溴代环丙烷与酰胺在Ullmann反应条件下的反应研究

在某些情况下,三元环的性质与烯基的C＝C双键相似,而烯基溴代物已被广泛应用于Ullmann反应,因此,本文考察了1-溴-2-苯基环丙烷与酰胺在Ullmann条件下的反应情况.结果显示,在此反应条件下,环丙烷结构发生了开环,开环后的产物会发生双分子偶联;当在体系中加入亲核体时,开环的物质同时会与亲核体发生偶联反应,反应效...     

由邻苯二甲酸二乙酯制备水合茚三酮的反应机理探讨

以邻苯二甲酸二乙酯为原料,经Claisen酯缩合反应、酸性酯水解反应、热脱羧反应、亚硝化反应、脱肟反应、羰基还原反应、Aldol反应、邻二醇氧化裂解反应制备了水合茚三酮,对各步的反应机理进行了详细的讨论。     

茚三酮与赖氨酸荧光反应的研究

茚三酮与赖氨酸的显色反应已广泛用于各种样品的测定,但高灵敏的氨基酸荧光测定法的研究还很不够。尽管茚三酮与某些氨基酸的荧光反应已有报道,但反应条件苛刻,反应时间长达60～120min,对赖氨酸的专一测定法尚未见报道^[1~3]。     

Reaction of Iodolevoglucosenone with Ethyl Cyanoacetate under Michael Reaction Conditions

The reaction of iodolevoglucosenone with the anion of ethyl cyanoacetate via succession of tandem intramolecular reactions leads to formation of tricyclic cyclopropanolevoglucosenone or tetracyclic imine.     

Deoximation Reaction in Room Temperature Ionic Liquids under Mild Conditions

Deoximation in metal chloride ionic liquids based on 1‐alkyl‐3‐methylimidazolium and triethylene ammonium cations, such as AmimBr(Cl)‐MCl_x(A=ethyl, butyl, benzyl; M=Al, Fe, Cu, Sn and Zn; x=2, 3) and Et₃NHCl‐FeCl₃ were investigated under mild conditions. Ferrate chloride ionic liquid was proved to be an effective catalyst for deoximation of cyclohexanone oxime, exhibiting high conversion of oximes and selectivity to cyclohexanone. Good performance for the deoximation of other oximes such as salicylald oxime, acetone oxime, benzophenone oxime, 4‐nitrobenzald oxime, acetophenone oxime, 2‐chlorobenzaldehyde oxime, Acetald oxime, 2‐butanone oxime and (1R)‐camphor oxime was also achieved with bmimBr‐FeCl₃ as catalyst and solvent. The deoximation was determined to carry out via acid‐catalytic hydrolysis and the reaction mechanism was proposed.     

Intramolecular Cyclization of 4-Isocyanato-3-(2-naphthyl)-1-phenylpyrazole Under Friedel-Crafts Reaction Conditions

4-Isocyanato-3-(2-naphthyl)-1-phenylpyrazole cyclized under the influence of AlCl₃ to give 2H-benzo[h]pyrazolo[4,3-c]isoquinoline.     

无溶剂条件下硒酚对末端环氧化合物的开环反应及其在1,3-噁唑烷-2-酮衍生物合成中的应用

Regioselective ring-opening reactions of 1,2-epoxides with ArSeH catalyzed by Ti（O^tPr）4 under solvent-free conditions were investigated. A variety of β-hydroxyselenides were obtained in excellent yields of 90%-97% and regioselectivities by a simple, atom economic and environment-friendly procedure. Several N-tosyl- 1,3-oxazolidin-2-ones were prepared starting from the corresponding 1,2-epoxides and ArSeH by a one-pot three-step procedure.     

以氯代酰氯为试剂的聚砜膜材料的付-克酰基化反应

采用氯乙酰氯和氯丁酰氯两种ω-氯代酰氯化试剂,在Lewis酸催化剂存在下,于室温下分别对聚砜（PSF）材料实施了Friedel-Crafts酰基化反应,制备了氯代酰基化（CA）聚砜材料CAPSF。用FT-IR、1H-NMR与佛尔哈德分析法表征了该产物的化学结构与组成。结果表明：在室温（25°C）下,以CH2Cl2为溶剂...     

Fe-catalyzed regioselective Friedel–Crafts hydroxyalkylation of N-substituted glyoxylamide with indoles

An efficient regioselective Friedel–Crafts hydroxyalkylation of N-substituted glyoxylamide with various indoles catalyzed by Lewis acids was developed. The reactions proceeded smoothly at room temperature and the 2-hydroxy-2-(1H-indol-3-yl)-N-substituted acetamide resulted from the reactions catalyzed by FeSO_4 were synthesized in excellent yields(up to 93%). While the bisindole compounds were obtained when FeCl_3 was used as a catalyst in excellent yields(up to 92%). A possible mechanism was proposed.     

Study on Reaction of α‐Benzoylhemithioacetal with Alkylamines

α‐Benzoylhemithioacetal (1) reacted with alkylamines under mild conditions to give 2‐alkylamino‐2‐thiomethyl acetophenones (3) in good yields.     

Temperature‐controlled ionic liquid dispersive liquid‐phase microextraction combined with HPLC with ultraviolet detector for the determination of fungicides

Present study described a simple, environmental benign, easy to operate, and determination method for fungicides including thiram, metalaxyl, diethofencarb, myclobutanil, and tebuconazole. The method is based on temperature‐controlled ionic liquid dispersive liquid phase microextraction coupled to HPLC with ultraviolet detector. In the enrichment procedure, ionic liquid 1‐octyl‐3‐methylimidazolium hexafluorophosphate [C₈MIM][PF₆] was used as the extraction solvent. Variable affecting parameters such as the volume of [C₈MIM][PF₆], temperature, extraction time, centrifuging time, and salting‐out effect have been optimized in detail. Under the optimal conditions, this method has been found to have good linear relationship in the concentration range of 1.0–100 μg/L and excellent detection sensitivity with LODs (S/N = 3) in the range of 0.32–0.79 μg/L. Precisions of proposed method were in the range of 3.7–5.9% for intraday and 7.8–11.0% for interday (RSDs, n = 6). The proposed method was used for the analysis of real water samples and good spiked recoveries at two different spiked levels were achieved in the range of 84.6–102%.     

无溶剂无催化剂微波促进下 1-苯基-3-甲基-5-吡唑啉酮与芳醛的反应研究

无溶剂无催化剂条件下,微波促进1-苯基-3-甲基-5-吡唑啉酮与芳醛的缩合反应选择不同辐射功率将分别得到4-芳亚甲基-3-甲基-1-苯基-5-吡唑啉酮和4,4′-芳亚甲基-双(1-苯基-3-甲基-5-吡唑啉酮),产率良好.产物结构经1H NMR,13CNMR和IR进行了表征.     

Reaction of Isonitriles with Dibenzoylacetylene Leading to Furan and Difuropyran Derivatives

A mixture of an isocyanide and dibenzoylacetylene in dry CH₂Cl₂ undergoes a smooth addition reaction at ambient temperature to furnish 3‐[5‐(alkylimino)‐3,4‐dibenzoyl‐2‐phenylfuran‐2(2H)‐yl]‐ 1‐phenylprop‐2‐yn‐1‐ones (1 : 2 adduct) and {2,5‐bis(alkylimino)‐4,7,8a‐triphenyl‐5H‐difuro[2,3‐b:3′,4′‐e]pyran‐3(8aH)‐yl}(phenyl)methanones (2 : 2 adduct). Single‐crystal X‐ray analyses conclusively confirmed the structures of the adducts.     

Glaser Coupling Reaction without Organic Solvents and Bases under Near-critical Water Conditions

A Glaser coupling reaction of terminal alkynes in the presence of cupric chloride without organic solvents and bases under near-critical water has been developed.     

Hydrophosphonylation of Aldimines under Catalysts‐Free Conditions

Trimethylsilyl phosphite reacted with aldimines efficiently under catalysts‐free conditions, giving α‐aminophosphonates in good to excellent yields. Furthermore, the reaction can be scaled‐up easily and the high yield can be maintained.     

Transformations of Mono- and Bisphenylhydrazones of Aliphatic-Aromatic 1,5-Diketones under the Conditions of the Fischer Reaction

The mono- and bisphenylhydrazones of 3-R-1,5-diphenylpentane-1,5-diones were obtained, and their transformations in the Fischer indole synthesis under various conditions were studied. It was shown that 4-R-2,6-diphenylpyridines, 2-phenylindole, and 5-R-1,3-diphenyl-²-pyrazolines are formed as the main products in addition to the 3-R-1-phenyl-3-(2-phenyl-3-indolyl)propan-1-ones or their phenylhydrazones produced as a result of indolization. The ways of formation of these compounds are discussed. Some transformations of the obtained ketones were studied.     

The Reaction Studies of α‐Chloroformylarylhydrazines with Thiols,Thioureas and α‐Cyclodiketones

The reactions of α‐chloroformylarylhydrazines 1 with various types of mercaptan, thiourea and α‐cyclodiketone have been studied intensively. 1‐Arylhydrazinecarbothioates 2 were obtained via thioesterization when α‐chloroformylarylhydrazines reacted with thiols. On the other hand, compounds 3 were obtained when α‐chloroformylarylhydrazines reacted with thio‐containing heterocyclic compounds, which suggested a totally different mechanism in these types of reactions. Further studies on the reaction of α‐chloroformylarylhydrazines 1 with thiourea compounds confirmed a novel cyclization and de‐cyclization mechanism, which led to give 2‐arylhydrazinecarboximidamides 5 and 1,3,4‐thiadiazolin‐5‐ones 6 . In addition, various 1,3,4‐oxadiazines 9 were obtained by reacting α‐chloroformylarylhydrazines with α‐cyclodiketones, showing ring cyclization was involved in this type of reaction.     

Copper‐Catalyzed Cross‐CouplingLigand‐Free Conditions Reaction of Thiols with Aryl Iodides under

Commercially available CuO powder is found to be a suitable catalyst for C‐S coupling reaction between aryl‐ and alkyl thiols and aryl iodides. Functional groups including halides, ketone, unprotected amine and heterocycles were tolerated by the reaction conditions employed.