L-脯氨酸催化的香豆素-3-羧酸的“一锅法”合成

用二甲亚砜为溶剂,L-脯氨酸为催化剂,能简便高效地催化水杨醛与丙二酸二乙酯发生Knoevenagel缩合反应得到香豆素-3-羧酸乙酯,之后加入氢氧化钾进行水解,浓盐酸酸化得到香豆素-3-羧酸。本方法具有易于操作,反应收率较高,后处理方便,反应时间短,催化剂和溶剂廉价易得,绿色环保等优点。     

(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯的不对称合成

研究了异丁醛与乙醛酸乙酯不对称羟醛缩合反应合成(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯,考察了催化剂种类及用量、反应时间、反应溶剂对羟醛缩合反应的影响。确定较佳反应条件为:L-组氨酸作催化剂,用量为乙醛酸乙酯物质的量的30%,乙二醇为溶剂,反应时间24h。(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯的收率达75%,ee值为73%。产物结构经1H NMR,GC-MS进行了表征。     

氮杂环卡宾催化的氰基甲酸乙酯与醛亚胺的Strecker反应研究

以四氢呋喃为溶剂,氮杂环卡宾为催化剂,进行了氰基甲酸乙酯和亚胺的Strecker反应研究.实验中考察了催化剂的种类、用量及溶剂对反应的影响,确定了最优反应条件.结果显示氰基甲酸乙酯与芳香亚胺、脂肪亚胺都能发生Strecker反应,最终合成了14个α-氨基腈衍生物,产物产率最高达到93%.该反应具有操作简单,条件温和,产率高及环境友好等优点.     

锡粉促进下α-亚甲基-γ-氨基酸酯的合成

探索了锡粉促进下,以1,4-二氧六环为溶剂,在室温条件下,通过醛、芳胺和2-溴甲基丙烯酸乙酯的烯丙基化反应,合成α-亚甲基-γ-氨基酸酯的方法.该方法不需使用任何催化剂,具有高效、环境友好、价格低廉和操作简便等特点.     

奎宁修饰型Pt/Al2O3催化丙酮酸乙酯不对称加氢反应：乙酸溶剂与甲苯溶剂的比较

采用奎宁修饰型Pt/Al_2O_3作为加氢催化剂在常温常压下比较了乙酸和甲苯溶剂中丙酮酸乙酯的不对称加氢与一般的加氢反应的反应结果;研究了反应对映选择性与底物转化率的关系、丙酮酸乙酯用量对产物对映选择性的影响、三乙胺的作用以及乙酸-甲苯混合溶剂的使用. 实验结果表明, 乙酸作为反应溶剂的性能优于甲苯且溶剂化作用强于甲苯;两种溶剂中的不对称加氢反应均存在初始过渡期, 以乙酸为溶剂时, 催化反应速度较快;在乙酸溶剂中底物用量对产物对映纯度影响不大, 在甲苯溶剂中底物用量具有最佳值;在乙酸溶剂中加入三乙胺能显著提高反应的对映异构体选择性而在甲苯溶剂中则没有促进作用.     

丙酮酸乙酯多相不对称催化加氢反应的初始过渡期研究

采用奎宁修饰的Pt/Al2O3为催化剂,研究了在常压下,乙酸溶剂中丙酮酸乙酯的不对称加氢反应.考察了奎宁修饰剂浓度、反应温度、预修饰时间、底物起始浓度及氧的加入对内酮酸乙酯不对称氢化反应初始过渡期(ITP)特征的影响.结果表明,在不对称氢化反应的初期,存在对映选择性随底物转化率的增加而不断升高的现象(即ITP现象),反应条件的变化能不同程度地改变ITP特征,在奎宁修饰催化剂时加入O2能明显提高催化剂对产物的对映选择性,改善ITP现象.ITP特征取决于反应起始阶段反应体系中各组分在催化剂表面的相互作用及达到平衡的速度,其实质是手性修饰型催化剂表面的重排过程.     

5(R)-(l-氧基)-2(5H)-呋喃酮与溴代丙二酸二乙酯的反应

研究了5(R)-(l-?氧基)-2(5H)-呋喃酮与溴代丙二酸二乙酯在无水K2CO3和相转移催化剂四丁基溴化铵(TBAB)存在下,以乙腈为溶剂,在80℃下的反应及产物结构特征.在上述条件下得到了预期的具有两个乙酯基的手性环丙烷/丁内酯衍生物3,同时还得到了含有一个乙酯基的手性环丙烷/丁内酯化合物5以及少量的含溴产物6.通过对产物结构分析,提出了产物形成的可能机理.     

稀土固体超强酸SO2-4/TiO2/La3+催化合成苯乙酸乙酯

苯乙酸乙酯,常作为修饰剂和主香剂,应用于烟草、食品、日用化妆品等行业,还可以用于生产巴比妥类催眠药鲁米那,也可作溶剂.工业生产中采用硫酸催化合成苯乙酸乙酯,但硫酸有脱水和氧化作用,生成众多副产物,产物后处理工艺复杂,污水排放量大,严重腐蚀设备.本文合成了稀土固体超强酸SO2-4/TiO2/La3+催化剂,考察了影响催化活性的一些因数及催化合成苯乙酸乙酯的条件.此催化剂不仅克服了浓硫酸催化的一些缺点,而且酯化率高,反应时间缩短一半,反应温度降低15℃,容易回收、可以多次重复使用,适宜工业生产.     

对烷氧基取代 MeO-BIPHEP 型手性双膦钌配合物催化 β-酮酸酯不对称加氢反应

 报道了对烷氧基取代的 MeO-BIPHEP 型手性双膦配体钌配合物催化的β-酮酸酯不对称加氢反应, 考察了反应温度、压力、底物/催化剂摩尔比和溶剂对反应的影响. 结果表明, 在乙醇中该配合物催化 3-丁酮酸乙酯加氢反应的对映选择性达 98.0%,且对含不同取代基的β-酮酸酯均表现出较高的活性和对映选择性.     

5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯的合成

5-溴苯并呋喃-2-甲酸乙酯与4-叔丁氧基羰基哌嗪进行Buchwald-Hartwig偶联反应,若催化剂是Pd(OAc)2/BINAP,碱是Cs2CO3,则产物主要是5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯,转化率达70%;若催化剂是Pd(dba)2/P(t-Bu)3,碱是叔丁醇钾,则产物中几乎没有5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯.文中讨论了影响这个Buchwald-Hartwig偶联反应的因素.     

Solvent Effect on the Spectral Characteristics and Quantum Yields of the Photolysis of Alkylated 1,2-Dihydroquinolines

On the basis of spectral data and the reaction of photolysis and fluorescence quantum yields in different pure solvents and solvent mixtures, it has been concluded that hydrogen bonding between 1,2-dihydroquinolines (DHQs) and a solvent, where the solvent is a proton donor, plays the key role in the reaction of photoinduced solvent addition to the DHQ double bond. The high sensitivity of DHQ photolysis to the solvent composition was shown, allowing us to suggest this reaction as a probe for studying the microenvironment of related compounds in mixtures.     

Sulpholane--A new solvent for the Baylis-Hillman reaction

Sulpholane, a commercially available solvent, is used for the first time as a new solvent for the Baylis-Hillman reaction under ambient conditions; a wide variety of olefins as well as aldehydes participate very efficiently resulting in good to excellent yields of products. Acrylamide also underwent the Baylis-Hillman reaction with 4-nitrobenzaldehyde under these reaction conditions.     

The Combined Role of Catalysis and Solvent Effects on the Biginelli Reaction: Improving Efficiency and Sustainability

The traditional Biginelli reaction is a three‐component condensation between urea, benzaldehyde and an acetoacetate ester to give a dihydropyrimidinone. An investigation into catalytic and solvent effects has returned the conclusion that the diketo–enol tautomerisation equilibrium of the dicarbonyl reactant dictates the yield of the reaction. Whereas the solvent is responsible for the tautomerisation equilibrium position, the catalyst only serves to eliminate kinetic control from the reaction. Generally, to preserve reaction efficiency and improve sustainability, bio‐derivable p‐cymene was found to be a useful solvent. The metal–enolate intermediate that results from the application of a Lewis acidic catalyst often cited as promoting the reaction appears to hinder the reaction. In this instance, a Brønsted acidic solvent can be used to return greater reactivity to the dicarbonyl reagent.     

Effect of solvent on catalytic performance of anhydrous catalyst in acetylene dimerization to monovinylacetylene

The production of monovinylacetylene (MVA) through Cu(I)-catalyzed acetylene dimerization reaction was performed in different reaction media. Based on the analyses of crystals precipitated from the catalyst solution and UV-Vis spectra of the catalysts, the reaction mechanism and solvent dependence were studied. The highest yield of MVA can be obtained when dimethylformamide is used as solvent because of its strong coordination ability to Cu(I). The activation of C≡C bond is presumed to be improved when the catalytic metal ion is coordinated by a solvent with less steric hindrance and electron-rich coordination atom. The results of the present study provide a possible way to accelerate the metal-catalyzed homogeneous reaction of alkyne substrates through careful selection of a solvent.     

Sodium toluene-4-sulfonate as a reusable and ecofriendly catalyst for greener synthesis of 5-aminopyrazole-4-carbonitrile in aqueous medium

In these environmentally conscious days there is need to use eco-friendly greener technologies, such as solvent free, microwave, ultrasound and use of room temperature. Here report an efficient and green protocol for the synthesis of 5-aminopyrazole-4-carbonitrile from three component condensation of phenyl hydrazine, aldehyde, and malononitrile using NaPTS as catalyst in aqueous medium. Use of water has emerged as a versatile solvent for organic reaction; it is readily available, inexpensive, environmentally benign, neutral and natural solvent. Multicomponent reactions in water are of outstanding value in organic synthesis and green chemistry. The significant features of this article are short reaction time, provide excellent yield, removal of toxic solvent and use of water as green solvent.     

A Novel Non-phosgene Process for the Synthesis of Methyl N-Phenyl Carbamate from Methanol and Phenylurea： Effect of Solvent and Catalyst

A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selectivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.     

含氟脯氨酸类配体在亨利反应中的应用

以脯氨酸为前体,设计并合成了一种新的含氟配体,并将其应用到铜催化的亨利反应中。 以硝基甲烷和对硝基苯甲醛的反应为模板反应,考察了配体、铜源、溶剂和碱对反应收率的影响,对反应条件进行了优化。 以含氟脯氨酸衍生物为配体,乙酸铜为铜源,甲醇作溶剂,三乙胺作为碱,不同取代基的芳香醛和硝基烷烃在室温下反应,得到53%～98%的收率。     

Dramatic solvent and hydration effects on the transition state of soybean peroxidase

Enzymes are shown to function in nonaqueous media; however, relatively little information is available on the influence of the organic solvent as well as its associated water content on the properties of the enzymatic transition states. A better understanding of these effects will be useful in developing kinetic models that can then be used to predict optimal solvent and substrate choices for enzymatic reactions in organic media. The influence of the reaction media on soybean peroxidase-catalyzed oxidation of para-substituted phenols was studied using Hammett analysis for several organic solvent systems. The catalytic activity and substrate specificity of the enzyme are influenced by the nature of the solvent and its associated hydration. These findings may allow one to draw conclusions about the reaction mechanism and the roles of solvent and solvent hydration on enzyme function.