共查询到19条相似文献,搜索用时 93 毫秒
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肟已被广泛用于羰基化合物的表征、纯化以及酰胺的合成[1 ] 。人们可以从羰基和非羰基化合物来制备肟 (Barton反应[2 ,3] )。因此 ,肟的脱肟成酮也是合成羰基化合物的一种方法。近年来 ,文献中不断有各种脱肟试剂和催化剂 ,如 :三氧化铬 硅胶[4] 、镍 (Ⅱ )复合物[5] 等的研究报道。但这些方法都是在液相中进行的 ,通常需要计量或过量的有机试剂 ,而且反应时间长、产率低[6] 。为了寻找高效的脱肟方法 ,微波辐射下的干反应脱肟研究已愈来愈引起人们的兴趣[1 ,7] ,它具有反应速度快、副反应少、产率高等优点。前文[8] 我们报道了用甲酸… 相似文献
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单晶X射线衍射分析表明,几个新的α-单取代环十二酮与氨衍生物羟胺发生反应得到三种母体构象分别为[3333]和[2334],而取代基为边外向或角反向的α-单取代环十二酮肟.利用底物的"角位羰基参与反应"原理,"记忆效应"及进攻试剂与底物是否形成氢键解释了这一实验结果.通常取代基体积较大以及α-取代基与羰基形成分子内氢键情况下,试剂从空间障碍小以及远离氢键的一面进攻羰基生成α-角反取代环十二酮肟;当试剂与底物的取代基之间能够形成强的分子间氢键时,生成α-边外取代环十二酮肟;当试剂与底物的取代基之间只能形成弱的分子间氢键以及底物的取代基较小时,试剂从两面进攻羰基同时生成α-角反取代环十二酮肟和α-边外取代环十二酮肟. 相似文献
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染料木素和柚皮素分别为黄酮类天然活性分子,具有抗氧化和抗肿瘤等多种生物活性。以染料木素和柚皮素为母体,分别在染料木素7-位酚羟基和柚皮素4-位羰基上引入含氮的肟基和肟醚单元,合成了4个黄酮肟和6个黄酮肟醚,并通过核磁共振(1H NMR)及高分辨质谱(HR-MS)进行了结构表征。采用MTT法对胃癌细胞株SGC-7901体外抗肿瘤活性筛选。结果表明:含肟基的化合物活性优于肟醚,化合物3c对胃癌细胞株SGC-7901有较好的抑制作用。 相似文献
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Highly efficient oxidation of oximes to carbonyl compounds by molecular oxygen with benzaldehyde as an oxygen acceptor in the presence of metalloporphyrins has been reported. The simple structural manganese porphyrin showed an excellent activity for the oxidative deoximation reactions of various oximes. Moreover, different factors influencing oximes oxidation, that is, catalyst, solvent, and temperature, have been investigated. A possible mechanism for the deoximation reaction has been proposed. 相似文献
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Recent advances on the deoximation reactions are reviewed in this review. It was shown that catalytic deoximation with molecular oxygen as the mild oxidant should be the developing trend of the reaction. 相似文献
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Alexander O. Terent’ev Igor B. Krylov Vera A. Vil’ Zhanna Yu. Pastukhova Sergey A. Fastov Gennady I. Nikishin 《Central European Journal of Chemistry》2012,10(2):360-367
It was found that oximes undergo deoximation in the presence of the H2O2aq-HBraq system to form ketones and bromo ketones. This reaction provided the basis for the synthesis of dibromo ketones in yields
varying from 40% to 94%. This method is environmentally friendly, sustainable, and easy to perform. The results of this investigation
extend the potential of the use of oximes for the protection of carbonyl group, thus offering the ability to perform not only
conventional deoximation but also the subsequent bromination of ketones. The reaction is easily scaled up and dibromo ketones
can be prepared in gram amounts.
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Using novel nitrite-containing resin as an NO source and Amberlyst-15 as cocatalyst, we developed aerobic oxidation of oximes to corresponding carbonyl compounds with molecular oxygen as a clean oxidant reagent. It was distinguished from the previous related reports, and the experimental results indicated that additional water obviously decreased the yield. This process provides a better choice for oxidative deoximation with many advantages, such as high yield, simple procedure, high catalytic performance, and recyclable catalyst. 相似文献
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Sandeep Bhosale 《Tetrahedron》2010,66(50):9582-9588
Magtrieve™ (CrO2) and MnO2 mediated oxidation of aldoximes to nitrile oxides were studied in details. In presence of external radical source, TEMPO, these reagents did not furnish nitrile oxides, instead favoured deoximation to aldehydes. A common trend of deoximation was established from electronically tuned aldoximes, which is: aliphatic>aromatic>aldoximes with strong electron-withdrawing group, though the extent of deoximation was less in case of CrO2. Above effects were not observed with chloramine-T and diacetoxyiodobenzene, reagents known to produce nitrile oxides via hydroximoyl halide or equivalent ionic intermediates. A putative reaction mechanism is proposed for MO2 (M=Cr, Mn) mediated oxidation of aldoximes through formation of a nitroso-oxime tautomeric pair. Formation of nitrile oxide is possibly occurred from the oxime tautomer via a σ-type iminoxy radical intermediate. The deoximation process, dominating in presence of external radical environment, is explained following decomposition of the nitroso tautomer. 相似文献
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《中国化学快报》2023,34(1):107505
Polyaniline-supported tungsten (W@PANI) was easily prepared by immersing polyaniline (PANI) in the aqueous solution of Na2WO4. It was found to be an efficient catalyst for oxidative deoximation reaction, the very important transformation for pharmaceutical industry. Besides the green features, the method employed very few of catalytic tungsten (0.048 mol% vs. oxime substrates), resulting in the high turnover numbers (TONs) of the catalyst (ca. 103 mol/mol) and the low metal residues in product (<0.1 ppm). The reaction is applicable for a variety of substrates, including those containing heterocycles, which are key intermediates in medicine synthesis. It has also been successfully magnified to kilogram scale production to afford the desired carbonyl products smoothly. 相似文献
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The deoximation kinetics of some oximes was studied by using cetyltrimethylammonium dichromate (CTADC) in dichloromethane in the presence of acetic acid and a cationic surfactant. The rate of reaction is highly sensitive to the change in [CTADC], [oxime], [acid], [surfactant], polarity of the solvents, and reaction temperature. The reaction is found to be catalyzed by acid with an appreciable uncatalytic rate. The reaction is first order with respect to substrate. With increase in CTADC concentration, rate of the reaction increases with a fractional order dependency with respect to oxidant. Consistent to the observation, a mechanism has been proposed in which the substrate forms a complex with CTADC in the rate determining step followed by decomposition with a fast process to yield corresponding carbonyl compounds. The structure of the substituents has also a significant effect on the rate constant. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 482–488, 2011 相似文献
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A clean, mild, and efficient catalytic deoximation procedure compatible with several common functional groups has been developed using 30% hydrogen peroxide activated by iodine catalyst in aqueous acetonitrile under essentially neutral conditions. The mechanistic features of an iodonium ion–driven nucleophilic cleavage of oximic C[dbnd]N have been revealed. 相似文献
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The organic chemistry of polyvalent iodine compounds has experienced an unprecedented development during the last decade of 20th century.[1,2] On the other hand, despite its extensive use in industry, I2O5 (iodine pentoxide, IP) has rarely been employed in organic synthesis except as an alternative to iodoxybenzoic acid (IBX) for the dehydrogenation of aldehydes and ketones.[3] Generally, pentavalent iodine reagents, such as IBX and Dess-Martin periodinane (DMP)were used as mild and selective oxidants for oxidation of alcohols[1,2] and dehydrogenation of carbonyl compounds.[3] We wish to report herein that IP can serve as a mild and efficient reagent for the oxidative cleavage of oximes to aldehydes and ketones (Eq. 1). Most interestingly, IP can also activate hydrosilanes for reduction of alkenes. Hence, simultaneous deoximation and conjugate reduction of α,β-unsaturated ketoximes can be achieved by using IP and phenyldimethylsilane (Eq. 2). 相似文献