硼酸保护羟基法合成甘油单月桂酸酯

研究了以甘油、月桂酸为原料,用硼酸保护羟基进行酯化反应合成甘油单月桂酸酯的新方法。最佳合成条件是：ｍｏｌ甘油：ｍｏｌ硼酸：ｍｏｌ月桂酸＝２：１：２,对甲苯磺酸（催化剂）用量为月桂酸用量的１．２０％（ｗｔ％）,在２３０℃反应１ｈ,产品收率为９１．２％,单酯含量为９４．８％,产品经ＩＲ分析。     

氨磺酸催化合成丁酸丁酯的研究

以氨磺酸为催化剂催化合成了丁酸酯,确定了酯优化条件。实验结果表明：在酸用量为０．２ｍｏｌ,醇酸摩尔比值为１．８,催化用量１．０ｇ,带水剂甲苯１５ｍＬ,反应时间２．０ｈ,反应温度１１０℃－１３０℃的最佳反应条件下,酯化率为９８．２％。     

氯化高锡催化合成乙酸丁酯的研究

采用ＳｎＣｌ４作乙酸和丁醇的酯化催化剂,２．３５（ｗｔ）％ＳｎＣｌ４可在６０ｍｉｎ内催化丁醇和乙酸（１：１３（ｍｏｌ／ｍｏｌ）达到９７．５％的产率,其催化活性远远比固体超强酸高,与浓硫酸相当,而腐蚀性则比浓硫酸低得多,因而有希望取代浓硫酸作酯化催化剂。     

溴醇法合成环氧苯乙烷的研究

研究了溴醇法合成环氧苯乙烷原料配比和添加催化剂对收率的影响,当ＮａＢｒ的添加量为化学反应计量时,在添加催化剂的最佳反应条件下,收率可达８０．６（含量９７．５％）,将ＮａＢｒ溶液回收套用３次,当苯乙烯加料量为１ｍｏｌ时,获得环氧苯乙烷平均收率为７２．５％（含量９２．７％）,ＮａＢｒ平均消耗量为０．４６ｍｏｌ。     

强酸型离子交换膜催化合成丙酸异戊酯

以HF－101型强酸型离子交换膜为催化剂，对丙酸与异戊醇的催化反应进行了研究，考察了反应时间,催化剂用量，酸醇摩尔比及催化剂的套用次数对酯化率的影响，探讨其最佳反应条件为：酸醇摩尔比1：1．3，反应时间90min，催化剂用量为反应物总质量的6．5％，反应温度为回流温度，酯化率98％，催化剂套用8次后酯化率仍在80％以上。     

聚氯乙烯三氯化铁树脂催化合成肉桂酸甲酯

在聚氯乙烯三氯化铁催化下由肉桂酸和甲醇发生酯化合成了肉桂酸甲脂,当０．０２ｍｏｌ．肉桂酸,０．１０ｍｏｌ甲醇和１．５ｇ催化剂一起回流加热７．０ｈ时,产品收率达８４．４％。     

复合树脂超强酸对酯化反应的催化动力学研究

大孔磺酸树脂与氟硼酸制得的新型复合树脂超强酸ＤＳＦＢ催化乙酸和异丙醇（摩尔比为１：３）的酯化反应结果表明，此反应属二级反应．表观活化能为５６．１９ＫＪ／ｍｏｌｅ．在８０℃下ＤＳＦＢ树脂催化乙酸与正了醇（摩尔比为１：１３）时是假一级反应．复合树脂ＤＳＦＢ对这一反应的相对催化活性比大孔强酸树脂及其与四氯化钛的复合物高得多．     

微波辐射固体酸催化合成马来酸双酯

首次在微波辐射下，用活性炭固载对甲苯磺酸催化合成了马来酸双酯．当微波辐射功率为150W．正辛醇：酸酐＝3：1，催化剂用量为2．5g时，反应20min后，马来酸酐转化率达89．8％，产物的选择性为99．5％．同时，也发现随着醇的炭数增多，反应温度和反应速率增加；在微波辐射条件下，酯化反应速率、产物选择性都高于常规加热方式下的反应结果．     

超细Mo-Co-K催化剂合成低碳醇性能的研究

采用类凝胶法和超临界干燥技术制得超细Ｍｏ－Ｃｏ－Ｋ催化剂。研究了还原态催化剂上ＣＯ加氢合成低碳醇的反应性能,考察了不同钼钴比、钾盐助剂呈和反应条件对合成低碳醇性能的影响,在３００℃、６．０ＭＰａ,１００００ｈ＾－１的反应条件下,超细Ｍｏ－Ｃｏ－Ｋ（Ｍｏ／Ｃｏ＝７：１,Ｋ含量为１％）催化剂上低碳醇的时空产率达到６２４．４ｇ／ｋｇ－ｃａｔ．ｈ,醇选择性与４８．５％,ＯＨ／Ｃ１ＯＨ＝１．０８。     

苄醇的选择性间接电氧化

以Ｃｅ￣（４＋）／Ｃｅ￣（３＋）为氧化还原体系，以硫酸为支持电解质，采用槽内法研究了苄醇的选择性间接电氧化。得出最佳电解条件：电流密度，０．１Ａ／２０ｃｍ￣２；亚铈与反应物当量比，１：６；硫酸浓度，３ｍｏｌ／Ｌ；通过电量，２Ｆ／ｍｏｌ（Ｆ为理论电量）。在最佳电解条件下，反应产物为苯甲醛，产率高达９６％，不发生深度氧化。阳极液循环１０次以上，对反应产率无影响。反应中Ｃｅ￣（４＋）只起电子传递作用，反应仅消耗电能，因此此法十分经济，且无污染。     

有机溶剂中脂肪酶催化酯交换反应的研究

对几种有机溶剂中猪胰脂肪酸催化的酯交换反应进行了研究，详细考察了反应温度、反应时间、反应物摩尔比、反应物中水含量和不同溶剂对反应性能的影响。结果表明：1．反应温度在313K左右时酶显示出最高催化活性。2．在实验条件下，反应进行72h后，转化率不再随反应时间的延长而变化，即反应达到平衡。3．酯／醇摩尔比的增大对反应转化率的影响较小。4．反应系统中水含量为0．5％－1．3％时，酶的催化活性最高。5．酶的催化活性随溶剂极性增大而降低。     

脂肪酶直接与硅胶混合催化无溶剂酯化反应的研究

用硅胶作为载体，以癸酸与己醇的酯化反应作为模型，将脂肪酶和底物直接与硅胶混合，用于无溶剂体系催化酯化反应．结果表明体系中水的含量、底物用量比以及反应时间均对酯化反应有较大影响．在该体系中，脂肪酶催化酯合成反应的速度显著增加，反应2h后．转化率可以达到90％以上．而且沉积在硅胶上的脂肪酶可以反复使用多次．     

有机相中α-氰基-3-苯氧基苄醇乙酯的酶促醇解反应

研究了有机相中脂肪酶催化α-氰基-3-苯氧基苄醇乙酯的醇解化反应。制备α -氰基-3-苯氧基苄醇。考察了酶、溶剂、醇、醇用量、溶剂水含量以及底物浓度等 因素对反应的影响，结果表明Novozym435脂肪酶催化活性最高，经实验确定的最佳 条件为：脱水甲苯为溶剂，正辛醇为酰基受体，正辛醇、酯的摩尔比为1.5:1，酶 量为8 mg/mL时的最佳底物浓度为108.13 mmol/L，在上述条件下反应30 h酯的转化 率 > 96%。     

Synthesis of Long Chain Fatty Acids Acylated Coumarin Glycoside Esters with Lipase as Catalyst

A series of novel coumarin glycoside esters(1―9) was synthesized through the acylation reaction of 4-methylcoumarin-7-O-β-D-glucoside(11) with different long chain fatty acids catalyzed by lipase in organic medium. The acylation occurred regioselectively at the 6'-OH of glycosyl moiety. The enzymatic synthesis was optimized to achieve 54%―70% yield using immobilized lipase(Novozym 435, 10 mg/mL) as catalyst and acetone and pyridine(9:1, volume ratio, water content<1%) as solvent with an acyl donor/coumarin glycoside molar ratio of 10:1 at a temperature of 40―50 ℃ for 96 h. All the synthesized compounds were confirmed.     

Enzymatic Synthesizing of Phytosterol Oleic Esters

A method of synthesizing the phytosterol esters from oleic acid and sterols was studied, using immobilized lipase Candida sp. 99-125 as catalyst. Molar ratio (oleic acid/phytosterols), temperature, reaction period, organic solvents, catalyst, and silica-gel drier were optimized, and the result showed that 93.4% of the sterols had been esterified under the optimal synthetic condition: the molar ratio of oleic acid/phytosterol is 1:1 in 10 mL iso-octane, immobilized lipase (w, 140% of the sterols), incubated in an orbital shaker (200 rpm) at a temperature of 45 °C for 24 h. The immobilized lipase could be reused for at least 13 times with limited loss of esterification activity. The conversion still maintained up to 86.6%. Hence, this developed process for synthesizing phytosterol esters could be considered as simple and low-energy consumption compared to existing chemical processes.     

基于氯化镁饱和溶液中固定化脂肪酶Lipozyme TL IM催化光皮树油脂合成生物柴油

基于氯化镁饱和溶液反应体系中,对采用固定化脂肪酶Lipozyme TL IM催化光皮树油脂转化为生物柴油的工艺进行了研究。考察了固定化脂肪酶Lipozyme TL IM催化光皮树油转酯化的工艺中甲醇的用量、固定化脂肪酶的添加量、摇床的转速和反应时间对生物柴油产率的影响。实验结果表明,采用氯化镁饱和溶液反应体系,在醇油摩尔比为3∶1,固定化酶Lipozyme TL IM用量为光皮树油质量的20%,摇床转速为150 r/min,反应8 h时,生物柴油产率最高,达到86.5%。与传统的三步甲醇醇解或者有机溶剂反应体系比较,采用的氯化镁饱和溶液体系的酶稳定性更好,反应效率更高,有效地解决了酶在甲醇中失活的问题,生产成本低,可成为生产生物柴油的新工艺。     

Esterification Synthesis of Ethyl Oleate in Solvent-Free System Catalyzed by Lipase Membrane from Fermentation Broth

In this study, the immobilized lipase was prepared by fabric membrane adsorption in fermentation broth. The lipase immobilization method in fermentation broth was optimized on broth activity units and pH adjustments. The viscose fermentation broth can be used with a certain percentage of dilution based on the original broth activity units. The fermentation broth can be processed directly without pH adjustment. In addition, the oleic acid ethyl ester production in solvent-free system catalyzed by the immobilized lipase was optimized. The molar ratio of ethanol to oil acid, the enzyme amount, the molecular amount, and the temperature were 1:1, 12% (w/w), 9% (w/w)(based the total amount of reaction mixture), and 30 °C, respectively. Finally, the optimal condition afforded at least 19 reuse numbers with esterification rate above 80% under stepwise addition of ethanol. Due to simple lipase immobilization preparation, acceptable esterification result during long-time batch reactions and lower cost; the whole process was suitable for industrial ethyl oleate production.     

乳化体系中脂肪酶催化合成环十五内酯

对筛选的假丝酵母菌株Candida.sp.GXU08所产脂肪酶催化15-羟基十五烷酸甲酯合成环十五内酯进行了研究,使用超声震荡将脂肪酶酶液分散到环己烷中,以此形成水/有机溶剂乳化体系,考察了不同因素对环十五内酯产量的影响。实验结果表明,在水/环己烷乳化体系中,脂肪酶催化15-羟基十五烷酸甲酯合成环十五内酯的最适条件为:在40℃、180r/min的条件下,1g脂肪酶(pH=7.0)催化8mmol/L的15-羟基十五烷酸甲酯反应72h,单位酶活生成环十五内酯的最大质量为47.77×10-3mg,是在纯有机溶剂环己烷中单位酶活生成环十五内酯最大质量14.54×10-3mg的3.285倍。反应后的脂肪酶重复使用1次能大大提高环十五内酯的生成量。直接使用一定浓度的酶液代替酶粉催化合成环十五内酯具有转化率高、省时、节能等优点。     

Enhancing enzymatic properties by the immobilization method

Effects of some immobilized carriers on enzymatic properties have been studied. The following results were obtained: (1) When cholinesterase was immobilized on the hydrophobic carrier with either α-naphthylamine, benzylamine, orp-methylbenzylamine groups, the affinities of immobilized cholinesterase for toxic organophosphors, GB (Isopnopy 1-methylphophonofluoridate) and Vx [o-ethyl-S-(2-diisopnoylomino-thyl) methyl phosphonothiolate], were enhanced 60–90 times and 700–1200 times, respectively, whereas the thermal stability of the immobilized cholinesterase increased to 110%. Approximately 82–88% activity of the immobilized cholinesterase remained after continuously operating for 8 h; and (2) Lipase was immobilized on the carrier that was made up of 6% polyethylenimine, 1% alginate gel, and 1% glutaraldehyde. The initial reaction rate of the esterification of lauric acid with lauric alcohol catalyzed by this kind of immobilized lipase was increased 21 times, as compared to lipase powder. About 72% esterification activity of lipase remained after continuous operating for 10 d.     

Lipase-Catalyzed Condensation Reaction of 4-Nitrobenzaldehyde with Acetyl Acetone in Aqueous–Organic Cosolvent Mixtures and in Nearly Anhydrous Media

The nature of the product(s) in lipase-catalyzed reaction of acetyl acetone with 4-nitrobenzaldehyde was found to depend upon the source of lipase and the reaction medium. Mucor javanicus lipase was found to give 70% aldol with 80% enantiomeric excess in anhydrous t-amyl alcohol. A 2:2 adduct was formed by the dimerization of the aldol along with an unsaturated cyclic ether as the side products in varying proportions depending upon the reaction medium and the lipase used.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]