Acetal derivatives of methyl 9(10)-formylstearate: Plasticizers for PVC

Several acetals and an enol ether were prepared from methyl 9(10)-formylstearate and characterized with respect to their thermal, spectroscopic and chromatographic properties. These low-melting (below −80 C) compounds were generally compatible as secondary poly(vinyl chloride) plasticizers and imparted low-temperature properties that were intermediate between those obtained with dioctyl phthalate and dioctyl sebacate. Presented at AOCS Meeting, Atlantic City, October 1971. N. Market. Nutr. Res. Div., ARS, USDA.     

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.     

Poly(amide-acetals) and poly(ester-acetals) from polyol acetals of methyl 9(10)-formylstearate: Preparation and physical characterization

Condensation polymers were prepared from the pentaerythritol acetal of methyl 9(10)-formylstearate by reaction with diamines and with ethylene glycol. The glycerol acetal was self-condensed to a poly(ester-acetal) and also copolymerized with caprolactam. A novel step growth, addition polymerization was carried out with ethylene bis[9(10)-methoxymethylenesterate] and pentaerythritol. Physical and spectral (infrared and nuclear magnetic resonance) properties of the various products were determined. In general, the long C₈–C₉ side chains in the polymers of the pentaerythritol acetal of methyl 9(10)-formylstearate reduced crystallinity to such a degree that, unlike polymers from methyl azelaaldehydate pentaerythritol acetal, they were soluble in the more ordinary solvents, e.g., chloroform and tetrahydrofuran. Presented in part at the 45th Fall AOCS Meeting, Atlantic City, New Jersey, October 3–6, 1971.     

催化环氧脂肪酸甲酯制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯

采用强酸性离子交换树脂(D002-H)催化环氧脂肪酸甲酯合成9(10)-羟基-10(9)-甲氧基脂肪酸甲酯。首先,以油酸甲酯在甲酸催化下制备中间体环氧脂肪酸甲酯,考察了反应时间、反应温度、甲酸和双氧水加入量对产物环氧值的影响。其次,以D002-H为催化剂,以环氧脂肪酸甲酯和甲醇为原料,通过开环醚化制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯,考察了反应时间、反应温度、醇油质量比和催化剂加入量对转化率的影响,并通过IR以及GC-MS对产物进行了表征。结果表明,反应时间12 h,反应温度65℃,催化剂加入量为环氧脂肪酸甲酯质量的6%,甲醇加入量为100%,在该条件下其转化率高达99%以上。     

催化环氧脂肪酸甲酯制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯

采用强酸性离子交换树脂(D002-H)催化环氧脂肪酸甲酯合成9(10)-羟基-10(9)-甲氧基脂肪酸甲酯。首先,以油酸甲酯在甲酸催化下制备中间体环氧脂肪酸甲酯,考察了反应时间、反应温度、甲酸和双氧水加入量对产物环氧值的影响。其次,以D002-H为催化剂,以环氧脂肪酸甲酯和甲醇为原料,通过开环醚化制备9(10)-羟基-10(9)-甲氧基脂肪酸甲酯,考察了反应时间、反应温度、醇油质量比和催化剂加入量对转化率的影响,并通过IR以及GC-MS对产物进行了表征。结果表明,反应时间12 h,反应温度65℃,催化剂加入量为环氧脂肪酸甲酯质量的6%,甲醇加入量为100%,在该条件下其转化率高达99%以上。     

Conversion of polyhydroxybutyrate (PHB) to methyl crotonate for the production of biobased monomers

Within the concept of the replacement of fossil with biobased resources, bacterial polyhydroxybutyrate (PHB) can be obtained from volatile fatty acids (VFAs) from agro‐food waste streams and used as an intermediate toward attractive chemicals. Here we address a crucial step in this process, the conversion of PHB to methyl crotonate (MC), which can be converted via cross‐metathesis with ethylene to methyl acrylate and propylene, two important monomers for the plastics industry. The conversion of PHB to MC proceeds via a thermolysis of PHB to crotonic acid (CA), followed by an esterification to MC. At pressures below 18 bar, the thermolysis of PHB to CA is the rate‐determining step, where above 18 bar, the esterification of CA to MC becomes rate limiting. At 200°C and 18 bar, a full conversion and 60% selectivity to MC is obtained. This conversion circumvents processing and application issues of PHB as a polymer and allows PHB to be used as an intermediate to produce biobased chemicals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42462.     

9(10)-Carboxyoctadecylamine and 9(10)-aminomethyloctadecanoic acid: Synthesis and polymerization to polyamides with lateral substitution

9(10)-Carboxyoctadecylamine (I) and 9(10)-aminomethyloctadecanoic acid (II) have been prepared from selectively hydroformylated oleonitrile and oleic acid, respectively. Polymerization of I gave a transparent hard, somewhat brittle, polyamide, whereas polymerization of II gave a soft, rubbery polymer that flowed slowly at room temperature. Copolymers of I with II had properties reflecting those of the component homopolymers, although II exercised a disproportionate softening effect. The same was generally true of copolymers of I or II with nylon-66 salt, caprolactam, and 9-aminononanoic acid. The copolymer of I with 25 mole % nylon-66 salt was transparent, was also elastic, and could be either drawn into fibers or made into a coherent film. The properties of the two amino acids and of their polymers agreed with those expected from simpler alkyl-substituted amino acids.     

Esterification and transesterification of 9(10)-carboxystearic acid and its methyl esters. Kinetic studies

9(10)-Carboxystearic acid and its mono- and dimethyl esters were esterified and transesterified with 1-butanol, 2-methoxyethanol, 2-chloroethanol, 2,2-dimethylpentanol, 2-ethylhexanol and 1-octanol. Rate studies for the sulfuric acid-catalyzed esterification of 9(10)-carboxystearic acid to alkyl 9(10)-carboxystearate and alkyl 9(10)-carboalkoxystearate indicate than on an average the terminal carboxyl is approximately 26–27 times more reactive than the branched carboxyl group. Esterification is highly dependent on catalyst concentration. Steric hindrance in 2,2-dimethylpentanol and the electrophilic character of 2-methoxyethanol and 2-chloroethanol markedly retard the rate. In addition to the expected diesters, 2-chloroethanol yields esters containing extra-O-CH₂CH₂- groups. The rate of transesterification of the terminal ester group of mono- and dimethyl esters of 9(10)-carboxystearic acid is about two times faster than the rate of esterification of the branched carboxyl group. Transesterification of the branched 9(10)-ester group is extremely slow. Presented at the AOCS Meeting, Atlantic City, October 1971. N. Market. Nutr. Res. Div., ARS, USDA.     

Conversion of unsaturated fatty acids — Nucleophilic additions to methyl (E)-12-Oxo-10-octadecenoate [1]

Methyl ricinoleate is converted in 57% yield into methyl (E)-12-oxo-10-octadecenoate ( 4 ) by oxidation of the 12-OH group and conjugation of the double bond. The enone fatty acid methylester 4 reacts in high yield with anions of 1,3-dicarbonyl compounds, nitroalkanes, acylanions from aromatic aldehydes and cyanide to new C10-functionalized fatty acids. The nitroalkyl adducts can be converted into pyrroloid and furanoid fatty acids.     

Preparation and characterization of methyl 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate and methyl 8-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate

Allylic amination of methyl oleate with bis(N-p-toluenesulfonyl) sulfodiimide results in a mixture of methyl 11-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate and methyl 8-amino-(N-p-toluenesulfonyl)-9-E-octadecenoate in 58% yield. These novel products were isolated and characterized by nuclear magnetic resonance, infrared spectroscopy, mass spectrometry, and melting point. The reaction was analyzed by highperformance liquid chromatography and thin-layer chromatography.     

Conversion of methyl ricinoleate to methyl 12-ketostearate with Raney nickel

A convenient laboratory preparation of methyl 12-ketostearate is described. Methyl ricinoleate is converted to methyl 12-ketostearate in 70–75% yield by Raney nickel. The type and quantity of Raney nickel have a marked influence on the yield as well as on the time and temp required for the conversion. The reaction is not a direct isomerization as previously assumed but appears to be a two-step process. Methyl ricinoleate is hydrogenated rapidly to methyl 12-hydroxystearate which is then dehydrogenated slowly to the product. Hydrogenolysis of the alcohol function is a competing reaction which is minimized by the proper choice of reaction conditions. A laboratory of the W. Utiliz. Res. & Dev. Div., ARS, USDA.     

Convenient preparation of methyl 10-(1,3,2-Oxazaphospholidin-2-one)undecanoate and methyl 10-(1,3,2-diazaphospholidin-2-one)undecanoate

Synthesis and spectral studies of methyl 10-(1,3,2-oxazaphospholidin-2-one)undecanoate and methyl 10-(1,3,2-diazaphospholidin-2-one)undecanoate are reported. These fatty products were obtained in excellent yields when methyl 10-hydroxyundecanoate was reacted with phosphorus oxychloride, and the resultant intermediate was treated with aminoethanol and ethylenediamine in two different reactions.     

Synthesis and Characterization of 9(10)-Bromo-9-octadecenoic Acids

9(10)-Bromo-cis-9-octadecenoic acid, m. p. 36.7° C, was prepared by dehydrobromination of threo-9,10-dibromo-stearic acid with bases and by polar addition of hydrogen bromide to stearolic acid. The trans isomer, m. p. 6°–8° C, was obtained from the corresponding erythro-dibromide. Both compounds were characterized by IR and NMR spectroscopies and a reaction scheme for their formation by dehydrobromination is suggested.     

Microwave polymerization of poly(methyl acrylate): Conversion studies at variable power

Methyl acrylate (MA) was polymerized by microwave radiation at three different powers, namely, 200, 300, and 500 W. The percentage conversion of the reaction was followed by Fourier transform infrared (FTIR) spectroscopy. The specimen temperature during the polymerization process was measured to select a suitable temperature for comparison with the conventional method. The results indicate that a similar comparable temperature of about 52° was found for all the microwave power settings tested. The microwave polymerization process was compared with that of the thermal method at 52(±1)° under comparable reaction conditions. The reaction rate enhancement of the microwave polymerization compared to the thermal method was found to be as follows: 275% for the 500 W, 220% for the 300 W, and 138% for the 200 W, indicating a significant correlation between the reaction rate enhancement and the level of microwave power used.     

Catalytic autoxidation of 9(10)-formylstearic acid

A procedure has been developed for the preparation of carboxystearic acid by catalytic autoxidation of hydroformylated oleic acid. This autoxidation is catalyzed effectively with Ca, Cu, Co, Fe, Mn and Ce naphthenates in either acetone or glacial acetic acid at 20 C. With the exception of Ca, all these catalysts produce from 2 to 10% keto- and hydroxystearic acids as by products. Yields of up to 95% 9(10)-carboxystearic acid are obtained by autoxidation for 24 hr with Ca naphthenate (0.5% Ca based on formylstearate). This autoxidation period was shortened to 7 hr by using a binary catalyst (0.5% Ca and 0.05% Mn), which affords a minimum of side products.     

Volatiles from thermal decomposition of isomeric methyl (12S, 13S)-(E)-12,13-epoxy-9-hydroperoxy-10-octadecenoates

Two epimers of methyl (12S,13S)-(E)-12,13-epoxy-9-hydroperoxy-10-octadecenoate were isolated after esterification of a mixture of fatty acids obtained from decomposition of (13S)-(9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid by an Fe⁺⁺-cysteine catalyst. These epimeric epoxyhydro-peroxyoctadecenoates were decomposed by heat (210 C) in the injection port of a gas chromatograph, and the cleavage fragments were subsequently separated by gas chromatography (GC) and identified by mass spectrometry (MS). Among the scission products obtained, the most prominent in the GC peak profile were methyl octanoate and methyl 9-oxononanoate. Other peaks were identified as pentane, 1-pentanol, hexanal, 2-heptanone, 2-pentylfuran, methyl heptanoate, 2-octenal, 4,5-epoxy-2-decenal, methyl 8-(2-furyl)-octanoate, 11-oxo-9-undecenoate and methyl 13-oxo-9,11-tridecadienoate. In addition, 3,4-epoxynonanal, methyl 8-oxooctanoate, 3-hydroxy-2-pentyl-2,3-dihydrofuran and methyl 10-oxodecanoate were tentatively identified. Except for the furan compounds, the formation of the fragmentation products could be explained by conventional free-radical scission mechanisms. The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

合成10-硝基蒽酮的一种新方法

在醋酸、相转移催化剂聚乙二醇存在下,蒽与硝酸铈铵反应生成10-硝基蒽酮。聚乙二醇作为相转移催化剂,可以提高反应的选择性。最佳反应条件为:n蒽∶n硝酸铈铵为1∶1.05,反应温度50℃,反应时间1.4h。10-硝基蒽酮的产率达74.1%。     

Conversion of linoleic acid to 10-hydroxy-12(Z)-octadecenoic acid byFlavobacterium sp. (NRRL B-14859)

A new microbial isolate,Flavobacterium sp. strain DS5, converts linoleic acid into 10-hydroxy-12(Z)-octadecenoic acid (10-HOA) with 55% yield. The product was characterized by gas chromatography (GC), GC/mass spectrometry, nuclear magnetic resonance and Fourier transform infrared spectroscopy. The specific optical rotation of 10-HOA is [α] _D ²⁴ =−5.58 (methanol). The optimum time, pH and temperature for the production of 10-HOA were 36h, 7.5 and 20–35°C, respectively. The enzyme(s) that converts linoleic acid to 10-HOA is soluble and located intracellulary in strain DS5. Two minor products, 10-methoxy-12-octade-cenoic acid and 10-keto-12-octadecenoic acid, were also identified. 10-HOA was further metabolized by strain DS5. Among the unsaturated fatty acids studied, the order of reactivity for the DS5 enzyme(s) is oleic>palmitoleic> linoleic>linolenic>γ-linolenic>myristoleic acid.     

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.     

Germinal hydroxymethyl compounds from 9(10)-formylstearic acid

9(10)-Formylstearic acid and methyl 9(10)-formylstearate reacted with formaldehyde in basic methanolic or aqueous medium to undergo the Tollens condensation, followed by a crossed Cannizzaro reaction to give 9,9(10,10)-bis(hydroxymethyl)-octadecanoic acid in essentially quantitative yield. This 2,2-disubstituted-1,3-propanediol has been esterified on the carboxyl group and the hydroxymethyl groups have been acetylated and acetalated with acetone to give a series of stable liquids boiling at ca. 200 C/0.005 mm and freezing at <−70 C.