Synthesis of glycidyl esters

A novel method of synthesis of glycidyl carboxylates (2,3‐epoxypropyl carboxylates, RCOOCH₂CH‐CH₂O) has been developed by carrying out the reaction of epichlorhydrin with a carboxylic acid in the presence of chromium acetate catalyst and subsequent dehydrochlorination of the resulting mixture of chlorohydrin esters followed by their separation. © 1999 Society of Chemical Industry     

Glycidyl esters. II. Synthesis of esters of commercial and pure fatty acids

The reaction of salts of earboxylic acids with epichlorohydrin in the presence of quaternary ammonium halides to form glycidyl esters has been demonstrated to be applieable to a variety of acids derived from fats, including commercial mixtures. The glycidyl esters of pelargonic, lauric, oleic, dimerized linoleic, ricinoleic, behenic, and sebacic acids as well as those of the fatty acids derived from tallow, wool wax, and soya oil have been prepared in 80–95% yields and purities. Eastern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Crystal properties of stearate esters of racemic and L(+) propylene glycol

The 1-monostearate and the distearate of pro-pylene glycol were prepared with racemic propylene glycol and L ( + ) propylene glycol, and their crystal properties were compared. Racemic propylene glycol-l-monostearate shows four dif-ferent polymorphic modifications whereas opti-cally active propylene glycol-1-monostearate is monomorphic, with a melting point of 54.0C and a long spacing of 50.6A. Racemic propylene glycol distearate has an unstable Form II, which transforms irreversibly to Form I near 44C. Form I melts at 58.8C. The two forms have long spacings of 53.4A (Form II) and 43.4A (Form I). Optically active propylene glycol distearate exhibits three crystalline modifications: an un-stable Form II which transforms irreversibly to Form I near 37C, with Form I melting at 53.9C, and a third, stable form, termed Form III, melt-ing at 58.80. The long spacings of the three forms are 51.9A, 43.6A, and 46.9A respectively. Heats of transition for the various phase changes are given.     

Copolymerization of styrene. IV. Copolymerization with esters of benzylidenecyanoacetic acid

Styrene was copolymerized in bulk with a number of esters of benzylidenecyanoacetic acid. The kinetic scheme of all pairs fitted the improved scheme of copolymerization, taking into account the effect of the penultimate unit. The Alfrey-Price Q and e values were calculated. Using the modified Taft equation, log (1/r₁) = ρ^*σ^* + δE_s, it was found that the relative reactivities of the ester monomers toward the polystyryl radical were correlated by the polar substituent constants σ^* of the ester alkyl groups (ρ^* = 0.14) and not by their steric substituent constants E_s (δ = 0.008).     

Physical properties of fatty acid methyl esters. IV. Ultrasonic sound velocity

The ultrasonic sound velocity of the unsaturated fatty acid methyl esters from acetate to nonadecanoate, methyl oleate, linoleate, linolenate, and erucate have been measured at 20C and 40C in the liquid state. Data of the saturated compounds were correlated with the Smittenberg relation and a reasonable fit was noted. The molar sound velocity according to Rao was computed from the observed values and increments for the CH₂ group and for the double bond are presented.     

Arylsulfonate esters of fatty alcohols: IV. Effects on cholesterol catabolism

Hypercholesterolemic rats, fed 1% cholesterol and 0.5% glycocholate, were treated with arylsulfonates in various ways to observe the pattern of cholesterol elimination. Dietary linoleyl p-toluene-sulfonate (LTS) hastened return to normocholesterolemia and lowered hepatic cholesterol either with or without continued cholesterol feeding. LTS administered via the portal vein significantly lowered plasma cholesterol in 48 hr; ethyl linoleate and monoolein produced no lowering. LTS administered via the portal vein to glycocholate-infused rats increased the biliary excretions of label from [4-¹⁴C]cholesterol administered intracardially and also increased total bile acid excretion 21% without increased bile volume when compared to similar injection of ethyl linoleate. No change in biliary excretion of cholesterol was seen. Bile acid kinetics were studied by using isotopic dilution techniques. Cholate turnover was enhanced by feeding oleyl p-toluenesulfonate (OTS) and oleylp-(n-decyl)-benzenesulfonate (ODS) as suggested by a 16–35% decrease in half-life in both normal and hypercholesterolemic rats. Rats consuming a grain-based colony diet had a 54% increase in cholate synthesis when OTS was included in the diet. The composition of bile was changed when either OTS or ODS was fed; an increase in chenodeoxycholate was noted. This change was gradual with OTS but rapid with ODS and paralleled enhanced decay of chenodeoxycholate specific radioactivity in response to treatment. ODS and OTS also increased¹⁴CO₂ expiration from oral [26-¹⁴C] cholesterol in hypercholesterolemic rats. Dietary OTS and ODS elevated hepatic free cholesterol in hypercholesterolemic rats; ODS also elevated plasma free cholesterol and increased cholesteryl ester hydrolase activity in the liver. The data suggest that arylsulfonates stimulate cholesterol catabolism, in addition to the reported inhibition of cholesterol absorption [Lipids 12:819 (1977)]. Published as Journal Paper No. 6699, A.E.S., Purdue University.     

Analysis of autoxidized fats by gas chromatography-mass spectrometry. IV. Soybean oil methyl esters

An unusual isomeric distribution of hydroperoxides has been found in soybean oil esters oxidized at low levels (peroxide values below 50). The unexpectedly high concentration of the 12-hydroperoxide isomer is in marked contrast to the isomeric composition of oxidized pure linolenate. The different isomeric hydroperoxides observed at low levels of oxidation may contribute through their decomposition to the unique flavor deterioration of soybean oil. Quantitative gas chromatographymass spectrometry (GC-MS) used in this study provides for the first time an answer to the basic question of which hydroperoxides contribute to the state of oxidation of soybean oil. Results of GC-MS were confirmed by capillary gas chromatography. Analyses of highly oxidized soybean esters (peroxide values 468 and 2352) reveal the same main compounds as those found in oxidized pure linoleate, together with small amounts of oleate and linolenate hydroperoxides. Presented at AOCS Meeting, St. Louis, Missouri, May 14–18, 1978. 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.     

Acid curing of epoxides: an unexpected mechanism for the reaction of glycidyl esters with acids

Summary Products from the reaction of acids with glycidyl esters of other acids were analyzed by¹³C-NMR-spectroscopy and HPLC. Besides the two isomeric structures that are normally formed during the ring-opening of epoxides by acids (- and \-hydroxy ester), a third structure was observed. This structure was identified by comparative studies as abnormal \-hydroxy ester. A mechanism for the reaction of glycidyl esters with acids is postulated.     

缩水甘油月桂酸酯的制备

论述了由环氧氯丙烷与月桂酸钠在相转移催化条件下反应制取缩水甘油月桂酸酯的方法。产率在９０％以上。     

Polymerization of chlorophenyl glycidyl ethers. VI

Summary Polymerization of p-chlorophenyl glycidyl ether initiated by potassium glycolates (ethylene, propylene and 2-methyl propylene glycolatea) in DMSO containing some 18-crown-6 ether or glycol was investigated. For the reaction system containing the propylene glycolate asymmetrically substituted with a methyl group, relatively high polymerization rates were obtained as compared with those found for the other systems studied, the resultant polymers also having higher molecular weights and comparatively low polydispersities. Aliphatic double bonds were found to be absent in the polymers synthesized, which would suggest that in the anionic polymerization process studied the growing chain is not transferred to the monomer.Dedicated to Prof. C.I. Simionescu on the occasion of the 60th anniversary of his birthday     

Periodate-permanganate oxidations. IV. Determination of the position of double bonds in unsaturated fatty acids and esters

Summary The reaction of the periodate-permanganate reagent with unsaturated fatty acids, including oleic, elaidic, eicosenoic, 10-undecenoic, and linoleic acids proceeded smoothly to give the expected end-products in quantitative yields. The latter were conveniently isolated and determined by partition chromtography on silicic acid columns in 10 to 100 mgm. quantities. Some compounds, which were unreactive due to insolubility in the reagent, gave satisfactory results when the media contained 5 to 10% of pyridine. This was true also for methyl linoleate even though solution was incomplete. However methyl oleate and triolein did not give quantitative results even in media containing 20% or more of pyridine in which the esters were completely dissolved. Presented at fall meeting, American Oil Chemists’ Society, Philadelphia, Pa., Oct. 10–12, 1955. Issued as Paper No. 214 on the “Uses of Plant Products” and as N.R.C. No. 3882.     

愈创木酚缩水甘油醚的合成

以愈刨木酚和环氧氯丙烷为原料,采用一步法合成医药中间体愈创木酚缩水甘油醚。经红外光谱确认了产品结构。研究了反应时间、原料配比、催化剂种类与用量、碱用量、反应操作步骤等条件对反应总收率的影响,得出优化反应条件：将愈创木酚：环氧氯丙烷：无水碳酸钾(物质的量比1：8：2),相转移催化剂(2％),回流反应5h,蒸除溶剂后再减压蒸馏,取132℃/0．67kPa馏分,反应总收率92．3％。该法操作简单,适于工业化生产。     

缩水甘油基叔基丁基醚的合成

以环氧氯丙烷和叔丁醇为基本原料,经加成反应和环化作用,合成了缩水甘油基叔丁基醚(TBGE);用正交实验方法优化了TBGE的合成条件,气相色谱法分析了产品中TBGE含量,GC-MS和FT-IR等表征了产物结构.结果表明,在以BF3-乙醚为催化剂时,合成TBGE的适宜条件为:加成反应的温度和时间分别为50.0℃和5.0h,...     

Non-volatilea-branched chain fatty acid derivatives: IV. Addition of aryl esters to long chain olefins

The di-tertiary butyl peroxide initiated free radical addition of methyl phenylacetate, methylp-tolylacetate and methylp-methoxyphenylacetate to 1-decene gives two types of products. In addition to the expecteda-branched esters, dehydrodimer (bothmeso anddl) esters were also obtained. The highest yield ofa-branched ester was obtained from methyl phenylacetate. Higher yields of the dehydrodimer esters were obtained from the substituted phenyl esters. Attempts to add methylp-nitrophenylacetate to 1-decene were not successful and no evidence for the formation of a dehydrodimer product was observed.     

脱氢枞酸缩水甘油酯的合成

以脱氢枞酸(DHA)与Na OH作用后生成的脱氢枞酸钠(DHA-Na)和环氧氯丙烷(ECH)为原料,经缩合反应制备标题化合物DHAGE。探讨了溶剂类型、催化剂类型、反应时间、反应温度及物料比对产物收率的影响,用FT-IR、GC-MS表征了产物结构,环氧值分析法测定产物中DHAGE的含量。实验结果表明,制备脱氢枞酸缩水甘油酯的适宜条件为:二甲苯作溶剂,四丁基溴化铵(TBAB)作催化剂,反应时间为4.0 h,反应温度为95℃,n(ECH)∶n(脱氢枞酸钠)=4.0∶1.0;在此条件下DHAGE的收率为83.1%。     

缩水甘油硝酸酯的绿色合成

研究了一种五氧化二氮为硝化剂,选择性硝化缩水甘油合成缩水甘油硝酸酯的温和、高效方法.考察了摩尔配比、反应温度、反应时间等因素对硝化过程的影响.结果表明,当五氧化二氮与缩水甘油的摩尔比为1∶1,在-15℃下反应6 min,缩水甘油硝酸酯的选择性为100%,收率达94%.     

甲基丙烯酸缩水甘油酯-苯乙烯-丙烯腈聚合物的合成

采用悬浮聚合方法,使甲基丙烯酸缩水甘油酯(GMA)、苯乙烯(St)和丙烯腈(AN)单体发生自由基聚合,获得数均摩尔质量M_n=7×10~4g/mol,分散度D=2.36,外观无色透明的三元共聚物珠粒.通过红外分析发现其在1727 cm~(-1)处有羰基的强烈伸缩振动吸收峰,在1253 cm~(-1)(环氧基团的对称振动吸收峰)、915 cm~(-1)和861 cm~(-1)(环氧基团的不对称振动的两个吸收峰)处的红外吸收峰,表明了环氧基团的存在;3200～3600 cm~(-1)范围没有明显的羟基吸收峰,说明聚合物中GMA的环氧基团很少或基本上没有开环,据此可以初步认定GMA单体在参与聚合反应时,是以打开双键的形式进行加成聚合反应.     

Combined effect of lignosulfonate and carbonate on pure portland clinker compounds hydration. IV. Hydration of tricalcium aluminate-sodium oxide solid solution

The combined effect of lignosulfonate and sodium carbonate on the hydration of C₃A and C₃ANa₂O solid solution was examined by DTG and TG curves, by XRD analysis and by zeta potential measurements. It is confirmed that the simultaneous addition of lignosulfonate and carbonate completely blocks the C₃A hydration with an induction period whose length is proportional to the percentage of admixtures. On the other hand, no induction period was observed in the hydration of C₃ANa₂O solid solution in the presence of both lignosulfonate and carbonate. The effect of the admixtures on the zeta potential is substantially the same for C₃A and C₃ANa₂O solid solution. The liquefying effect of NC and lgs combined addition seems to be more pronounced on C₃A than on C₃ANa₂O solid solution.     

The STOBBE condensation with substituted succinic esters. Part IV. A Synthesis of Substituted Naphthalene and Maleic Anhydride

The condensation of piperonal with dimethyl phenylsuccinate using sodium hydride as condensing agent, gave predominantly the corresponding (E)-half-ester 1 . Cyclisation of this product led to the formation of the naphthalene derivative 2a , which upon hydrolysis produced the hydroxy acid 2b . The latter gave upon subsequent methylation and hydrolysis the naphthalene derivatives 2c, d . When benzaldehyde, p-chioro-, and p-methoxy-benzaldehydes were condensed under the above mentioned conditions, they produced the corresponding anhydrides 6a—c ; which were hydrolysed to the corresponding sodium salts 9 . The anhydride 6c gave with aniline the amide 7 .