of corresponding halogen-bearing derivatives has been developed. The one-pot treatment of the haloenoates, haloenones or haloenals with thiols in the presence of organic base leads either to vicinal dithiosubstituted carbonyl-bearing compound or captodative systems with good to excellent yield. The major reaction direction strongly depends on the type of base used.     

Properties and uses of some unsaturated fatty alcohols and their derivatives

A number of unsaturated fatty alcohols are known, but only those of the C₁₆ and C₁₈ chain lengths are of much importance. In particular, oleyl alcohol., 9,10-octadecenol-1, is by far the most important. A variety of grades of oleyl alcohols is produced and used in the USA ranging from high purity material having iodine values (IV) of 90–95 to those having IV of 45–55, with the other components being primarily cetyl (hexadecanol-1) and stearyl (octadecanol-1) alcohols. This paper takes a brief look at the various grades of unsaturated alcohols used in the USA, methods of preparation, and the change in physical and chemical properties as the octadecanol-1 content and IV decline. Uses of these alcohols industrially and in cosmetic and pharmaceutical preparations are also discussed. Unsaturated alcohols are useful chemical intermediates since they have two reactive sites, the hydroxyl group and the carbon-carbon double bond. Particular attention is paid to the properties, uses and potential uses of some of their sulfates, ether sulfates, ethylene oxide adducts and ethylene/propylene oxide adducts as detergents and emulsifiers for ultimate use in cosmetics and light-duty and heavy-duty systems. Current estimated consumption of unsaturated alcohols in the USA is discussed.     

Addition of glyoxylic acid ethyl ester to unsaturated fatty acid derivatives

The addition of glyoxylic acid ethyl ester to unsaturated fatty acid derivatives occurs with a maximum yield of 89%. The products are the corresponding 1:1-adducts. Temperature, reaction time, stoichiometry, and the concentration of the fatty acid derivative were investigated and optimized. A maximum yield was obtained with a fourfold excess of oleic acid ethyl ester, a reaction temperature of 200 °C, a reaction time of 24 h, and an oleic acid ethyl ester concentration of 1.3 mol/l.     

The synthesis of silicon oleochemicals by hydrosilylation of unsaturated fatty acid derivatives

The hydrosilylation of fatty acid esters with terminal or internal double bonds catalysed by H₂ PtCl₆ is described. The reaction was carried out with good yields at ambient pressure under mild conditions. Methyl undec‐10‐enoate was reacted with chloro‐ or alkoxyhydrosilanes giving moderate to good yields (41—77%) and even its reaction with alkylhydrosilanes produced low yields (below 20%). Under optimised conditions the hydrosilylation of methyl linoleate gave only with reactive chlorohydrosilanes acceptable yields, between 25 to 83%, of regioisomers. The hydrosilylation of methyl α‐linolenate with dimethylchlorosilane gave a mixture of regioisomeric 1:1‐ and 2:1‐hydrosilylation adducts in a total yield of 40%. The hydrosilylation of ethyl oleate did not proceed at all under our conditions. In the case of methyl undec‐10‐enoate a biphasic solvent system permitted the simple separation and reuse of the homogeneous catalyst.     

Homogeneously catalysed hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols

The use of copper and cadmium oxides or soaps as catalysts for the hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols has been investigated. It is shown that copper soaps homogeneously activate hydrogen. When copper and cadmium oxides are used as catalysts, they react with the acid under formation of a homogeneous soap solution. A continuous reaction system for the preparation of unsaturated fatty alcohols by hydrogenation under the influence of copper and cadmium soaps is described.     

Interaction of tocored with unsaturated fatty esters

Tocored, an oxidation product of tocopherol and its model, 2,2,7,8-tetramethyl-5,6-chromanquinone reacted with methyl linoleate at an elevated temperature to form an adduct with isomerized linoleate. Oxidation of tocored in fatty esters produced a variety of products, depending on the degree of unsaturation of the esters. With methyl palmitate no addition product was detected but tocopurple and tocoreddimer were identified as minor products irrespective of the degree of saturation. A mechanism involving the interaction of tocored with lipid radicals to yield an adduct as the consequence of antioxidative action of tocored is postulated.     

Conversion of unsaturated fatty acids – cycloadditions with unsaturated fatty acids [1]

Diels-Alder reactions with methyl conjuenate ( 2 ) at room temperature, with methyl E-12-oxo-10-octadecenoate ( 11 ) as dienophile and radical cation catalyzed cycloadditions of 2 are described. 2 is prepared from methyl linoleate by base catalyzed isomerization with sodium dimethylsulfoxide in 90% yield. It undergoes readily Diels-Alder reactions at room temperature in the presence of 1–1.8 equivalents of a Lewis acid and catalytic amounts of iodine to form cycloadducts in 55–90% yield. At 140°C 2 reacts with dimethyl maleate and dimethyl acetylenedicarboxylate to cycloadducts in 86% and 73% yield, respectively. Methyl E-12-oxo-10-octadecenoate ( 11 ) can be combined in a Diels-Alder reaction with the dienes 2-(trimethylsilyloxy)-1,3-butadiene and 2,3-dimethylbutadiene in 69% and 86% yield, respectively. By way of radical cation catalysis 2 undergoes [4+2]-cycloadditions with dienes in high yield.     

Sulfur dichloride diadducts of unsaturated fatty derivatives. I. preparation and oxidation

Sulfur dichloride diadducts of oleate esters, oleylnitrile, elaidate esters and ethyl linoleate were prepared by addition of the theoretical amount of sulfur dichloride to the fatty derivative. Similar diadducts were also prepared from commercial oleate esters including esters of ADM's monoenoic acid. Several of the resultingβ,β′- dichlorosulfide diesters were then oxidized with peracetic acid to β,β′-dichlorosulfoxide diesters and to β,β′-dichlorosulfone diesters. The latter materials were converted to the divinyl sulfone diacids. Cis andtrans-2-butene were used as model compounds for studying the addition of sulfur dichloride to oleates and elaidates respectively. The results on these systems, which paralleled the results with the fatty materials, indicated that substitution reactions were negligible and that the addition was stereoselective, that is, oleates and elaidates gave stereochemically different products.     

Selective vapor phase hydroformylation of ethylene over cluster-derived cobalt catalyst

Vapor phase hydroformylation of ethylene was studied with silica-supported metal catalysts. A cobalt metal catalyst derived from Co₂(CO)₈ gave propanal and its derivatives in as high selectivity of about 36% as Rh/SiO₂ catalyst under the reaction conditions of 1.1 MPa of a gas-mixture of ArCOC₂H₄H₂ = 1333 at 423–503 K. On the other hand, conventional cobalt catalysts derived from cobalt nitrate, chloride, or acetate, and other noble metal catalysts (Pd/SiO₂ and Ir/SiO₂) produced mainly ethane.     

Homogeneous hydroformylation of cyclohexene with bis(acetylacetonato)diaquo cobalt (II)

Hydroformylation of cyclohexane by bis(acetylacetonato)diaquo cobalt(II) [Co(acac)₂ (H₂O)₂] in benzene solution produced the corresponding aldehyde, alcohol and saturated hydrocarbon. The influence of various experimental conditions on the product distribution has been investigated and the optimum conditions for the maximum yield of aldehyde (45%) and alcohol (55%) have been established. A tentative mechanism for hydroformylation has been suggested on the basis of the isolated green complex [Co(acac)₂]₂(C₆H₁₀) having catalytic activity comparable with Co (acac)₂(H₂O)₂ which has been isolated from the product mixture and also synthesised separately.     

1-辛烯氢甲酰化反应Co/CNTs催化剂的制备与表征

用浸渍法、化学气相沉积法（MOCVD）、乙二醇液相还原法制备碳纳米管负载钴催化剂, 以1-辛烯的氢甲酰化反应为探针反应, 对比研究了所制得的Co/CNTs催化剂的催化性能, 并用XRD和TEM等技术研究了催化剂的粒子大小及粒径分布, 考察了1-辛烯的氢甲酰化反应性能与催化剂粒径大小的关系.发现用MOCVD法制备的Co/CNTs催化剂的平均粒径最小, 其平均粒径为7.5 nm左右且分布均匀; 该催化剂在1-辛烯的氢甲酰化反应中具有最高的催化活性和C₉-醛的选择性.