Denitrosation of N-Nitrososulfonamide as Chemical Probe for Determination of Binding Constants to Cyclodextrins

The influence of β-CD concentration on the acid hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) has been studied in the presence and absence of different alcohol concentrations. The rate of the denitrosation reaction in bulk water decrease as the β-CD concentration increases due to MNTS complexation in the CD cavity and the reaction taking place exclusively outside the cyclodextrin. Changes in this inhibition due to the presence of β-CD allow us to obtain the binding constants of different alcohols to the cyclodextrin. These binding constants are in very good agreement with those determined in the bibliography by other methods.     

Ferric(III) Nitrate Supported on Kieselguhr: A New Reagent for Selective Oxidation of Alcohols

A selective and effective oxidation of alcohols into the corresponding aldehydes and ketones, respectively, with a new reagent, ferric(III) nitrate supported on kieselguhr, under heterogeneous conditions is reported.     

Borohydride Exchange Resin,a New Reducing Agent for Reductive Amination

A system consisting of tosyl chloride-dimethyl formamide-pyridine was found to ensure oxidation of poly(vinyl alcohol) and some molecular alcohols.     

Ritter Reactions between Alcohols and Acetonitrile Mediated by the Conducting Polymer Poly-(3,4-ethylenedioxy Thiophene) (PEDOT)

Herein, we report new reactivity of the conducting polymer, poly-(3,4-ethylenedioxy thiophene) (PEDOT), where PEDOT mediates a Ritter reaction between alcohols and acetonitrile. The yields were variable and in most cases competitive with results obtained using sulfuric acid. Attempts at a stoichiometric reaction between benzonitrile and diphenylmethanol are also reported herein. Finally, described here are preliminary mechanistic studies that suggest PEDOT is behaving as an alcohol-selective or specific Lewis acid.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for full experimental and spectral details.     

An efficient synthesis of β-ketoesters via transesterification and its application in Biginelli reaction under solvent-free,catalyst-free conditions

A simple and efficient transesterification process for the synthesis of β-ketoester derivatives has been achieved by the reaction of methyl β-ketoester with higher alcohols at 110 °C under solvent-free, catalyst-free conditions and its application in synthesis of 3,4-dihydropyrimidin-2(1H)-ones C-5 ester derivatives via Biginelli reaction has been described.     

含环氧基团的聚合物微球固载2,2,6,6-四甲基哌啶氮氧自由基催化剂的制备及其催化分子氧氧化苯甲醇

以甲基丙烯酸缩水甘油酯(GMA)为单体, 以乙二醇二甲基丙烯酸酯(EGDMA)为交联剂, 采用悬浮聚合法制得交联聚甲基丙烯酸缩水甘油酯(CPGMA)微球, 然后以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(4-OH-TEMPO)为试剂, 使CPGMA微球表面的环氧基团发生开环反应, 从而制得了TEMPO固载化微球TEMPO/CPGMA, 考察了制备条件对固载化反应的影响, 并采用多种方法对微球TEMPO/CPGMA进行了表征. 将微球TEMPO/CPGMA与CuCl组成共催化体系, 用于分子氧氧化苯甲醇, 考察了反应条件对催化体系性能的影响. 结果表明, 以含环氧基团的聚合物微球CPGMA为载体, 通过开环反应, 可成功地实现TEMPO的固载化, 开环反应属S_N2亲核取代反应, 适宜采用溶剂N,N''-二甲基甲酰胺和反应温度85℃. 非均相催化剂TEMPO/CPGMA与助催化剂CuCl构成共催化体系, 在室温、常压O₂条件下可高效地将苯甲醇氧化为苯甲醛, 产物选择性和产率分别为100%和90%. 主催化剂TEMPO与助催化剂CuCl适宜的摩尔比为1:1.2; 主催化剂适宜用量为0.90 g. 此外, TEMPO/CPGMA固体催化剂具有良好的循环使用性能.     

A catalyst-free protocol for direct oxidative esterification of alcohols and aldehydes

A fast, simple, and efficient protocol for the direct conversion of alcohols and aldehydes to methyl ester has been developed using TsNBr₂ without any catalyst. The one pot reaction proceeds in the presence of a base at room temperature in methanol, to produce the corresponding methyl ester in high yield within a short time.     

Highly efficient deprotection of phenolic tetrahydropyranyl and methoxymethyl ethers and sequel cyclization to indanones using Sn(IV)Cl4 catalyst

Sn(IV)Cl₄ catalyst provided a rapid and efficient deprotection method for the phenolic THP and MOM ethers and sequel intramolecular Friedel–Crafts alkylation reaction of THP and MOM protected chalcone epoxides under mild conditions. The reaction took 2–3 min to give the products in excellent yield (90–98%) at 0 °C without affecting the other functional groups.     

Magtrieve™: a convenient catalyst for the oxidation of alcohols

We find that Magtrieve™ (CrO₂) catalyzes the oxidation of a wide variety of alcohols with periodic acid as the terminal oxidant. Mild conditions, short reaction times, and facile aqueous work-up make this a most attractive method. Olefins are not oxidized under these conditions; thus alcohols react selectively in the presence of alkenes. Conditions have been optimized with respect to catalyst loading, solvent, and co-oxidant; and the scope of the reaction includes primary and secondary benzylic, allylic, and aliphatic alcohols.     

Gas chromatographic determination of some phenolic compounds in fuels and engine oil after simultaneous derivatization and microextraction

In this study, a simultaneous derivatization/air‐assisted liquid–liquid microextraction method has been developed for sample preparation of some phenolic compounds in fuels and engine oil. Analytes are transferred by back liquid–liquid extraction into NaOH solution and then are derivatized with butyl chloroformate and extracted simultaneously into carbon tetrachloride. The extracted derivatized analytes are analyzed using gas chromatography with flame ionization detection. The effect of extracting solvent type, derivatization agent and extraction solvent volumes, ionic strength of the aqueous solution, number of extraction cycles, etc., on the extraction efficiency is investigated. The calibration graphs are linear in the range of 3–10 000 μg/L. Enhancement factors, enrichment factors, and extraction recoveries are in the ranges of 497 to 1471, 571 to 991, and 60 to 109%, respectively. Detection limits are obtained in the range of 0.8 to 2.0 μg/L. Relative standard deviations for the extraction of each selected phenols are in the ranges of 2–4% for intraday (n = 6) and 3–6% (n = 5) for interday precisions for 200 μg/L. This technique is successfully applied for the extraction, preconcentration, and determination of the selected phenols in gasoline, kerosene, gas oil, and engine oil.