2-吡啶甲醛的合成

2-甲基吡啶经N-氧化、重排、水解得2-吡啶甲醇．该中间体再用TEMPO—NaClO-NaBr氧化体系氧化制备2-吡啶甲醛。     

Synthesis of poly(styrene-block-methylphenylsilane-block-styrene) via TEMPO-mediated controlled free radical polymerisation

ABA block copolymers of styrene and methylphenylsilane were synthesized using a methodology based on 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated controlled free radical polymerisation. Samples of α,ω-dihalo(polymethylphenysilane) were reacted with a hydroxyl derivative of TEMPO to give suitable macroinitiators for the controlled (‘living’) free radical polymerisation of styrene. The polymerisation of styrene was carried out in bulk at 130 °C. Block copolymers were characterised using size exclusion chromatography and ¹H and ¹³C NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

TEMPO抑制K_2S_2O_8氧化甲苯生成苯甲醛过程中的过度氧化

采用TEMPO/Cu(OAc)2为催化剂,探究其在抑制苯甲醛过度氧化成苯甲酸方面的能力,考察反应时间、反应温度、催化剂用量等因素对苯甲醛收率的影响。研究结果表明,TEMPO以及TEMPO衍生物在Cu(OAc)2催化下,可以有效地抑制甲苯合成苯甲醛过程中苯甲醛进一步氧化成苯甲酸。优化条件下,甲苯氧化生成苯甲醛的收率高达78%,而且没有苯甲醇和苯甲酸生成。     

无碱条件下氧气催化氧化2-乙基己醇合成2-乙基己酸

以2-乙基己醇作为原料,O_2作为氧化剂,无碱参与下催化氧化合成2-乙基己酸。使用气相色谱(GC)进行定量分析,气质联用仪(GC-MS)进行定性分析。考察了催化剂、溶剂、反应温度、时间及氧压力对反应的影响。结果表明:2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)/硝酸铜为合适的催化剂体系,乙酸乙酯为合适的溶剂。适宜的反应条件是:催化剂TEMPO用量为2-乙基己醇物质的量的5%、硝酸铜用量为2-乙基己醇物质的量的4%,100℃、0.5 MPa O_2压力下反应6 h,2-乙基己酸收率可达77.1%。O_2恒压条件下该反应是拟一级反应,反应活化能为59.9 k J/mol。主要副产物是3-庚醇和3-庚酮。     

Copper‐Catalyzed Cyanomethylation of Substituted Tetrahydroisoquinolines with Acetonitrile

A novel method for the synthesis of cyanomethylated tetrahydroisoquinolines has been developed with mild reaction conditions, good yields and a broad substrate scope. Acetonitrile, a common solvent, is for the first time used as a pronucleophile for this type of two sp³ C−H bonds cross‐dehydrogenative coupling (CDC) reaction. A new oxidative system (CuCl₂/TEMPO/Cs₂CO₃) has been established by our group, in which the mild TEMPO reagent was found to be a highly efficient oxidant.

     

Silver‐loaded lyocell fibers modified by tempo‐mediated oxidation

The purpose of this research was to accomplish antimicrobial properties in lyocell fibers by Ag⁺ ions sorption from aqueous silver nitrate solution. Sorption properties of lyocell fibers were improved by the selective TEMPO‐mediated oxidation, i.e. oxidation with sodium hypochlorite and catalytic amount of sodium bromide and 2,2,6,6‐tetramethylpiperidine‐1‐oxy radical (TEMPO). The most suitable experimental conditions for the selective TEMPO‐mediated oxidation were determined by changing oxidation conditions: concentration of sodium hypochlorite, as well as duration of sorption. The obtained results showed that the maximum sorption capacity (0.809 mmol of Ag⁺ ions per gram of fibers) of modified lyocell fibers was obtained for the sample modified with 4.84 mmol NaClO per gram of cellulose, during 1 h. The antifungal activity of the TEMPO‐oxidized lyocell fibers with silver ions against fungi from the Candida family, Candida albicans (ATCC 24433), and antibacterial activity against two strains: Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 25922) were confirmed in vitro. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on peroxide vulcanization thermodynamics of ethylene–vinyl acetate copolymer rubber using 2,2,6,6,‐tetramethylpiperidinyloxyl nitroxide

A step forward in the understanding of rubber vulcanization with organic peroxides is provided by combining a proper arrangement between polymer, vulcanizing agent and cure conditions. For this purpose, an ethylene–vinyl acetate copolymer with a high content of vinyl acetate (70 mol%) was used since a fully saturated polymer backbone allows its vulcanization via peroxide. For the range of conditions analysed here, it is shown that the predominant process taking place is crosslinking via radical recombination, minimizing or even avoiding undesirable secondary reactions such us polymer degradation. Once conditions had been optimized, peroxide vulcanization was analysed in more depth in the presence of 2,2,6,6‐tetramethylpiperidinyloxyl, which is a mediating stable free radical commonly used in controlled radical polymerization. Consequently, it was possible to differentiate the termination reaction from the initiation and propagation steps, allowing the determination of the enthalpy of formed C–C crosslinks as measured using calorimetry. It was possible to isolate and determine the contribution of the crosslinking pathway from the global vulcanization reaction by means of calorimetric methods at optimum conditions. In fact, this simple methodology could be an important tool for understanding in detail the complex peroxide vulcanization of elastomers since reactions involved in this process determine the final network structure, and thus the final elastic properties of these compounds.     

One‐Pot Homogeneous and Heterogeneous Oxidation of Glycerol to Ketomalonic Acid Mediated by TEMPO

Glycerol, an increasingly abundant by‐product of biodiesel production, is selectively converted to ketomalonic acid in one pot at pH 10 using NaOCl as regenerating oxidant in water at 2 °C in the presence of catalytic Br⁻ along with the radical TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl). The reaction can also be conducted at completion over a sol‐gel silica glass doped with the nitroxyl radical. Considering the stability and versatility of such doped glasses, these materials show real promise as reusable metal‐free catalysts for the conversion of a readily available and renewable biofeedstock into a highly valued compound.     

纳米纤维素的氧化法制备工艺及其在气凝胶、水凝胶和膜材料领域的应用研究进展

本文综述了基于氧化工艺制备纳米纤维素的研究进展,包括利用2,2,6,6-四甲基哌啶氧化物(TEMPO)、NaIO₄、过硫酸铵、Fe²⁺和含氯体系制备纳米纤维素相关研究,并介绍了氧化纳米纤维素在气凝胶、水凝胶和膜材料等领域的应用研究进展。     

Oxidation of Amino Diols Mediated by Homogeneous and Heterogeneous TEMPO

The conversion of amino diols to aminohydroxy acids by oxidation of the primary hydroxy group mediated by homogeneous and heterogeneous TEMPO (2,2,6,6‐tetramethylpiperidine 1‐oxyl radical) is reported. The synthesis uses NaOCl as primary oxidant and TEMPO, either dissolved in the homogeneous phase or entrapped in a sol‐gel matrix, as catalytic mediator. Homogeneous TEMPO is suitable for the oxidation of aliphatic methylamino diols, while the hybrid organic‐inorganic silica sol‐gel catalysts are more selective mediators for the oxidation of benzylic amino diols like the potent antibiotic chloramphenicol which, under homogeneous conditions, are unselectively oxidized to benzoic acids.