Synthesis and antimicrobial activity of fatty 2-morpholinones prepared from epoxy fatty acid methyl esters

Reactions of methyl 10,11-epoxyundecanoate (I), methyl 9,10-epoxyoctadecanoate (II) methyl 12,13-epoxy-cis-9-octadecenoate (III) and methyltrans-2,3-epoxyhexadecenoate (IV) with glycine in dimethylformamide (DMF) in the presence of anhydrous AlCl₃ as catalyst have yielded 5(6)-[8′-carbomethoxyoctyl]-2-morpholinone (V); 5(6)-[7′'-carbomethoxyheptyl]-6(5)-octyl-2-morpholinone (VI);5(6)-[10′-carbomethoxydec-cis-2-enyl)-6(5)-pentyl-2-morpholinone (VII), and 5-tridecyl-6-carbomethoxy 2-morpholinone (VIII), respectively in excellent yield. The products have been characterized with the help of spectral data and microanalysis. Antifungal and antibacterial screening of (V–VIII) showed pronounced activity against four bacteria and seven fungal species. Presented in part at the 43rd Annual Convention of the Oil Technologists' Association of India (OTAI) held in Bombay, India In February 1988.     

A study of fatty acid methyl esters with epoxy or alkyne functionalities

Described are the physical and chemical properties of the methyl esters of two uncommon fatty acids: vernolic acid, containing an epoxy group, and crepenynic acid, containing a triple bond. The incorporation of an epoxy or alkyne group into the fatty acid structure is shown to greatly affect the properties compared to conventional unsaturated fatty acids. The methyl esters have been characterized and compared with ordinary fatty acid methyl esters (i.e., methyl oleate and linoleate) with respect to spectroscopic characterization [¹H nuclear magnetic resonance (NMR)], ¹³C NMR, and Fourier transform infrared), rheological properties, and oxidative reactivity (using chemiluminescence). Both methyl vernoleate and methyl crepenynate could successfully be produced by transesterification under basic conditions without reaction of the epoxy or alkyne groups. Rheological measurements showed that the methyl esters had a significantly lower viscosity compared to their triglyceride analogs. Smaller differences were seen when comparing the different methyl esters where methyl vernoleate had the highest viscosity due to the presence of the more polar oxirane group. Very large differences were found with respect to the oxidation rate of the different methyl esters. Methyl crepenynate was shown to oxidize extremely rapidly, whereas methyl vernoleate was very stable toward oxidation.     

Nonvolatilealpha-branched-chain fatty esters

Nonvolatilealpha-branched carboxylic acids and esters have been prepared by a free radical reaction. Various esters of the reaction products of hexadecanoic and octadecanoic acids with the terminal olefins, octene, decene, and dodecene have been synthesized. Fractional crystallization from acetone is a useful method for preparing these compounds in a highly purified state. Mass spectra confirm that branching is found exclusively at thealpha- or 2-position.     

Allyl esters and allyl epoxy esters from crambe oil

Room temperature transesterification of crambe oil with allyl alcohol gave allyl esters previously prepared by hydrolysis of the oil and reesterification of the mixed acids at elevated temperatures. Treating the esters with m-chloroperbenzoic acid in the presence of sodium bicarbonate resulted in the selective epoxidation of ethylenic bonds and suppression of side reactions. Bifunctional allyl epoxy esters produced in 88% overall yield by this method contain 5.08% oxirane oxygen and an unsaturation equivalent to 91% allyl group; they are prospective monomers for various types of polymerization.     

Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions

Extremely rapid hydrogenation of fatty acid methyl esters (FAME) to fatty alcohols (FOH) occurs when the reaction is conducted in a substantially homogeneous supercritical phase, using propane as a solvent, over a solid catalyst. At these conditions, the limitations of hydrogen transport are eliminated. At temperatures above 240°C, complete conversion of the starting material was reached at residence times of 2 to 3 s, which is several orders of magnitude shorter than reported in the literature. Furthermore, formation of by-products, i.e., hydrocarbons, could be prevented by choosing the right process settings. Hydrogen concentration turned out to be the key parameter for achieving the above two goals. As a result of the supercritical conditions, we could control the hydrogen concentration at the catalyst surface independently of the other process parameters. When methylated rapeseed oil was used as a substrate, the hydrogenation catalyst was deactivated rapidly. However, by using methylated sunflower oil, a catalyst life similar to that obtained in industrial processes was achieved. Our results showed that the hydrogenation of FAME to FOH at supercritical conditions is a much more efficient method than any other published process.     

Saturated keto esters from lesquerolic,dimorphecolic, and densipolic acids

Summary The naturally occurring, unsaturated, hydroxy fatty esters, methyl lesquerolate (methyl 14-hydroxy-cis-11-eicosenoate), methyl dimorphecolate (methyl 9-hydroxy-trans, trans-10,12-octadecadienoate), and methyl densipolate (methyl 12-hydroxy-cis,cis-9,15-octadecadienoate) have been converted to the corresponding saturated keto esters by tow routes. The unsaturated esters were subjected to a hydrogenation-dehydrogenation reaction in the presence of Raney nickel or their saturated derivatives were dehydrogenated by copper chromite catalysis. Yields of the keto esters are 65–82% in the nickel-catalyzed reactions, and 71–94% by copper chromite-catalyzed dehydrogenation. In the hydrogenation-dehydrogenation system the order of reactivity is: methyl lesquerolate>methyl dimorphecolate>methyl densipolate. Relationships between structure and reactivity of these compounds, methyl 12-hydroxystearate, and methyl ricinoleate are discussed. W. Utiliz. Res. Dev. Div., ARS, USDA.     

Surfactants from glucamines and ω‐epoxy fatty acid esters

The ring‐opening reaction of ω‐epoxy fatty acid methyl esters (9,10‐epoxy decanoic acid methyl ester, 10,11‐epoxy undecanoic acid methyl ester and 13,14‐epoxy tetradecanoic acid methyl ester) with N‐methyl glucamine or glucamine was studied. A new method (in methanol under reflux) leads to products, which are surfactants of linear‐ or γ‐type‐structure, in fair yields and purities. In a following step the ring‐opening products were saponificated by enzymatic catalysis or by conversion with sodium hydroxide leading to amphoteric surfactants. The surface‐active properties of the methyl esters and their corresponding acids or salts were studied at various pH‐values by measurement of surface tension of aqueous solutions and by examination of foaming properties. Depending on the chain length of the used epoxides, the structure of the obtained sugar‐based surfactant and the pH‐values, different surface‐active properties were observed. Several of the achieved products reduce the surface tension of aqueous solution down to 26—40 mN/m. Examination of foaming properties of the latter show rather poor or good foamers, depending on the surfactant used or the pH‐value of the solution.     

Metathesis of fatty acid esters

In metathesis reactions, unsaturated compounds are converted into new compounds via an exchange of alkylidene groups: 2 RCH=CHR′⇌RCH=CHR+R′CH=CHR′ Since its discovery in 1964, this catalytic reaction has found several large-scale applications in petrochemistry. One of the most promising synthetic applications of metathesis is to functionalized olefins such as unsaturated esters, ethers, amines, etc., because this allows single-step syntheses of a variety of mono- and difunctional hydrocarbon derivatives. Unfortunately, however, most metathesis catalysts are easily poisoned by polar groups. In 1972 in our institute, the WCl₆-(CH₃)₄Sn system was found to be effective as a catalyst for monogeneous metathesis of fatty acid esters. Thus methyl oleate was converted into 9-octadecene and dimethyl 9-octadecene dioate, starting materials for the synthesis of valuable chemical products. In 1977 we developed a heterogeneous catalyst system: Re₂O₇ on Al₂O₃, activated with a small amout of (CH₃)₄Sn. Systematic research has led to intersting applications of metathesis and cometathesis reactions with these catalysts. An example is the cometathesis of methyl oleate with ethene, to produce shorter-chain compounds with terminal double bonds: CH₃(CH₂)₇CH=CH(CH₂)₇COOCH₃+CH₂=CH₂⇌CH₂=CH(CH₂)₇CH₃+CH₂=CH(CH₂)₇COOCH₃ Cometathesis of olive oil (mainly triolein) with ethene opens the possibility of producing both α-olefins in the C₁₀ range and fatty oils with lower molecular weight (palm oil type). Until now, metathesis of fatty esters has been restricted mainly to synthetic purposes. Large-scale applications depend mainly on the development of more active and cheaper catalyst systems.     

Addition of chlorine to unsaturated fatty acids and esters

Summary Methyl oleate, oleic acid, and ethyl linoleate were chlorinated with elemental chlorine at temperatures near −20°C. Approximately quantitative yields of the addition products were obtained, with little or no concurrent substitution. The products prepared in this manner had not previously been reported in the pure state. Two new compounds, ethyl tetrachlorostearate and tetrachlorostearic acid, were prepared. Methyl dichlorostearate was found to distil with no apparent decomposition at 190–200°C. under pressures below 1 mm. Removal of the chlorine atoms required more drastic conditions that removal of bromine atoms from the same positions and was accompanied by complicating side reactions. Journal Paper No. 755 of the Purdue University Agricultural Experiment Station, Lafayette, Ind.     

Hydroformylation of unsaturated fatty esters

Unsaturated fatty esters and vegetable oils were hydroformylated with H₂ and CO (3500–4600 psi) and Co₂(CO)₈ to give fatty aldehydes at 100–110 C and fatty alcohols at 175–190 C. Yields of distillable C₁₉ oxo products varied from 42% to 84%. Distilled products contained from 50% to 90% branched isomers and from 4% to 16% linear isomers. The proportion of linear isomers increased at higher reaction temperatures and in the presence of tributylphosphine-cobalt carbonyl complex. Linear and branched hydroxy products were separated by silicic acid column, thin-layer, and gas-liquid chromatography. The linear hydroxy product (from oleate and linoleate) was identified as methyl 19-hydroxynonadecanoate by nuclear magnetic resonance and mass spectrometry. Isomeric branched products were analyzed by mass spectrometry as the diester derivatives. They were identified as a mixture of 5- to 13-carbomethoxy methyl octadecanoate. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., March 1968. No. Utiliz. Res. Dev. Div., ARS, USDA. Bureau of Mines, U.S. Dept. of Interior.     

A novel keto fatty acid from cassia occidentalis seed oil

A keto fatty acid (Z)-7-oxo-11-octadecenoic acid) has been isolated in appreciable amount (27.1%) from Cassia occidentalis seed oil. The identification was based on chemical and spectroscopic methods.     

Derivatization of keto fatty acids,X: Synthesis of thiazanones

The synthesis of alkyl chain-substituted thiazanones from oxo fatty esters and a long chain aldehyde is reported. Four oxo compounds—methyl 10-oxoundecanoate, methyl 9-oxooctadecanoate, methyl 9,10-dioxooctadecanoate and octadecanal—were allowed to react with β-mercaptopropionic acid in the presence of ammonium carbonate in benzene to give the corresponding 4-m-thiazanones in high yields. The structures of these compounds were confirmed by combustion and spectral data.     

Enzymatic synthesis of wax esters from rapeseed fatty acid methyl esters and a fatty alcohol

Wax esters were transesterified from fatty acid methyl esters of rapeseed and a fatty alcohol (1-hexadecanol, 16:0). The amounts of both the substrates were fixed to 0.1 mmol and an immobilized enzyme, Lipozyme, was used as catalyst. The experiment was performed following a statistic central composite design with five variables. The enzyme/lipid ratio was varied between 0.3–0.9 of the substrate weight and the enzyme was equilibrated to different water activities varying from 0.11 to 0.44. A temperature range of 50–80°C was investigated and the reaction time lasted up to 40 min. A solvent, isooctane, constituted 0–30% of the substrate weight. The first experimental series was performed in small closed test tubes. In the second series the caps of the test tubes were off to evaporate the methanol produced during the reaction. The highest initial reaction rate was 9.6 g_{wax esters}/g_enzyme · h. It appeared when: the enzyme/lipid ratio was low, 0.3, the temperature was high, 80°C; no isooctane was present; and the water activity was below 0.11. The initial reaction rate was independent of the caps on the test tubes. With the large amount of enzyme the yield of wax esters was above 70% after 10 min in both experimental series. In the reaction with caps, the reaction reached equilibrium at 83% after 20 min at 80°C. However, without caps the continuous evaporation of methanol increased the equilibrium constantly, and after 40 min at 80°C a yield of 90% was reached.     

Enzymatic hydrolysis of long-chainN-heterocyclic fatty esters

Incubation of a 1-pyrroline ester [viz. methyl 8-(5-hexyl-1-pyrroline-2-yl)octanoate,1] with bakers' yeast (Saccharomyces cerevisiae) gave the corresponding free fatty acid (1a, 52%). The C=N bond of the 1-pyrroline was not reduced by the yeast. Complete hydrolysis of compound1 was successful using lipase ofCandida cylindracea (CCL) or Lipolase (Rhizomucor miehei) under stirred or ultrasound condition. Fatty esters containing a pyrrolidine [viz. methyl 8-(cis/trans-5-hexyl-pyrrolidine-2-) octanoate,2] orN-methyl pyrrolidine [viz. methyl 8-(cis-5-hexyl-N-methyl-pyrrolidine-2-)octanoate,3] system in the alkyl chain were not hydrolyzed by either CCL or Lipolase, unless conducted in an ultrasonic bath. The hydrolytic activities of the enzymes appeared to be strongly affected by the stereochemistry of theN-heterocyclic ring system. Chemical hydrolysis of compounds1–3 gave the corresponding fatty acidN-HCl salts.     

脂肪酸酯的技术与市场发展动向

论述了脂肪酸一元醇酯,多元醇酯的特性、合成及用途,并介绍了由脂肪酸酯开发“绿色”表面活性剂的最新技术动向。     

Derivatization of keto fatty acids: II. synthesis of long-chain enolacetates

Long-chain enolacetates were prepared by refluxing the keto fatty acids with acetic anhydride andp-toluene sulfonic acid (p-TSA). 10-Oxoundecanoic and 2-oxohexadecanoic acids gave mainly 10-acetoxy-10-undecenoic and 2-acetoxy-2-hexadecenoic acids, respec-tively. On the other harld, 12-oxooctadecanoic acid on similar treatment was assumed to yield an isomeric mixture of 12-acetoxy-12(11)-octadecenoic acids. The structure of the individual reaction products were established by spectral studies.     

Cryptolepis buchnani seed oil: A rich source of keto fatty acid

A keto fatty acid (9-oxo-cis-12-octadecenoic acid) has been isolated in appreciable amounts (45.9%) fromCryptolepis buchnani seed oil. The identification was based on chemical and spectroscopic methods.     

Biodegradable polymers: Photolysis and fungal degradation of poly(arylene keto esters)

Poly(keto esters) were prepared from 4,4′-bis(chloroacetyl) diphenyl ether, 4,4′-bis(bromoacetyl)diphenyl ether, and 4,4′-bis(2-bromopropionyl)-diphenyl ether and aliphatic diacids of 6, 8, 9, 10, and 12 carbon atoms. Low-molecular-weight polymers were found to support the growth of Aspergillus niger and Aspergillus flavus. Introduction of methyl group to the polymer chain decreased the susceptibility of the polymers to fungal attack. Although monomeric model compounds were found to undergo photodegradation the poly(keto esters) underwent mostly crosslinking when irradiated with UV light.     

Selective hydrogenation of fatty acids and methyl esters of fatty acids to obtain fatty alcohols–a review

In this paper, a review is presented of the evolution of different catalytic systems and operating conditions used in the selective hydrogenation of acids and esters of fatty acids to obtain fatty alcohols, which have broad industrial applications in the oleochemical industry. In addition, the current status of the different technologies used industrially (Lurgi, Davy and Henkel) for obtaining fatty alcohols, as well as major global sources of raw materials for the oleochemical industry are put forward. Finally, the reaction mechanisms of the selective hydrogenation process of oleic acid and methyl oleate to obtain the corresponding unsaturated alcohol as well as the new catalysts proposed by researchers are described. © 2016 Society of Chemical Industry