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     

羟基乙烷磺酸钙的合成及表征

以β-巯基乙醇和H2O2溶液为原料合成了羟基乙烷磺酸（ITA）,用ITA和CaCO3为原料合成了目标产物羟基乙烷磺酸钙[Ca（HOCH2CH2SO3）2.2H2O],其结构经TGA,FT-IR1,H NMR和元素分析表征。利用热重分析研究了羟基乙烷磺酸钙的热分解过程,在动态空气气氛下,其热分解过程分为两个阶段。第一阶段（30~300℃）失重率为11.06%,失重主要由所含结晶水引起,结晶水的个数为2。第二阶段（300~650℃）失重率为46.16%,这一阶段是其主要分解过程。通过红外光谱确定了羟基乙烷磺酸钙的热分解产物为CaSO4。25℃羟基乙烷磺酸钙在水中的溶解度为120g.100g-1。     

Consecutive reactions in an oleic acid and acetic anhydride reaction medium

When mixing acetic anhydride and oleic acid, two consecutive reactions take place. The first one yields acetic‐oleic anhydride (AOA) and acetic acid. In the second one, oleic acid reacts with AOA to form oleic anhydride at 5% in a mixture when the initial molar ratio is 1:1. Therefore, at equilibrium, the global reaction yields a mixture of AOA, acetic anhydride, oleic acid, acetic acid and oleic anhydride. Based on a new HPLC protocol, all the species of the reaction medium could be separated and quantified. This permitted for the first time to study the kinetics and thermodynamics of the reaction. In the 30–70 °C range, reactions were of order 2 with partial orders of 1 for each reactant. Equilibrium constants were determined for both reactions. Enthalpy, entropy and activation energies were calculated for the main reaction. The influence of molar ratio on the composition at equilibrium was also investigated. The synthesis of AOA could thus be understood and new data were obtained for this singular molecule scarcely cited in the CAS database.     

分子筛催化合成十三碳二元酸二异辛酯的研究

以3、ZSM-5、HZSM-5等分子筛为催化剂,考察了十三碳二元酸与异辛醇进行酯化的反应条件。结果表明,HZSM-5分子筛在常压、温度为469 K、酸醇摩尔比为1∶4、时间为4 h、催化剂用量为2.8%,十三碳二元酸的酯化率达99%以上,产物的最后收率达84%以上,催化剂重复使用5次以上,产率没有发生明显的变化。     

氟硼酸重氮盐裂解反应条件的探讨

讨论了以重氮化法合成4,4’-二氟二苯甲酮路线中的关键工艺——重氮盐裂解的各种影响因素。研究发现,通过加入Fe粉末作催化剂,将干燥的氟硼酸重氮盐分批次缓慢加入到m（重氮盐）：m（甲苯）=1：2．6的甲苯溶剂中裂解,反应可以十分平稳、温和地进行,并且其收率可以稳定在85％左右,含量达94％以上（气相色谱）。     

TA残渣制取混合型增塑剂

利用由聚酯生产中的固体废弃物ＴＡ残渣提取的对苯二甲酸和间苯二甲酸的混合二元酸与异辛醇反应制取混合型增塑剂。探索了合成工艺，反应条件等对产品收率及性能的影响。所获产品达到增塑剂ＤＯＴＰ企业标准，为环境保护，充分利用工业废弃物找到一条新途径     

2,3-环氧丙磺酸钠的合成及应用进展

综述了3 氯 2 羟基丙磺酸钠和2,3 环氧丙磺酸钠的合成及其在功能材料方面的应用。由环氧氯丙烷与亚硫酸氢钠反应可以生成3 氯 2 羟基丙磺酸钠,再由3 氯 2 羟基丙磺酸钠在碱性溶液中闭环生成2,3 环氧丙磺酸钠。2,3 环氧丙磺酸钠因其分子结构中既含有环氧基,又含有亲水性的磺酸盐基团,可通过环氧基的开环反应和共聚反应等制备许多性能优异的功能物质如:胶凝化剂、稠化剂、乳化剂、光敏材料、印染保护剂等。     

邻氯苯磺酰胺合成工艺改进

邻氯苯胺和盐酸以及哑硝酸钠反应生成重氮盐,重氮盐在催化剂存在下与二氧化硫进行反应,生成邻氯苯磺酰氯,磺酰氯再和氨水反应最终生成邻氯苯磺酰胺.收率为83.2%,纯度为99%.     

间苯二甲酸丙二醇酯-5-磺酸钠的合成工艺

以间苯二甲酸二甲酯-5-磺酸钠(SIPM)、1,3-丙二醇(1,3-PDO)为原料,采用酯交换法合成了间苯二甲酸丙二醇酯-5-磺酸钠(SIPP),并研究了催化剂种类及浓度、原料配比和反应温度对酯交换反应的影响。结果表明:通过工艺优化,当选择以钛酸四丁酯作为催化剂,其摩尔分数为0.1%(相对原料中SIPM的摩尔分数),1,3-PDO与SIPM的摩尔分数比为10.14∶1,反应温度为173℃时,酯交换反应速率较快且产物色泽良好。     

Synthesis of pinonic acid esters from ozonolysis of α-pinene

以天然产物松节油的主要成分α-蒎烯和醇为原料,二氯甲烷为溶剂,经臭氧氧化制得α-蒎烯臭氧化物,臭氧化物不加分离直接在三乙胺（TEA）催化下经乙酸酐重排（AA）裂解,一锅法合成了6种蒎酮酸酯类化合物。考察了乙酸酐用量、三乙胺用量、反应时间和反应温度等条件对蒎酮酸酯收率的影响,并通过正交试验对合成条件进行了优化。优化的实验条件为：nAA/nα-蒎烯 = 3.0∶1,nTEA/nα-蒎烯 = 0.75∶1,反应时间为60 min,反应温度为30 ℃,在该条件下合成的6种蒎酮酸酯收率均在60%以上,并采用1H NMR、13C NMR、IR、MS对6种化合物的结构进行了表征。该方法操作简便,条件温和,且收率高,是合成蒎酮酸酯类化合物的一种简易可行的方法。     

以丙二酸单乙酯钾盐为原料合成肉桂酸的新方法研究

研究了肉桂酸的简便高效的合成方法。以丙二酸单乙酯钾盐为原料,利用Knoevenagel缩和法,通过改变反应条件,最终确定反应的最佳方案。结果表明,以乙醇为溶剂,丙二酸单乙酯钾盐和苯甲醛为反应物,DMAP和乙二胺联合催化,采用先缩和后碱性条件下水解的方法得到最终产物反式肉桂酸,其产率为63.7%。红外光谱测定反式肉桂酸结构。该法反应物价廉易得,反应条件温和,有较好的产量和纯度。     

钛硅复合氧化物催化合成长链二元腈

以四氯化钛和硅酸乙酯为原料,制备了复合氧化物催化剂TiO2-SiO2(TSO),应用于催化十三碳二元酸氨化反应制得十三碳二元腈。按正交实验设计方法考察了催化剂组成、催化剂用量、温度、反应时间、搅拌速度及氨气流量对反应的影响。结果表明,最佳反应条件为:钛硅原子个数比3∶1,采用程序升温方式(280℃2 h,300℃3 h,320℃1 h),催化剂用量为酸质量的10%,搅拌速度1000 r/min,氨气流量120 L/h。最佳反应条件下制备的产物十三碳二腈的质量分数达96.70%,收率达86.28%。用TLC、IR、GC-MS检测产物的纯度和结构,并合成了一系列长链二元腈。     

在Br(o)nsted酸性功能化离子液体中室温无溶剂合成长链脂肪酸甲酯

该文以N-甲基咪唑、苄基氯、硫酸、氯磺酸为原料,经季铵化、离子交换、磺化3步反应合成了磺酸型Br(o)nsted 酸性离子液体:1-(4-磺酸基苄基)-3-甲基-咪唑硫酸氢根盐,通过FTIR、1HNMR对其结构进行了确证.以其作为反应介质与催化剂,考察了C4～C16的直链脂肪酸与甲醇的Fischer酯化反应,确定了最佳反应条件:n(酸):n(醇):n(离子液体)=1:1:0.1,反应温度25 ℃、反应时间3～4.5 h,产率84%～98%,产物气相色谱纯度≥96%.该法无需加热、分水,产物分离简便,离子液体经真空除水后可重复使用,循环使用3次,催化活性保持不变.     

The synthesis of sucrose esters from telomer monocarboxylic acids

Glycolipid biosurfactants possess excellent surfactant properties and can be useful model compounds for the synthesis of surfactants from materials available in large quantities. The incorporation of a long, branched alkyl group, which is a feature of glycolipids, into a synthetic surfactant was achieved by the transesterification of sucrose with the methyl ester of a selected telomer monocarboxylic acid mixture, in a solution reaction. Characterisation showed the product to be a mixture of mono- and diesters each comprising a different ratio of linear to branched alkyl chains in the substituted group. Surfactant properties of the mixture, and the chromatographically-separated components, when evaluated in both distilled water and a salt solution, were found to be superior to a range of sucrose stearates. In addition the biosurfactant analogues were found to be more effective than surfactants derived from β-keto alkyl esters of various sugars (including sucrose) but were not as efficient as these latter compounds.     

肉豆蔻酸-2-羟基-3-磺酸钠丙酯的合成

以亚硫酸氢钠、环氧氯丙烷、磷酸钠和肉豆蔻酸等为原料,合成了肉豆蔻酸-2-羟基-3-磺酸钠丙酯,探索了反应温度、催化剂、反应时间、反应物物质的量比等因素对合成的影响。结果表明,适宜的反应条件为:①合成3-氯-2-羟基丙磺酸钠:环氧氯丙烷滴加到亚硫酸氢钠溶液中,反应时间3.5 h,反应温度85℃,②合成环氧丙磺酸钠:3-氯-2-羟基丙磺酸钠加入磷酸钠溶液中,反应温度55℃,反应时间4.0 h;③合成肉豆蔻酸-2-羟基-3-丙磺酸钠:环氧丙磺酸钠溶液滴加到90℃的肉豆蔻酸溶液中,反应时间3.0 h,产率为85.2%。对产品进行了红外光谱表征,产品显示了较好的表面活性。     

油酸-2-羟基-3-磺酸钠丙酯的合成

以亚硫酸氢钠、环氧氯丙烷、磷酸钠和油酸等为原料,合成了油酸-2-羟基-3-磺酸钠丙酯,探索了反应温度、催化剂、反应时间、反应物物质的量比等因素对合成的影响,得到了适宜的反应条件：环氧氯丙烷滴加到亚硫酸氢钠溶液中,反应时间3．5h,反应温度85℃,合成3-氯-2-羟基丙磺酸钠;3-氯-2-羟基丙磺酸钠加入磷酸钠溶液中,反应温度55℃,反应时间4．0h,合成环氧丙磺酸钠;环氧丙磺酸钠溶液滴加到90℃的油酸溶液中,反应时间3．0h,合成油酸-2-羟基-3-丙磺酸钠,产率为85．2％。对产品进行了红外光谱表征,产品显示了较好的表面活性。     

HIV病毒抑制剂中间体5-戊基间苯二酚的合成

以3,5-二甲氧基苯甲酸为起始原料,与LiH在室温下反应5h生成苯甲酸盐,生成的盐再与正丁基锂进行酰化反应得到3,5-二甲氧基苯戊酮,进而在210℃以下进行乌尔夫-黄鸣龙反应将酮还原,生成3,5-二甲氧基戊苯,所得产物与吡啶盐酸盐熔融,于200℃回流2h,脱甲基制得5-戊基间苯二酚,总收率达60.9%,纯度≥98%。     

Impact of Fatty Acid Structure on CALB‐Catalyzed Esterification of Glucose

Enzymatic synthesis of fatty acid glucose esters from different fatty acyl donors are performed via enzymatic catalysis in the presence of Candida antarctica lipase B (CALB), using acetonitrile as the solvent. The acyl donor nature (fatty acid or fatty acid vinyl ester) and structure are varied. Lower reaction rates and lower conversions are obtained with fatty acids in comparison to their corresponding vinyl esters. Moreover, the acyl donor with the longest chain length gives the highest conversions. The presence of unsaturation on the acyl donor chain is also shown to be detrimental to the conversion. Practical Applications: The practical applications of the present work are related to the production of gluco‐esters that could be used as nonionic surfactants as detergents, cosmetics and food emulsifiers, emollients or conservatives, respectively. In this study, it is shown that in order to get high production yields, each reaction parameter has to be tuned properly.     

Methods for increasing estolide yields in a batch reactor

Estolides are formed when the carboxylic acid group of one fatty acid forms an ester link at the site of unsaturation of another fatty acid. These compounds have the potential to be used in a variety of applications, such as lubricants, greases, plastics, inks, cosmetics, and surfactants. By manipulating the reaction equilibrium, yields of 20% estolide in clay-catalyzed estolide reactions have been increased to 30%. Reactions conducted at 180°C, where water was vented out of the reactor at specific times, not only gave dimer-free estolides but also yields up to 30%. Steam has also been used instead of water with similar results. Estolides were quite stable at temperatures up to 250°C, even when they were exposed to air.     

新型固体钙锌复合稳定剂的直接法合成及其对PVC热稳定作用的研究

以一种简便的方法制备了以环氧脂肪酸钙、环氧脂肪酸锌为主的固体钙锌复合稳定剂,研究发现其对PVC不但有较好的长期热稳定作用,而且具有较好的初期着色性。可用于无毒制品,具有良好的社会效益和经济效益。