取代苯甲醛肟和取代苯乙酮肟电化学氧化机理的研究

研究了１０种取代苯甲醛肟和５种取代苯乙酮肟的电化学氧化机理。这二类肟的氧化电位随取代基吸电子能力的增大而增高，并与它们相应的Ｈａｍｍｅｔｔ常数有线性关系。它们在电化学氧化过程中均有ｉｍｉｎｏｘｙ自由基生成，但最后产物各不相同。用控制电位电解和紫外吸收光谱检法验证了部分电化学氧化产物。因此，电化学氧化法可作为由肟类产生ｉｍｉｎｏｘｙ自由基的一种方法。     

脱肟方法的综述

本文就羰基的保护形式之一-肟的脱肟方法作了综述。全面介绍了脱肟基再生为羰基的各种方法之特点, 并将它们分为五大类: 酸性水解脱肟; 还原脱肟;氧化脱肟; 电化学脱肟; 生物化学脱肟。同时出描述了一些反应的机理。     

头孢噻甲羧肟的伏安行为及其单扫描极谱法测定

以多种电化学手段研究了头孢噻甲羧肟的伏安行为。在磷酸盐缓冲溶液中，ＣＴＤ产生２个不可逆吸附还原波，峰电位分别为－０．６５Ｖ和－１．２０Ｖ。分别有１个电子与２个电子和１个质子参与了峰１与峰２的电极过程。探讨了电极反应机理。     

聚联吡啶-聚甲基丙烯酸复合物薄膜修饰电极

联吡啶衍生物是一类具有氧化还原能力的有机物,它们在生物系统、太阳电池以及光解水制氢等方面用作电子转移媒体.含取代基的联吡啶及其聚合物的一电子还原体(阳离子自由基)呈鲜艳的色彩,人们正研究其作为电致显色材料的可能性,为了抑制联吡啶发色基团的电化学老化,本文合成了聚二溴间二甲苯基联吡啶一聚甲基丙烯酸分子复合物(m-PXV-PMAA),并研究了这种聚离子复合物修饰电极的电化学性能.     

二茂铁基超支化聚氨酯的电化学性能

通过循环伏安法(CV)测定了二茂铁基超支化聚氨酯(HAPE-Fc)的电化学性能.结果表明:HPAE-Fc表现为单对氧化还原峰,在二茂铁接枝到超支化聚氨酯上以后,二茂铁基团依然保持着自身的氧化还原独立性,具有较强的电子转移速率,这是其具有电化学特性和催化作用的前提条件.通过分析扫描速率与HPAE-Fc电化学行为之间的关系,发现HPAE-Fc的电极过程既受扩散控制,同时也受电极反应的控制.     

维生素K3电化学反应机理的红外光谱电化学研究

用循环信安法及现场红外光谱电化学法研究了维生素Ｋ３在铂电极上,弱碱性水溶液介质中的电化学反应机理。循环伏安法实验结果显示ＶＫ３的电反应为两步电子准可逆电极过程,现场光谱电化学实验结果则从基团特征吸收频率的变化表明了ＶＫ３的电化学还原和氧化经历了从萘醌到萘酚的互变过程。据此进一步证实了ＶＫ３由萘醌到酚的电化学反应机理。     

间氯苯胺的乳液聚合及聚合物链结构表征

聚苯胺以其良好的电化学稳定性和掺杂可逆性 ,成为一类优良的电活性聚合物 [1,2 ] ,但其溶解性差 ,限制了它的加工及应用 .用取代基对聚苯胺的结构进行修饰 ,可有效地提高其加工性能 [3,4 ] ,但有关含吸电子取代基的苯胺衍生物聚合的报道尚少 .Ranger等 [5]指出 ,含强吸电子取代基团的聚苯胺不易用化学氧化聚合方法制备 ,并提出被氧化单体中的 N7和 C4位置必须具有相近的电子自旋密度 ,才能进行“头 -尾”偶联 ,而含强吸电子取代基团的苯胺单体中这两个位置的反应能力是不等价的 ,但可采用与母体共聚的方法可制备含强吸电子取代基 (如— C…     

2—氨基—9,10—蒽醌及其衍生物的光谱电化学研究

用循环伏安法研究了２－氨基－９，１０－蒽醌及其衍生物在ＤＭＦ－０．１ｍｏｌ／ＬＴＢＡＰ溶液中的电化学行为，结果表明它们在铂电极上均发生两步连续的单电子还原过程，取代基Ｒ及水和苯甲酸等质子性试剂的加对伏安曲线有很大的影响。     

含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化

有机小分子的电催化氧化是催化领域的一个重要研究内容.通过醇的选择性氧化合成相应醛或酮类化合物在精细化学品和有机化学中间体的合成领域均具有十分重要的意义.有机电催化合成用电子代替强氧化还原剂,可以使反应在比较温和的条件下进行.但在直接电氧化合成反应中,电极表面容易生成有机聚合物膜,使电极钝化,电流效率急剧下降.而在电子转移媒质作用下的有机电催化反应不仅可以避免电极表面钝化,还可以控制目标产物的过度氧化.三芳胺类化合物是一类新型的电氧化还原媒质,由于其具有较宽的电化学氧化还原电位已引起研究者的广泛关注.咔唑类化合物相比于三芳胺类具有更好的平面性,使得取代基效应更为显著.咔唑类化合物被广泛作为荧光材料,但用于电化学方面的研究很少.本文通过在咔唑类化合物中引入具有强吸电子性的硝基以提高该类化合物的氧化电位,并将其作为有机电催化媒质,采用间接电化学氧化的方式,在室温下研究醇的电化学催化氧化反应,合成相应醛类化合物.
　　我们合成了三种含硝基咔唑类有机电催化剂,通过1H NMR对其结构进行了鉴定.采用循环伏安法测试了该类有机电催化剂的电化学氧化还原性能.发现取代基的电子效应对有机电催化剂的氧化还原电位及电化学氧化还原可逆性有很大的影响,供电子基(–OCH3)的引入使氧化电位负移(0.717 V),吸电子基(–Br)的引入使氧化电位明显正移(1.282 V).同时,取代基的引入有效改善了有机电催化剂的电化学可逆性,从而可以作为有效的电氧化还原媒质应用于电化学氧化反应中.而当把化合物中的NO2还原为NH2后,咔唑类化合物的电化学氧化还原可逆性完全消失,表明硝基的引入对咔唑类有机电催化剂的电化学性能有很大的影响.
　　循环伏安结果发现,在咔唑类硝基化合物的作用下,对甲氧基苯甲醇(p-MBzOH)的电化学氧化峰电位从1.350 V降至1.286 V,表明可以在较低电位下进行电解,有效降低了电氧化反应的能耗,同时氧化峰电流明显增加,说明该类有机电催化剂对p-MBzOH具有良好的电催化性能.随着p-MBzOH浓度的增加,氧化峰电流也明显增大,说明在咔唑类有机电催化剂的作用下, p-MBzOH可以在比较高的浓度下进行电化学氧化电解.通过对不同对位取代基的苯甲醇类化合物进行循环伏安研究,发现含硝基咔唑类化合物对具有较高氧化电位的反应底物均表现出良好的电催化氧化性能.
　　在含硝基咔唑类有机电催化剂的氧化电位(1.28 V)和室温下,对不同浓度的p-MBzOH进行恒电位电解6 h,发现当催化剂的用量为底物的2.5 mol%时, p-MBzOH可以完全转化为相应的醛类目标产物.而且恒电位电解后分离回收的含硝基咔唑类有机电催化剂仍具有良好的电化学氧化还原可逆性.     

含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化（英文）

有机小分子的电催化氧化是催化领域的一个重要研究内容.通过醇的选择性氧化合成相应醛或酮类化合物在精细化学品和有机化学中间体的合成领域均具有十分重要的意义.有机电催化合成用电子代替强氧化还原剂,可以使反应在比较温和的条件下进行.但在直接电氧化合成反应中,电极表面容易生成有机聚合物膜,使电极钝化,电流效率急剧下降.而在电子转移媒质作用下的有机电催化反应不仅可以避免电极表面钝化,还可以控制目标产物的过度氧化.三芳胺类化合物是一类新型的电氧化还原媒质,由于其具有较宽的电化学氧化还原电位已引起研究者的广泛关注.咔唑类化合物相比于三芳胺类具有更好的平面性,使得取代基效应更为显著.咔唑类化合物被广泛作为荧光材料,但用于电化学方面的研究很少.本文通过在咔唑类化合物中引入具有强吸电子性的硝基以提高该类化合物的氧化电位,并将其作为有机电催化媒质,采用间接电化学氧化的方式,在室温下研究醇的电化学催化氧化反应,合成相应醛类化合物.我们合成了三种含硝基咔唑类有机电催化剂,通过~1H NMR对其结构进行了鉴定.采用循环伏安法测试了该类有机电催化剂的电化学氧化还原性能.发现取代基的电子效应对有机电催化剂的氧化还原电位及电化学氧化还原可逆性有很大的影响,供电子基(–OCH~3)的引入使氧化电位负移(0.717 V),吸电子基(–Br)的引入使氧化电位明显正移(1.282 V).同时,取代基的引入有效改善了有机电催化剂的电化学可逆性,从而可以作为有效的电氧化还原媒质应用于电化学氧化反应中.而当把化合物中的NO~2还原为NH~2后,咔唑类化合物的电化学氧化还原可逆性完全消失,表明硝基的引入对咔唑类有机电催化剂的电化学性能有很大的影响.循环伏安结果发现,在咔唑类硝基化合物的作用下,对甲氧基苯甲醇(p-MBzOH)的电化学氧化峰电位从1.350 V降至1.286 V,表明可以在较低电位下进行电解,有效降低了电氧化反应的能耗,同时氧化峰电流明显增加,说明该类有机电催化剂对p-MBzOH具有良好的电催化性能.随着p-MBzOH浓度的增加,氧化峰电流也明显增大,说明在咔唑类有机电催化剂的作用下,p-MBzOH可以在比较高的浓度下进行电化学氧化电解.通过对不同对位取代基的苯甲醇类化合物进行循环伏安研究,发现含硝基咔唑类化合物对具有较高氧化电位的反应底物均表现出良好的电催化氧化性能.在含硝基咔唑类有机电催化剂的氧化电位(1.28 V)和室温下,对不同浓度的p-MBzOH进行恒电位电解6 h,发现当催化剂的用量为底物的2.5 mol%时,p-MBzOH可以完全转化为相应的醛类目标产物.而且恒电位电解后分离回收的含硝基咔唑类有机电催化剂仍具有良好的电化学氧化还原可逆性.     

Nitrosylsulfuric acid as an oxidant in the synthesis of 3,5-diarylisoxazoles

By six examples, it was demonstrated that nitrosylsulfuric acid can be successfully used for oxidation of 3,5-diaryl-4,5-dihydroisoxazoles to the corresponding 3,5-diarylisoxazoles. If the starting isoxazolines contain the aromatic substituents activated towards electrophilic substitution, nitration of both newly formed isoxazole and substituted benzene rings occurred.     

Préparation de quelques 4-nitroisoxazoles à partir de pseudonitrosites de cétones éthyléniques du type chalcone

The Synthesis of some 4-Nitroisoxazoles from Pseudonitrosites of Chalcones The action of dinitrogen trioxide with α,β-unsaturated ketones of the chalcone type leads to pseudonitrosites (Table 1) which are cyclized to 4-nitro-3,5-diarylisoxazoles (Table 2).     

An Easy Access to Oxime Ethers by Pd‐Catalyzed C—O Cross‐Coupling of Activated Aryl Bromides with Ketoximes and Chalcone Oximes

An efficient Pd‐catalyzed method for C—O cross‐coupling of ketoximes and chalcone oximes with activated aryl bromides and bromo‐chalcones has been developed. All oxime ethers were obtained in good to excellent yields by [(π‐allyl)PdCl]₂/tBuXPhos ( L7 ) catalyst system. TrixiePhos ( L11 ) was also found to be effective for the oxime coupling. This method offers an easy and smooth coupling of chalcone oximes with activated aryl bromides and bromo‐chalcones, which has not been previously explored.     

Effect of structure in benzaldehyde oximes on the formation of aldehydes and nitriles under photoinduced electron-transfer conditions

The mechanistic aspects of the photosensitized reactions of a series of benzaldehyde oximes (1a-o) were studied by steady-state (product studies) and laser flash photolysis methods. Nanosecond laser flash photolysis studies have shown that the reaction of the oxime with triplet chloranil (3CA) proceeds via an electron-transfer mechanism provided the free energy for electron transfer (DeltaG(ET)) is favorable; typically, the oxidation potential of the oxime should be below 2.0 V. Substituted benzaldehyde oximes with oxidation potentials greater than 2.0 V quench 3CA at rates that are independent of the substituent and the oxidation potential. The most likely mechanism under these conditions is a hydrogen atom transfer mechanism as this reaction should be dependent on the O-H bond strength only, which is virtually the same for all oximes. Product studies have shown that aldoximes react to give both the corresponding aldehyde and the nitrile. The important intermediate in the aldehyde pathway is the iminoxyl radical, which is formed via an electron transfer-proton transfer (ET-PT) sequence (for oximes with low oxidation potentials) or via a hydrogen atom transfer (HAT) pathway (for oximes with larger oxidation potentials). The nitriles are proposed to result from intermediate iminoyl radicals, which can be formed via direct hydrogen atom abstraction or via an electron-transfer-proton-transfer sequence. The experimental data seems to support the direct hydrogen atom abstraction as evidenced by the break in linearity in the plot of the quenching rates against the oxidation potential, which suggests a change in mechanism. The nitrile product is favored when electron-accepting substituents are present on the benzene ring of the benzaldehyde oximes or when the hydroxyl hydrogen atom is unavailable for abstraction. The latter is the case in pyridine-2-carboxaldoxime (2), where a strong intramolecular hydrogen bond is formed. Other molecules that form weaker intramolecular hydrogen bonds such as 2-furaldehyde oxime (3) and thiophene-2-carboxaldoxime (4) tend to yield increasing amounts of aldehyde.     

Relationship between Structure and SHG Effect of Substituted Thienyl Chalcone

1INTRODUCTIONRecentlyorganicnonlinearoptical(NLO)materialsarebeingdevelopedforfre-quencyconversionoflaserinopto-electrics-Especiallybluelightisrequiredforopti-calmemoryofhighdensityrecording.Becauseadiodelaserisusedasalightsource,thenonlinearmaterialswhichhaveextremelyhighvalueofNLOcoefficientsandthetransmissionofblueregionarenecessary.Sincethesecond-orderNLOpropertyoforganiccompoundisderivedfromconjugateddelocalizedrrelectrons,thecompoundswhichhavebeenreportedhavefocusedonthenitroanil…     

Electrochemical and Opto-Electronic Properties of Carbazole-Based Derivatives with Symmetric A–CZ–A Architecture

In this work novel bisheterocyclic derivatives of alkylcarbazole with A–CZ–A architecture are investigated (CZ stands for alkylcarbazole). The study presents their opto-electronic and electrochemical properties which influence on the possibility of their prospective application. Monomers undergo electropolymerisation with formation of conducting layer of polythiophene derivatives, while presence of chalcone moiety hampers the process. Two-step oxidation processes of polymers results in generation of polaron and bipolaron types of charge carriers on the macromoleculs’ chains. The charge is delocalized over center and side subunits (bithiophene or bithiazole one) in first stage of oxidation. It is possible to influence on the properties of the polymers and their composition by variation of synthesis condition like solvent polarity and applied potential boundaries. Obtained conducting polymers show high stability under ambient conditions. Their energy gap values are estimated with electrochemical and spectroscopic methods.     

Voltammetric analysis of some carbamate pesticides

The electrochemical activity of 13 carbamate pesticides has been investigated in the potential range of a glassy carbon electrode, over a pH range from 2.5 and 10. Four compounds, pirimicarb, methiocarb, aminocarb and zectran, give oxidation waves; however, only those for aminocarb and zectran are suitable for analytical electrochemical detection in association with high-pressure liquid chromatography. The oxidation reaction has an ECE mechanism, proposed to involve formation of a carbamate cation radical. This hydrolyses to form a phenol which is in turn oxidized, the end product being a substituted dimethylamino-benzoquinoneimine.     

Spectroelectrochemical Study on the Electrooxidation in Aqueous Medium of some 1,4‐Dihydropyridines: Effects of Substitution in 1‐Position and 4‐Position

Spectroelectrochemical and HPLC characterization of the electrochemical oxidation in aqueous medium of a series of six N‐1 and C‐4 substituted 1,4‐dihydropyridines is presented. Based on the analysis of spectra obtained by in situ spectroscopic measurements it was possible to detect the generation of final oxidation products, which resulted in differences depending of the nature of the substitution on the nitrogen in the dihydropyridine ring. Controlled potential electrolysis (CPE) in aqueous medium was followed by the HPLC technique using EC and PDA detectors. This latter resulted adequately to follow the parent 1,4‐DHP derivatives and their respective oxidation products. Electrochemical oxidation of parent N‐H substituted 1,4‐dihydropyridines generated the corresponding neutral pyridine derivative as final oxidation product. However, the N‐ethyl substituted 1,4‐dihydropyridine derivatives gave rise to the pyridinium salt derivatives.     

Chemistry of N,N‐Bis(silyloxy)enamines,Part 5

Aliphatic nitro compounds can be considered as good precursors of a wide variety of α‐azolyl‐substituted oximes. The double silylation of convenient aliphatic nitro compounds and the subsequent N,C‐coupling of the resulting N,N‐bis(silyloxy)enamines 3 with N‐silylated azoles 4 lead to the formation of the silylated α‐azolyl‐substituted oximes 6 , which can be smoothly desilylated to give the target α‐azolyl‐substituted oximes 5 . The mechanism of the key step of this process – N,C‐coupling – includes the generation of corresponding conjugated nitrosoalkenes 7 (Schemes 4 and 5). The contribution of the chain mechanism in the overall process is considered as well. The studies of the scope and limitations of this reaction, as well as the optimization of its conditions were accomplished. The configuration of the CN bond in oximes was established by NMR.