镍催化环丁酮肟酯与芳基锌试剂的Negishi偶联反应（英文）

发展了一种镍催化环丁酮肟酯和芳基锌试剂之间Negishi偶联的方法.镍既作为亚胺自由基的引发剂,也作为芳基锌试剂与烷基自由基偶联反应的催化剂在反应中起作用.本方法可避免使用剧毒的氰化物,且具有很广的底物适应性和官能团兼容性,因此可能是一种具有潜在吸引力的高效合成烷基腈类化合物的新策略.初步的机理研究显示,该反应极可能经历自由基历程.     

镍催化环丁酮肟酯与芳基锌试剂的Negishi偶联反应

发展了一种镍催化环丁酮肟酯和芳基锌试剂之间Negishi偶联的方法.镍既作为亚胺自由基的引发剂,也作为芳基锌试剂与烷基自由基偶联反应的催化剂在反应中起作用.本方法可避免使用剧毒的氰化物,且具有很广的底物适应性和官能团兼容性,因此可能是一种具有潜在吸引力的高效合成烷基腈类化合物的新策略.初步的机理研究显示,该反应极可能经历自由基历程.     

取代苯基烷基酮与叔丁基氯化镁反应的机理研究

通过EPR技术观察到一系列典型的烷基或甲氧基取代的苯基烷基酮ArCOR(Ar=2,5-二甲基苯基(1);2,5-二甲氧基苯基(2);4-叔丁基-2,5-二甲氧基苯基(3))与t-BuMgCl反应中形成的自由基阴离子中间体[ArC(R)OMgCl]。产物分析表明,反应主要生成还原产物[ArCH(R)OH]和1,2-加成产物[ArC(R)(t-Bu)OH]。降低溶剂极性及反应温度都有利于还原产物的生成。对上述反应的可能历程作了简单讨论。     

一种有效合成3-芳基-4-氟烷基-2-噁唑烷酮的方法

报道了一种方便有效地合成3-芳基-4-氟烷基-2-噁唑烷酮的方法.用芳基胺作为起始原料通过与氯甲酸烯丙基酯反应以95.8%～99.5%的收率得到芳基氨基甲酸烯丙基酯.芳基氨基甲酸烯丙基酯与氟烷基碘在乙腈和水的混合液中由连二亚硫酸钠引发在室温下发生自由基加成反应得到氟烷基化的加成产物.加成产物在碱性条件下发生分子内的N-环合反应得到3-芳基-4-氟烷基-2-噁唑烷酮.整个反应都在室温下进行,并且没有用到光气合成了3-芳基-4-氟烷基-2-噁唑烷酮,该方法具有原料易得,条件温和,绿色环保的优点.     

铁催化下二芳基锌和芳基格氏试剂的二氟烷基化反应

随着医药、农药、材料等领域对含氟化合物日益增长的需求,发展向有机分子中直接引入氟原子和含氟基团的方法受到了化学家们的广泛重视.近些年来,过渡金属催化的氟烷基化反应,作为一种温和可控向有机分子引入含氟基团的策略得到了快速发展.与此同时,从反应的高效简洁和绿色温和性角度出发,发展廉价金属作为催化剂以及使用廉价易得的氟卤烷烃作为氟烷基试剂是非常具有吸引力的.本文以绿色低毒的Fe（acac）₃为催化剂,首次实现了铁催化下二芳基锌与α,α-二氟炔丙基溴的交叉偶联反应.该反应条件温和、原料廉价易得,产物可以放大到克量级制备,并能进行多种转化.此外,这一铁催化体系还可以实现芳基格氏试剂与二氟烷基溴代的偶联反应,为合成二氟烷基芳烃化合物提供了一种有效方法.初步的机理研究表明,该反应可能经历了单电子转移的自由基反应历程,偕二氟炔丙基自由基存在反应催化循环中.     

2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

2,5-二甲氧基苯基烷基酮, 4-叔丁基-2,5-二甲氧基苯基烷基酮, 2,5-二甲基苯基烷基酮及其还原产物和加成产物的合成及光谱研究

本文报道一系列芳基烷基酮, 如2,5-二甲氧基苯基烷基酮, 4-叔丁基-2,5-二甲氧基苯基烷基酮2,5-二甲基苯基烷基酮及相应的一些衍生物的合成及MS, NMR,IR和UV光谱的分析结果. 并讨论了一些改进后的合成方法和有意义的副反应以及由光谱数据所揭示的这些化合物的特征结构.     

超声条件下芳基格氏试剂与4-烷基苯乙酮的反应

二芳基乙烯;超声条件下芳基格氏试剂与4-烷基苯乙酮的反应     

P,P,P',P'-四氯联苯二膦的合成

芳环的二氯膦化产物是有机合成中的重要中间体,广泛应用于不对称合成领域制备手性膦配体,紫外光固化领域合成膦酰氧光引发剂等。文献报道的芳环二氯膦化方法有如下几种：(1)由芳基溴制备格氏试剂或由芳基溴直接锂化,然后与三氯化膦反应。(2)由芳基溴经格氏试剂或直接锂化,然后与二(二乙胺基)氯化膦反应,最     

可见光促进下氟烷基砜对芳基烯烃的自由基氟烷基化反应

自由基氟烷基化是向有机分子中引入氟烷基的一类非常重要的方法,也是目前有机化学研究的热点之一.近几年来,由于广泛的官能团兼容性和温和的反应条件等优点,可见光促进的氧化还原催化反应得到了长足的发展,已经成为化学键的构建和活化的有力工具.因此,光氧化还原催化的自由基氟烷基化反应,作为向有机化合物中引入氟烷基的有效途径,受到了广泛关注.本文报道了我们发展的氟烷基砜作为一类方便易得的新型氟烷基自由基前体,在可见光氧化还原催化下实现对烯烃的自由基氟烷基化反应.该反应可以高效地向芳基烯烃中引入三氟甲基、二氟甲基、1,1-二氟乙基、苯基二氟甲基等各种含氟烷基基团,并实现对芳基烯烃的双官能团化转化.     

紫外分光光度法测定苯基硅油的苯基含量

采用水解缩合法合成了苯基硅油,并进行傅立叶红外(FTIR)、氢谱(1H NMR)表征.根据氢谱的积分,计算得产品的苯基含量.基于苯基基团在紫外区的特征吸收,以自制苯基硅油为标准品,建立了一种紫外分光光度法测定苯基硅油中苯基含量的方法.以二氯甲烷为溶剂,264 nm为最大吸收波长,苯基浓度在0.277×10-3～2.13×10-3 mmol· mL-1范围内,符合比尔定律,其R2 =0.99946.实际样品测定的相对标准偏差小于1.81％,平均回收率为99.0％左右.该方法线性相关性好、精密度及准确度高、便捷、成本低,适合科研及工业生产中苯基含量的日常分析.     

Baylis‐Hillman Reaction of Arylaldehydes with Phenyl Vinyl Ketone,Phenyl Acrylate,and Phenyl Thioacrylate

In the Baylis‐Hillman reaction of aryl aldehydes with phenyl vinyl ketone, we found that the diadduct 4 was exclusively formed, and that the yield of 4 can reach 80% with increasing amounts of phenyl vinyl ketone. But, for phenyl acrylate and phenyl thioacrylate, only the normal Baylis‐Hillman adduct was obtained. The substituent effects were also examined, and a plausible reaction mechanism was proposed for the formation of 4 .     

Polarographic Reduction of Phenyl Arsenoxide

Abstract

The differential pulse polarography of phenyl arsenoxide (C₆H₅AsO) and its use in the indirect determination of chlorine and ozone is described.     

Iodonium-Promoted Glycosylations with Phenyl Selenoglycosides

Abstract

Fully benzylated or benzoylated phenyl selenoglycosides can be activated by the promoters iodonium di-sym-collidine perchlorate (IDCP) or N-iodosuccinimide and catalytic triflic acid (NIS/TfOH). The potential of the iodonium ion-mediated glycosylations with phenyl selenoglycosides is illustrated in the chemoselective synthesis of 1,2-cis-and 1,2-trans linked disaccharides.     

Phenyl(fluoro)chlorodisiloxanes

Cohydrolysis of phenyltrichlorosilane with phenyl(fluoro)dichloro- and phenyl(difluoro)-chlorosilanes and thermolysis of the formed siloxanes leading to the formation of phenyl(difluoro)chlorosilane are studied. The scheme of thermal decomposition of disiloxanes possessing fluorine atoms in the 1,3 positions is suggested. The scheme is based on the intermediate formation of an active four-membered cyclic complex closed by the fluorine bridge between the silicon atoms. In agreement with the scheme, no thermolysis of 1,3-diphenyl-1-fluoro-1,3,3-trichlorodisiloxane is observed under the studied conditions.     

Phenyl derivatives of 2-pyrone

Several phenyl dichloropentadienyl ketones containing a hydroxy or methoxy group in the benzene ring as well as a number of 2-pyrones based on them were synthesized. The possibility of the conversion of the latter to the corresponding 2-pyridones on heating them with ammonium salts is demonstrated.See [2] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 579–581, May, 1971     

Phenyl polypropanoids from Lindelofia stylosa

A phytochemical investigation on the aerial parts of Lindelofia stylosa has resulted in the isolation of seven phenyl propanoids. This includes three analogs of lithospermic acid, along with rosmarinic acid and its ester derivatives. Compound 1 was identified as a new natural product. These compounds were studied for their antioxidant properties.     

Photo-Trifluoromethylthiolation of Cyclopropyl Phenyl Propargyl Alcohol

Seven compounds are formed in various amounts when a solution of cyclopropopyl phenyl propargyl alcohol and trifluoromethylsulfenyl chloride in acetonitrile is exposed to UV light. The probable mechanism of formation and the mass spectral characterization of these compounds are described.     

NMR Study on Substituted Phenyl Furoisoxazolines

The configurations of substituted phenyl furoisoxazolines were determined by study on their ^1H-NMR and 1D NOESY.The characteristic chemical shifts of the γ-lactone ring protons in ^1H-NMR were also discussed.     

Diastereocontrolled Synthesis of Cyclopropane Phenyl Sulfoxides

Good diastereocontrol of three stereocentres is obtained in the synthesis of cyclopropane pheny¹ sulfoxides.