氰氟草酯的合成

以（S）-乳酸甲酯为原料，与对甲苯磺酰氯反应制备（S）-对甲苯磺酰乳酸甲酯，再与对苯二酚反应制备（R）-2-（4-羟基苯氧基）丙酸乙酯，然后与3，4-二氟苯腈反应制备（R）-2-[4-（4-氰基-2-氟苯氧基）苯氧基]丙酸乙酯，经水解、酯化合成氰氟草酯，总收率49％，化学纯度95％，光学纯度98％。     

O，O－二叠氮烷基－a－对甲苯磺酰胺基－a－取代苄基磷酸酯的合成研究

首次合成了未见文献报道的系列O，O－二（β－叠氮乙基）－a－对甲苯磺酰胺基－取代苄基磷酸酯和O，O－二（β，β′－二叠氮异丙基）－a－对甲苯磺酰胺基－m－硝基磷酸酯Mannich化合物，分别用IR，^1HNMR以及元素分析对这些化合物结构进行了鉴定，并对上述化合物进行了谱图解析。此外，用DTA分析了Mannich碱的热稳定性。     

R(+)对羟基苯氧基丙酸炔丙酯的合成

报道了合成超高效除草剂炔草酯的中间体R(+)对羟基苯氧基丙酸炔丙酯的方法。以(S)-(-)乳酸甲酯为原料,先与对甲苯磺酰氯反应制备S-对甲苯磺酰乳酸甲酯,再与对苯二酚和丙炔醇反应,制备R(+)对羟基苯氧基丙酸炔丙酯,总收率76%。旋光度为[α]2D5=+37.5。     

精馏法合成乳酸乙酯的研究

采用带分水器的精馏装置，使乳酸酯化的原有脱水－酯化两步过程，能在该装置上一步进行。通过正交试验， 考察了乙醇的用量、催化剂的用量、带水剂的用量三个因素对乳酸乙酯收率的影响。确定了最佳的配比，并由验证实验得到证明，脱水－酯化反应在2h基本完成，乳酸乙酯的收率可达到96％以上。     

一种(R)-2-(4-氯-2-甲基苯氧)丙酸辛酯阻根剂的制备方法

<正>本发明公开了一种可用做阻根剂的(R)-2-(4-氯-2-甲基苯氧)丙酸辛酯的制备方法,包括:以L-乳酸乙酯为原料,与对甲苯磺酰氯磺化,得到相应的磺酰酯化合物;将磺酰酯化合物与4-氯邻甲酚醚化,得到相应的芳香醚酯化合物;该类醚酯化合物最后与正辛醇进行酯交换,得到(R)-2-(4-氯-2-甲基     

固体酸催化合成乳酸乙酯

用乳酸和乙醇为原料，在ＨＹ型固体酸存在下制备了乳酸乙酯。催化剂用量为１１－３０ｇ，在１００－１６０℃下，乳酸与乙醇反应８－１０ｈ，酯化率可达６０％以上，催化剂可重复使用。     

S-(-)-对甲苯磺酰乳酸甲酯的合成

研究了以三乙胺为催化剂,二氯甲烷为溶剂,S-(—)-乳酸甲酯和对甲苯磺酰氯发生酰化反应,合成S-(—)-对甲苯磺酰乳酸甲酯的方法,讨论了反应温度、时间、溶剂、催化剂和对甲苯磺酰氯对反应产率的影响。结果表明：n(三乙胺)：n(S(—)-乳酸甲酯)：1：1．2,0～5℃下,对甲苯磺酰氯的二氯甲烷溶液加入S-(—)-乳酸甲酯中,得到S-(—)-对甲苯磺酰乳酸甲酯。通过旋光度、熔点测定及IR分析,证实其结构与预期结构相符。收率为95％,光学纯度95％。     

α-甲基-缩二乙醇酸二乙酯的合成研究

2,5-二甲基-4-羟基-3（2H）-呋喃酮是一种非常重要的原料,而α-甲基-缩二乙醇酸二乙酯是合成呋喃酮的重要中间体。本论文采用苯的同系物为溶剂,用金属钠和乳酸乙酯为原料制得乳酸乙酯钠盐,然后与氯乙酸乙酯制得该中间体。研究了加料顺序、反应温度、反应时间、物料摩尔比、溶剂效应对收率的影响,找到了最佳反应条件;采用正加的加料方式;反应温度90％;反应时间3h;n（Ethyl chloracetate）：n（Na）=1.2：1.0;所用溶剂为甲苯。在此条件下该中间体的总收率高达58.6％。     

SO24^2-／La2O3_TiO2固体超强酸催化合成乳酸乙酯

乳酸乙酯是一种食用合成香料。本论文研究了在固体超强酸so4^2-／La2O3-TiO2催化下,由乳酸与乙醇直接合成乳酸乙酯的新工艺。通过红外光谱及其它方法对产物乳酸乙酯进行检测。     

C1—5醇乳酸酯及丙交酯制备的初步研究

用Ｃ１－５醇酯化Ｄ,－Ｌ乳酸制得相应的乳酸酯,其中用Ｃ４－５醇酯化乳酸不用带水剂,产率可达８０％以上,用Ｄ,Ｌ－乳酸酯制丙交酯会生成等量的外消旋与内消旋体。外消旋丙交酯为目标产物,内消旋丙交酯可回收作原料。由此计算外消旋丙交酯单程产率将不大于５０％,实验中除乳酸甲酯外,乳酸酯单程消耗和丙交酯单程产率分别为２６％－３５％和２２％－３５％。     

Key fuel properties of palm oil alkyl esters

Methyl esters of vegetable oils have been successfully evaluated as diesel substitute. In the present study, other alkyl esters, namely ethyl and isopropyl esters of crude palm oil and crude palm stearin were synthesized via chemical transesterification reactions and subsequently evaluated for their fuel properties. Generally, these alkyl esters exhibit higher viscosity (4.4×10⁻⁶m²/s–5.2×10⁻⁶ m²/s) compared to that of petroleum diesel (4.0×10⁻⁶ m²/s). However, compared to petroleum diesel, these alkyl esters exhibit acceptable gross heat of combustion (39–41 MJ/kg). Originated from renewable origin, the low sulfur content in alkyl esters emits much lower SO₂. These alkyl esters are much safer than petroleum diesel in terms of safety for storage and transportation as they possess high flash points. They may find applications in the fuel industry besides utilization as oleochemicals.     

Comparison of Antioxidant Capacities of Rosmarinate Alkyl Esters in Riboflavin Photosensitized Oil-in-Water Emulsions

Effects of the alkyl chain length of rosmarinate alkyl esters on the oxidative stability in photosensitized oil-in-water (O/W) emulsions were determined by lipid hydroperoxides and headspace volatile analyses. Antioxidant capacities of 20 μM rosmarinate esters with alkyl chain length of 0, 4, 8, 12, 18, and 20 were tested in O/W emulsion containing stripped soybean oil, Tween 20 as an emulsifier, and riboflavin as a photosensitizer. Synergistic or antagonistic effects of 20 μM α-tocopherol in the presence of rosmarinate alkyl esters were also determined. Samples containing rosmarinate with 4 and 8 alkyl esters showed lower lipid hydroperoxides and headspace volatiles than those without rosmarinate and those with 0, 12, 18, and 20 alkyl esters, which indicates that phenolic free radical scavengers showed antioxidant capacities non-linearly in riboflavin photosensitized O/W emulsions. Antagonistic rather than synergistic effects were observed in all rosmarinate alkyl esters with α-tocopherol in current conditions although rosmarinates with 4, 8, and 12 alkyl esters showed better antioxidant capacities than those with other alkyl chain length. The results of this study clearly showed that rosmarinates need the proper length of non-polar groups to show optimum antioxidant capacities in O/W emulsions with Tween 20 as an emulsifier under riboflavin photosensitization.     

Cholesteryl ester compounds containing alkyl branched acyl groups — their preparations,properties and applications

Cholesterol having a reactive hydroxyl group at C₃-position can react with fatty acids to give the corresponding cholesteryl esters. Most of the natural cholesteryl esters consist of straight alkyl chain fatty acids with a high melting point. In oleochemistry it is well known that alkyl branched fatty acids, which are derived from petroleum or the fat and oil industry, have low melting points (mp.) and are chemically more stable if they are saturated acids. We designed alkyl branched fatty acid cholesteryl esters by means of common esterification and found some esters having a low mp. (mostly as a liquid). They had no irritative effect on both animal and human skin. They showed characteristic emulsification properties, namely the formation of either O/W or W/O emulsion coexistence together with other lipid components. Applying them onto human skin, they were able to penetrate towards the stratum corneum and improve the water-retaining ability and the barrier function of the stratum corneum. Based on these properties we have been applying the alkyl branched fatty acid cholesteryl ester, especially the methyl branched isostearic acid cholesteryl ester (IS-CE), to a shampoo and a rinse as hair cosmetics, skin care cosmetics and bath-additive products in the past decade.     

Poly(alkyl lactate acrylate)s having tunable hydrophilicity

Four alkyl lactates and alkyl lactate acrylates having methyl, ethyl, propyl, and butyl as alkyl moiety were synthesized by azeotropic distillation. Their formation was confirmed by Fourier transform infrared (FTIR), mass, ¹H nuclear magnetic resonance (NMR) and proton decoupled ¹³C NMR spectroscopic techniques. Solution polymerization was carried out for these alkyl lactate acrylates and the formed homopolymers were characterized by FTIR, ¹H NMR, proton decoupled ¹³C NMR spectroscopic, and gel permeation chromatographic techniques. Shear thinning behavior was observed for all the polymers. Wide angle X‐ray Diffraction studies showed that the polymers were amorphous in nature and also exhibited odd‐even effect among alkyl lactate groups with respect to average molecular interchain spacing. Depending on the length of the alkyl lactate groups, relative humidity and time, the hydrophilicity of the polymers decreased with increase in the length of the alkyl lactate group among the odd and even series. Among the studied polymers, poly(ethyl lactate acrylate) may have the potential for hydrogel applications, due to its highly hydrophilic nature. T_g decreased with increase in length of alkyl lactate groups. Trend observed on the thermal stabilities of poly(alkyl lactate acrylate)s could be explained on the basis of average molecular interchain spacing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40962.     

乳酸酯催化脱水制备丙烯酸酯

以NaY分子筛与Li型蒙脱土复配为催化剂,乳酸酯催化脱水制备丙烯酯,考察催化反应温度和溶剂对乳酸酯类脱水的影响,并对催化脱水机理进行探讨。结果表明,温度升高有利于乳酸酯类的脱水,乳酸甲酯与乳酸乙酯最佳脱水温度分别为320 ℃和290 ℃。溶剂效应显示脱水产物与溶剂相关,乳酸酯催化脱水机理为E2消除机理。     

Mixed Alkyl Esters from Cottonseed Oil: Improved Biodiesel Properties and Blends with Diesel Fuel

Transesterification of refined cottonseed oil (CSO) was carried out with methanol, ethanol, 1-butanol, and various mixtures of these alcohols to produce biodiesel. In the mixed alcohol transesterifications, formation of methyl esters was favored over ethyl and butyl esters. The influence of ester head group on fuel properties was determined. Specifically, cold flow properties, lubricity, and energy content improved in the order: CSO butyl esters (CSBE, best) > ethyl esters (CSEE) > methyl esters (CSME). Higher kinematic viscosities (KVs) as well as lower iodine values (IVs) and wear scars were observed with larger ester head groups. Blends of CSME, CSEE and CSBE exhibited properties intermediate to the neat esters. All ester samples were within the limits prescribed in ASTM D6751 and EN 14214 for cetane number, acid value (AV), glycerol (free and total) content, sulfur, and phosphorous. Also examined was the influence of blending alkyl esters with petrodiesel. All blends exhibited improved cold flow properties versus unblended alkyl esters. Enhanced lubricity was observed after blending. With increasing content of biodiesel, higher KVs and lower energy contents were observed. Finally, all blends were within the limits specified in ASTM D975 and D7467 for AV, KV and sulfur.     

Low-temperature properties of alkyl esters of tallow and grease

The low-temperature properties of mono-alkyl esters derived from tallow and recycled greases were determined for neat esters and 20% ester blends in No. 2 low-sulfur diesel fuel. Properties studied included cloud point, pour point, cold filter plugging point, low-temperature flow test, crystallization onset temperature, and kinematic viscosity. Compositional properties of the alkyl esters determined included water, residual free fatty acids, and free glycerol content. In general, the secondary alkyl esters of tallow showed significantly improved cold-temperature properties over the normal tallow alkyl ester derivatives. The low-temperature flow test did not show a 1:1 correlation with cloud point as previously observed with methyl soyate and methyl tallowate. For the homologous series methyl to n-butyl tallowate, ethyl tallowate had the best broad-spectrum low-temperature properties, both neat and when blended in diesel fuel. For the greases studied, both the normal and branched alkyl ester derivatives showed improved properties over corresponding tallow esters, especially with neat esters.     

Production of alkyl esters from tallow and grease using lipase immobilized in a phyllosilicate sol-gel

The lipase-catalyzed synthesis of alkyl esters from tallow and grease using Pseudomonas cepacia lipase (PS-30) immobilized within a phyllosilicate sol-gel matrix was investigated. The effects of the presence of alcohol and of the amount of enzyme used were studied. The matrix-immobilized PS-30 lipase effectively converted grease and tallow to ethyl esters in greater than 95% yield when using ethanol. The final conversion of grease or tallow to alkyl esters was aided by the addition of molecular sieves (0.4 wt% of substrates) to the reaction mixture. The matrix-immobilized PS-30 enzyme was easily recovered and could be reused at least five times without losing its activity. Accordingly, the phyllosilicate sol-gel immobilized PS-30 lipase is potentially useful for the economic production of biodiesel fuel.     

富马酸烷·3-PG酯的合成研究

研究 5种具有良好的抗氧化和抗菌活性的新型化合物———富马酸甲 (乙、丙、丁、戊 )·3 PG酯的合成工艺条件并揭示了其规律。发现富马酸单酯单酰氯与没食子酸丙酯 (PG)的理想反应条件为 :在c(PG) =5 7 0 1mol/L的吡啶溶液中 ,吡啶正常回流温度下 ,分别缓慢滴加富马酸单甲 (乙、丙、丁、戊 )酯单酰氯 ,反应 4 0～ 6 0min ,可获得产率为 75 6 % (78 3%、83 8%、83 3%、76 5 % )的富马酸甲 (乙、丙、丁、戊 )·3 PG酯。随烷基碳链的增长 ,马来酸酐与醇的物质的量比减小 ,反应温度升高和反应时间延长     

Continuous Lipase-Catalyzed Alcoholysis of Sunflower Oil: Effect of Phase-Equilibrium on Process Efficiency

Phase-equilibrium diagrams of biodiesel synthesis substrate (oil/alcohol/alkyl esters) and product (alkyl esters/glycerol/alcohol) mixtures containing methanol, ethanol and propanol, respectively, were used for the identification of those composition ratios leading to mixture homogeneity. Based on the diagrams, complete conversion of the substrate oil contained in a sunflower oil/ethanol/ethyl ester mixture at a weight ratio of 7.6:11.4:81.0 resulted in the generation of an amount of glycerol capable of remaining in solution in the product mixture. In contrast, complete conversion using a mixture of a lower alcohol and ethyl ester content (19.0:6.0:75.0) leads to the separation of phases. A continuous reactor charged with Lypozyme TL-IM and fed with the former mixture showed constant conversion and productivity with time, whereas process efficiency was found to decrease drastically when the latter mixture was fed. When a sunflower oil/isopropanol/isopropyl ester mixture at a weight ratio of 35:35:30 was fed in the reactor charged with Novozym 435, the output glycerol concentration was equivalent to that theoretically expected. In contrast, feeding a sunflower oil/ethanol/ethyl ester mixture of equal proportions as above, the glycerol concentration was lower than expected, suggesting the occurrence of glycerol adsorption on the enzyme support.