相转移催化法合成2-氯-3-氯甲基-噻吩及噻康唑

相转移催化法合成2-氯-3-氯甲基-噻吩及噻康唑;相转移催化;氯氯甲基噻吩;氯甲基化;噻康唑     

N,N-二烯丙基甲基胺的相转移催化合成

相转移催化剂;聚乙二醇-400;N;N-二烯丙基甲基胺的相转移催化合成     

Oxidation of Benzyl Ethers via Phase Transfer Catalysis

A convenient procedure for the oxidation of benzyl ethers to benzoate esters is reported. Potassium permanganate in dichloromethane with phase transfer catalysis by triethylbenzylammonium chloride (TEBAC) affords products regiospecifically in fair to excellent yields.     

Synthesis of 5‐Cyano‐2‐Carbethoxythieno[2,3‐b]thiophenyl‐3,4‐Diisothiocyanates and Its Utility IN Heterocyclic Synthesis under Phase Transfer Catalytic Technique

Regarding to the importance of thieno[2,3‐b]thiophens and isothiocyanaetes reactiveties in the physical, chemical and pharmaceutical fields, this study has been undertaken to prepare the target compound 5‐cyano‐2‐carbethoxythieno[2,3‐b]thiophenyl‐3,4‐diisothiocyanates via a safe method. The formed isothiocyanates derivative was reacted with aromatic amines, acid hydrazied and some active methylene groups, followed by cyclization reaction for the formed intermediates to give new series of heterocyclic compounds     

反应控制相转移催化合成环氧大豆油

以磷钨杂多酸盐作为反应控制相转移催化剂,1,2-二氯乙烷为溶剂,30%H2O2为氧源,研究了中性条件下大豆油的环氧化反应,并考察了各反应条件对环氧化反应的影响。结果表明,在催化剂质量分数为3%,n(H2O2)∶n(双键)=1.2∶1,m(溶剂)/m(大豆油)=3.2,反应温度70℃,反应时间4h时,生成环氧大豆油中的碘值小于0.04g(I)/g,环氧值大于6%,催化剂循环使用5次后不降低催化活性。整个反应过程中,催化剂显示出良好的反应控制相转移催化性能。     

Synthesis of Diacyl Sulfides by Phase Transfer Catalysis

The symmetrical monothioanhydrides or diacyl sulfides have been synthesized by several methods. They are formed by acylation of free monothioacids or their anions¹, by acylation of potassium² or lithium³ sulfide, from the reaction of monothiocarboxylic acids with dicyclohexylcarbodiimide⁴ or by treatment of trimethylsilyl thiocarboxylates with acyl chlorides⁴. The recent publication about diacyl disulfides synthesis using phase transfer catalysis⁵ promted us to communicate our own results applying this technique to the preparation of the closely related diacyl sulfides. These compounds may be obtained by a more simple procedure than the published methods and in very high yields by the reaction of acylchlorides (1) with sodium sulfide nonahydrate in a solid-liquid system consisting of dichloromethane, the mentioned salt and hexadecyltributylphosphonium bromide as a phase transfer catalyst.     

相转移催化合成硫氰酸铵

以氨和二硫化碳为原料的传统合成硫氰酸铵 ( NH4 SCN)工艺分为加压法 [1,2 ]和常压法 [3,4 ] 2种 .常压法设备投资小 ,操作灵活 ,但常压因互不相溶的 CS2 、NH3两相反应体积小 ,速度慢 ,反应时间达 2 5 h以上 ,且 CS2 易挥发 ,使 NH4 SCN产率仅有 60 %左右 .表面活性剂作为相转移催化剂加快反应速度的应用已有报道 [5] .本文采用壬基酚四氧乙烯醚 ( OP- 4)和壬基酚二十一氧乙烯醚 ( OP- 2 1 )混合型催化剂用于 n( CS2 )∶ n( NH3) =1∶ 2 .5反应体系 ,在常温、常压及高速搅拌下 ,第 1步反应缩短为 4h,NH4 SCN产率提高到 70 %以…     

Synthesis of Substituted Diphenylamines Under Phase Transfer Catalysis

A convenient procedure for the synthesis of N-[(trifluoromethyl) nitrophenyl] substituted anilines by means of a chloro-substitution reaction under conditions of phase-transfer catalysis (PTC) is reported. The ipso-substitution product is obtained with high yield. This method provides a general procedure for the synthesis of diphenylamines bearing electron-withdrawing groups in both aromatic rings.     

The Reaction of 1‐Phenylpyrazolidine‐3,5‐dione with Active Nitriles Using Phase Transfer Catalysis Conditions Technique

Heterocyclization reaction of 1‐phenylpyrazolidine‐3,5‐dione with some active nitriles and acrylonitriles is described. These cyclization reactions afforded novel heterocyclic derivatives such as pyrano[2,3‐c]pyrazoles, pyrazolyl‐thiazole, pyrazolyl‐1,3‐thiazines, and pyrazolyl‐1,3‐oxathiino[6,5‐c]pyrazoles. Heating 1‐phenylpyrazolidine‐3,5‐dione alone under phase transfer catalysis conditions afforded the tricyclic dipyrazolofurandione. The structure of the new products has been characterized by IR, NMR, mass spectra, and their elemental analyses.     

N,N′‐Dialkyl‐4‐Aryl‐3,4‐Dihydropyrimidinones and Thiones: Ceric Ammonium Nitrate Catalyzed Synthesis and Molecular Structure Determination by X‐ray Crystallography

This work presents a microwave assisted solvent‐free synthesis of N,N ′‐dialkyl‐4‐aryl‐3,4‐dihydropyrimidinones/thiones in the presence of Ceric Ammonium Nitrate (CAN) via direct condensation of aromatic aldehydes, β‐keto ester, and N,N ′‐dialkylurea/thiourea. The highlights of the methodology adopted are (i) facile condensation of the reactants into product without any side‐products, and (ii) short reaction time with high yield and good purity. All the compounds synthesized were characterized and established by spectroscopic techniques such as FTIR, ¹H NMR, ¹³C NMR, and Mass. The structure of the compound is further corroborated by single crystal X‐ray diffraction analysis.     

Synthesis of 1‐(3,4‐dimethoxyphenylmethyl)‐3‐phenyl‐6,7,8‐trimethoxy‐3,4‐dihydroisoquinoline

In an attempt to ascertain the scope of using ethyl polyphosphate in the Bischler‐Napieralsky annelation reaction, a title compound was synthesized and reduced to the respective 1‐(3,4‐dimethoxyphenylmethyl)‐3‐phenyl‐6,7,8‐trimethoxy‐1,2,3,4‐tetrahydroisoquinoline.     

Synthesis of Hydroxypropyl Guar Gum by Phase Transfer Catalysis

HGG (Hydroxypropyl guar gum) was synthesized by phase transfer catalysis for the first time. The effects of alkalinity, phase transfer catalyst, etherification, pH value, temperature,reaction time and stirring speed were investigated. An optimal synthetic reaction technology was established, namely, dose of guar gum is 100 g, propylene oxide 40-50 g, HTAC (hexadecyl trimethyl ammonium chloride ) 1.3-1.7 g, pH value 10-10.5, temperature 45-50~C, and reaction time 3-4 hours. The result shows that the improved HGG has high viscosity. Its dissolution speed, content of insoluble residue, colloid light transparency and stability are apparently superior to guar flour.     

Efficient Synthesis of 5‐Carboxanilide‐Dihydropyrimidinones Using Cobalt(II) Nitrate Hexahydrate

5‐Carboxanilide‐dihydropyrimidinone derivatives were synthesized in good yield in a three‐component and efficient process by the condensation reaction of acetoacetanilide, aldehyde and urea/thiourea in the presence of cobalt(II) nitrate hexahydrate as catalyst in ethanol at ambient condition.     

逆向相转移催化在有机合成中的应用

系统地总结了逆向相转移催化在有机合成中的应用,逆向相转移催化的作用在于逆向相转移催化剂能将底物分子从有机相转移至水相中发生反应,着重介绍了几种典型的逆向相转移催化剂如吡啶及其衍生物;杯芳烃;环糊精及其衍生物,水溶性过渡金属配合物在有机合成中的应用。     

三相相转移催化法制备二氧化双环戊二烯

以氯甲基化大孔聚苯乙烯-二乙烯基苯交联树脂（PS）接枝N-苄基-N,N-二甲基十二烷基季铵磷钨杂多酸盐为三相相转移催化剂,质量分数为50%的工业双氧水为氧化剂,制备了二氧化双环戊二烯（DCPDDO）。 采用FTIR和¹H NMR对产物进行表征。 考察了溶剂和催化剂用量、物料摩尔比、反应温度和时间对环氧化反应的影响。 采用正交试验法获得的最佳反应条件为（以0.05 mol双环戊二烯（DCPD）计）：1,2-二氯乙烷18 mL,催化剂2.25 g,n(DCPD)∶n(H₂O₂)=1∶2.75,反应温度60 ℃,反应时间12 h。 在此条件下,DCPDDO的收率可达89%以上,催化剂回收方便且重复使用7次未见活性明显降低。     

逆相转移催化

主要介绍一种国内未见专题报道的逆相转移催化 (InversePhaseTransferCatalysis ,简称IPTC)技术 ,介绍该技术的定义、特点及典型应用