由紫苏油合成超级甜味剂1,8—对Meng二烯—7—肟的研究

采用亚硫酸氢钠加成法从紫苏油中单离出紫苏醛,并以此为原料,通过肟化反应合成了超级甜味剂,１,８－对Ⅱ二烯－７－肟。对合成工艺的最佳技术条件进行了报导。     

由紫苏油合成超级甜味剂1,8-对二烯-7-肟的研究

采用亚硫酸氢钠加成法从紫苏油中单离出紫苏醛,并以此为原料,通过肟化反应合成了超级甜味剂１,８－对二烯－７－肟。对合成工艺的最佳技术条件进行了报导。     

PEG相转移催化法合成香茅腈

研究了用ＰＥＧ作相转移催化剂由香茅醛合成香茅腈的工艺条件,产品纯度９６．７％,产率８７．３％,ｎＤ＾２０１．４４９１;最佳实验条件为：用ＰＥＧ－４００和ＫＯＨ作催化剂,物料比为香茅肟：ＰＥＧ－４００;氢氧化钾＝１００：１５：１０（ｍｏｌ）,在１２５℃下反应２．５ｈ,并用适量甲苯作带水剂。     

直接氧化法合成维生素E中间体2,3,5-三甲基氢醌

利用新的氧化剂体系醋酸—过氧化氢—盐酸，通过直接氧化法合成得到纯度大于９８％的２，３，５ 三甲基氢醌。在氧化反应中，以石油醚为溶剂，反应物料醋酸、过氧化氢、盐酸与２，３，６ 三甲基苯酚摩尔比为６５∶６５∶２５∶１，在回流状态下反应１～１５ｈ，２，３，５ 三甲基氢醌的产率为５４６％。     

以松节油为原料制取紫苏醛

以松节油中的α-蒎烯为原料,采用活化SeO_2作氧化剂,无水乙醇作溶剂先制得桃金娘烯醛,后用Cu-Zn作催化剂,在小于5mmHg、430℃下异构化反应,再经亚硫酸氢钠法提取紫苏醛,纯度可达98％。     

2-氨基-4-氯-5-硝基苯酚的合成

以对二氯苯为原料,经双硝化、水解羟基化、选择还原氨化的路线,合成了双酰胺基苯酚型青成色剂的主要中间体２ 氨基 ４ 氯 ５ 硝基苯酚（Ⅲ）。硝化产率７４％,纯度８０５３％;羟基化产率４５％,纯度９９８３％;选择还原产率６４％,纯度９９８９％。     

杂多酸(盐)催化合成肉桂酸异戊酯的研究

以杂多酸（盐）为催化剂,３Ａ分子筛为脱水剂,肉桂酸和异戊醇为原料合成肉桂酸异戊酯,考察了醇酸比、催化剂种类、催化剂用量、反应时间对酯产率的影响。结果表明,在肉桂酸用量为０１ｍｏｌ情况下,用ＡｌＰＷ１２Ｏ４０为催化剂,催化剂用量为１００ｇ,醇酸摩尔比为２５∶１,反应时间３ｈ,反应温度１３５～１４０℃是最适宜的反应条件。酯产率超过９６％。     

超声波相转移催化合成β-萘乙醚

采用超声波作用下的相转移催化技术合成了香原料β 萘乙醚。经正交实验确定了最佳条件为：β 萘酚∶溴乙烷∶四丁基溴化铵＝１４∶１０∶００３（摩尔比），反应温度７５℃，反应时间５ｈ。产品纯度９９８％，产率可达９４２％，比传统的硫酸催化法（６０％）和常规的相转移催化法（８４６％）的产率都高。     

柠檬醛甲硫醇缩醛的合成研究

０１ｍｏｌ柠檬醛和过量甲硫醇在１２ｍｍｏｌ无水氯化锌催化下发生反应,合成了相应的缩硫醛,产率７４８％。并通过红外光谱、元素分析、核磁共振检测对产物结构进行了确证。     

用KOH-Al_2O_3催化合成柠檬腈初探

从柠檬醛与盐酸羟胺反应制备柠檬肟,后者在１１０～１１２℃温度下经ＫＯＨ－Ａｌ２Ｏ３催化脱水生成柠檬腈,柠檬腈的合成产率为６８％。     

Shelf‐life prediction of perilla oil by considering the induction period of lipid oxidation

Kinetic models for the induction period (IP) of lipid oxidation were developed to predict the shelf‐life of perilla oil during storage. The degree of lipid oxidation was measured in terms of peroxide values (PV). The perilla oil was stored in the dark at various temperatures. The IP was measured at the intersection point of two linear lines and in terms of time and PV at the IP. The IP was expressed by an Arrhenius‐like relationship. Before and after the IP, the reaction followed pseudo‐zero‐order kinetics. The oxidation degrees according to storage times were computed by considering the variables, IP and reaction rate constants. The prediction model equation that was developed to determine shelf‐life is more accurate than in previous studies. Conclusively, considering the IP of lipid oxidation is essential for predicting the shelf‐life of perilla oil and is expected to be applicable to other vegetable oils. Practical applications : In kinetic modeling for shelf‐life estimation in terms of lipid oxidation, induction period (IP) is rarely considered. Thus the estimation of peroxide values (PV) from such models might be inaccurate. The IP was observed in perilla oil oxidation and kinetic models involving the IP were developed. This work enables a better estimation of oxidation. Besides, a shelf‐life diagram of perilla oil has been constructed as a valuable tool for quality control in the food industry.     

Recovery of gossypol from cottonseed gums

Summary A process has been developed for the isolation of pure gossypol from the gums obtained by water-washings of crude hexane-extracted cottonseed oil. Gums are heated with methyl ethyl ketone containing phosphoric acid to cleave gossypol-phosphatide reaction products and are cooled to separate a ketone phase containing the gossypol from a phosphatide-water phase. After concentration by distillation, gossypol is isolated from the methyl ethyl ketone concentrate by addition of glacial acetic acid to form the acetic acid addition compound of 92–94% purity. Two recrystallizations as the acetic-acid complex produce gossypol acetic acid of 99% purity. The purified product can be dissociated by solution in dilute sodium carbonate, from which pure gossypol is recovered by acidification with mineral acid. Yield data from pilot-plant experiments indicated that about 47% of the gossypol in gums is recovered as crude gossypol acetic acid. Depending on the degree of purification of the crude product, the over-all yield of purified gossypol from gums will range from 41% for a product of 98% purity to 36% for a gossypol of 99% purity. Presented at the 50th Annual Meeting of the American Oil Chemists Society, New Orleans, La., April 20–22, 1959. One of the laboratories of the Southern Utilization Research and Development Division of the Agricultural Research Service of the U. S. Department of Agriculture.     

固体超强酸催化异构桃金娘烯醛合成紫苏醛

以桃金娘烯醛为原料,以低温浸渍法制备的SZT-15固体超强酸为新型催化剂,在裂解反应装置中进行催化异构桃金娘烯醛合成紫苏醛反应。考察了异构反应条件对反应转化率和选择性的影响规律,并对催化剂的酸度和晶体结构表征。结果表明：在浸渍浓度1.0 mol/L,焙烧温度550 ℃,进样速度1.0 mL/min,反应温度400 ℃条件下,转化率达87.51%,选择性可达40.56%。催化剂的酸度H0可达?16.0,出现了较强的锐钛矿晶相衍射峰。     

Methanol recycling in the production of biodiesel in a membrane reactor

Membrane reactor technology was used to overcome challenges in biodiesel production. The membrane reactor produces a permeate stream which readily phase separates at room temperature into a fatty acid methyl ester (FAME)-rich non-polar phase and a methanol- and glycerol-rich polar phase. To decrease the overall methanol:oil molar ratio in the reaction system, the polar phase was recycled. Three recycle ratios were tested: 100%, 75% and 50%, at the same residence time and operating conditions. The permeate consistently separated to yield a FAME-rich non-polar phase containing a minimum of 85 wt.% FAME (the remainder being methanol) as well as a methanol/glycerol polar phase. At the highest recycle ratio, the FAME concentration ranged from 85.7 to 92.4 wt.% in the FAME-rich non-polar phase. In addition, the overall molar ratio of methanol:oil in the reaction system was significantly decreased to 10:1 while maintaining a FAME production rate of 0.04 kg/min. As a result, a high purity FAME product was produced.     

甲基膦酸二甲酯的合成

甲基膦酸二甲酯是一种添加型有机磷系阻燃剂,具有含磷量高、阻燃性能优异、价格低廉和添加量少等优点。以亚磷酸三甲酯为原料,对甲基苯磺酸甲酯为催化剂,通过重排反应合成甲基膦酸二甲酯。结果表明,在催化剂用量为亚磷酸三甲酯质量的8%、反应温度180℃和反应时间6 h条件下,产品收率约96%,催化剂可重复使用20次。气相色谱分析表明,亚磷酸三甲酯转化率为100%,甲基膦酸二甲酯粗品纯度大于99%,提纯后甲基膦酸二甲酯产品纯度大于99.7%。     

Dietary Perilla Oil Inhibits Proinflammatory Cytokine Production in the Bronchoalveolar Lavage Fluid of Ovalbumin-Challenged Mice

To evaluate the anti-inflammatory effects of different dietary oils on ovalbumin-sensitized and -challenged mice. Experimental BALB/c mice were fed with different diets containing 5% corn oil [rich in linoleic acid, 18:2n-6 polyunsaturated fatty acids (PUFA), as a control diet], 5% perilla oil (rich in alpha-linolenic acid, 18:3n-3 PUFA) or 5% compound oil containing 50% corn oil and 50% perilla oil, for 5 consecutive weeks. The leukocyte count, inflammatory mediators, and cytokine levels, including proinflammatory and Th1/Th2 cytokines in the bronchoalveolar lavage fluid (BALF) from the mice were determined. The results showed that 5% compound oil administration significantly (P < 0.05) decreased eosinophilic infiltration. Dietary perilla oil could not significantly (P > 0.05) decrease the eosinophil accumulation or the secretions of inflammatory mediators such as prostaglandin E2 (PGE2), histamine, nitric oxide and eotaxin. However, dietary perilla oil significantly (P < 0.05) reduced proinflammatory cytokine (TNF-alpha, IL-1beta and IL-6) and Th1 cytokine (IFN-gamma and IL-2) production. The production of Th2 cytokine IL-10, but not IL-4 and IL-5, was also significantly inhibited by perilla oil administration. The results suggest that dietary perilla oil might alleviate inflammation via decreasing the secretion of pro-inflammatory cytokines in BALF, but failed to regulate the Th1/Th2 balance toward Th1 pole during the Th2-skewed allergic airway inflammation.     

由丁香油提取99%丁香酚的生产技术研究

研究一种以碱液(NaOH)处理丁香油提取纯度99%以上丁香酚的工艺方法。在丁香油中加入碱,使丁香酚与碱反应生成丁香酚钠以除去非酚成分,然后加酸中和,获得丁香酚粗产品,再经高效精馏制备高纯度(99%以上)丁香酚,所获取丁香酚的回收率可达95%~100%,若以70%的丁香油加工生产99%丁香酚,丁香酚加工收率达65%,所获产品质量稳定,香味纯正。     

Synthesis of N-vinyl caprolactam

The synthesis of N-vinyl caprolactam (NVCL), with acetylene as alkylene agent, was studied in a stirred reactor system. With potassium hydroxide (KOH) being used as catalyst and 18-crown-6 ether as cocatalyst, NVCL was synthesized by the reaction of acetylene with caprolactam (CL). Crude products were purified by vacuum distillation. The addition of 18-crown-6 ether accelerates the reaction rate of the nucleophilic addition much greatly. The initial explanation suggests that the hole radius of 18-crown-6 ether is close to the one of K⁺. A complex is formed between 18-crown-6 ether and K⁺ ion on the formed intermediate of potassium caprolactam, so the addition reaction between acetylene and caprolactam was accelerated greatly. In the stirred tank reactor (500 mL four flask bottle), the CL conversion is 30.5% and the product selectivity is up to 73.4%. The experimental data indicate that the product mixture is a non-ideal liquid mixture. A single process of distillation is difficult to obtain a high purity NVCL product. The combination of extraction and distillation is an ideal separation process for producing high purity NVCL.     

Optimization of reaction conditions for the production of DAG using immobilized 1,3-regiospecific lipase lipozyme RM IM

Oils with a high DAG (1,3-DAG) content have attracted considerable attention as a healthful food oil component. In this study, we report on the synthesis of 1,3-DAG from a mixture of FA, constituted largely of oleic and linoleic acids, using an immobilized 1,3-regioselective lipase from Rhizomucor miehei in a solvent-free system. The kinetics of 1,3-DAG production from FA and glycerol were investigated on the basis of a simplified model, taking into consideration the acyl migration reaction, the removal of water, and glycerol dissolution in the oil phase in addition to the esterification reactions. Both the yield of 1,3-DAG and the purity of DAG were evaluated under a variety of experimental conditions, including reaction temperature, pressure, and amount of enzyme present. When either the reaction temperature or the amount of enzyme used was increased, the 1,3-DAG production rate increased, but yield remained relatively constant. The 1,3-DAG yield as well as the purity of DAG gradually decreased because of the enhancement of acyl migration at later stages of the reaction after the 1,3-DAG concentration reached a maximum. Vacuum was important for attaining high yields of 1,3-DAG. Under conditions of a high vacuum (1 mm Hg) at 50°C, 1.09 M 1,3-DAG was produced from 1.29 M glycerol and 2.59 MFA in an 84% yield and in 90% purity.     

Unusual effects of some vegetable oils on the survival time of stroke-prone spontaneously hypertensive rats

Preliminary experiments have shown that a diet containing 10% rapeseed oil (low-erucic acid) markedly shortens the survival time of stroke-prone spontaneously hypertensive (SHRSP) rats under 1% NaCl loading as compared with diets containing perilla oil or soybean oil. High-oleate safflower oil and high-oleate sunflower oil were found to have survival time-shortening activities comparable to that of rapeseed oil; olive oil had slightly less activity. A mixture was made of soybean oil, perilla oil, and triolein partially purified from high-oleate sunflower oil to adjust the fatty acid composition to that of rapeseed oil. The survival time of this triolein/mixed oil group was between those of the rapessed oil and soybean oil groups. When 1% NaCl was replaced with tap water, the survival time was prolonged by ∼80%. Under these conditions, the rapeseed oil and evening primrose oil shortened the survival time by ∼40% as compared with n-3 fatty acid-rich perilla and fish oil; lard, soybean oil, and safflower oil with relatively high n-6/n-3 ratios shortened the survival time by roughly 10%. The observed unusual survival time-shortening activities of some vegetable oils (rapeseed, high-oleate safflower, high-oleate sunflower, olive, and evening primrose oil) may not be due to their unique fatty acid compositions, but these results suggest that these vegetable oils contain factor(s) which are detrimental to SHRSP rats.