由炔的金属烯丙化合成二烯烃和环烯烃

炔的金属烯丙化(allylmetallation)是炔的金属烃化反应(carbometallation)的一种,是立体专一地合成多取代烯烃的有效途径。铝烯丙化(allylalumination)和锌烯丙化(allyl-     

傅立叶红外光谱法测定丙烯-乙烯共聚物中丙烯单元含量

应用傅立叶红外光谱法,根据丙烯-乙烯共聚物的红外特征性,寻找较好的峰位,使用通用型制膜机制得厚度均匀一致的膜片,制作标准曲线,建立了快速检测丙烯-乙烯共聚物中丙烯单元含量的方法。将红外光谱法分析结果与核磁共振法分析结果进行比较,相对误差在2%以内,测得不同丙烯单元含量的样品的相对标准偏差(n=6)为0.47%~1.1%。     

硫酸氢钠催化合成羧酸烯丙酯

硫酸氢钠能够代替硫酸作为酯化催化剂。利用－水硫酸氢钠催化合成了甲酸烯丙酯、乙酸烯丙酯、丙酸烯丙酯、丁酸烯丙酯和戊酸烯丙酯,产物用折射率、元素分析和红外光谱表征。研究了硫酸氢钠用量对丙酸烯丙酯收率的影响。     

羟基药物及毒物荧光检测探针的设计合成

通过相应的酸和亚硫酰氯反应合成了３种新的稠环芳基取代酰氯类化合物（９－蒽丙烯酰氯，９－蒽丙酰氯和１－芘丙烯酰氯）作为羟基药物及毒物超微量分析的荧光探针。     

人造芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯的气相色谱分析

采用２ｍ×３ｍｍ玻璃柱，涂布０．５％ＥＧＡ的８０～１００目ＧａｓｃｈｒｏｍＱ为固定相，以异辛醇为内标物，分析芥子油中异硫氰酸烯丙酯与硫氰酸烯丙酯异构体。该方法既可用于人造芥子油的含量分析，也可用于市售芥子油的质量鉴定。     

NBS优先进行烯丙位取代的讨论

在烯丙位或苄基位上引进溴的温和而选择性高的方法,是采用NBS(N-溴代丁二酰亚胺),通常这一反应称为Wohl-Ziegler反应。早年,Bloomfield对这一反应曾提出了一个通过丁二酰亚胺游离基夺取氢的自由基链反应历程,以丙烯作为烯烃的代表,表示如下:     

丙烯酰氯的气相色谱分析

1 引言丙烯酰氯易挥发,暴露于空气与水份作用产生盐酸酸雾,具有强烈的刺激性和腐蚀性.本文用苯胺作衍生反应试剂,使丙烯酰氯与苯胺定量反应生成N-苯基丙烯酰胺,氯化氢与过量苯胺生成氯化苯铵沉淀,从而消除了游离氯化氢对仪器的腐蚀性和给操作带来的不便,再以邻苯二甲酸二异丙酯为内标,经OV-17柱分离,FID检测器测定,实现了丙烯酰氯的无腐蚀简便快速气相色谱分析.2 实验部分2.1 仪器和试剂 GC-9A气相色谱仪(日本岛津公司),FID检测器,CR-3A记录仪.玻璃色谱柱1.1m×3mm,OV-17固定液5%,担体Shimalite W(AW-DMCS)粒径180～154μm.丙烯酰氯对照品98%(贵州省冶金化学研究所).邻苯二甲酸二异丙酯溶液(内标溶液):60g/L苯溶液.苯胺溶液:10%(V/V)的苯溶液.所用溶剂     

环丙烯研究新进展

环丙烯类化合物是自然界中可能存在的最小的不饱和环状化合物, 它独特的结构和电性使其在有机合成中有着非常广泛的用途. 环丙烯类化合物有着很大的环张力, 具有很高的张力能和反应活性, 一直以来都作为一类明星分子得到了化学家们的广泛关注. 尤其是近年来当金属有机化合物介入环丙烯化学, 通过各种加成反应, 环加成反应, 开环反应等, 可作为一个三碳结构单元用于构筑各类有机化合物. 本文则主要从环丙烯的合成、环丙烯的转化和参与的反应, 以及环丙烯的应用三个方面概述了2011年至今关于环丙烯的最新研究进展.     

氰基丙二烯与乙烯环加成机理的理论研究

应用AM1方法研究了氰基丙二烯和乙烯环加成反应的反应机理,讨论了氰基对反应机理的影响。结果表明乙烯和氰基丙二烯之间的反应是自由基反应,乙烯进攻氰基丙二烯的中心碳原子从能量上考虑比进攻两端碳原子更为有利,且位垒比丙二烯上无取代基时低,比氨基取代时高,说明吸电子基团氰基取代氢原子后,使环加成反应易于进行,但没有供电子基团氨基的作用大。以上结论均与实验结果一致。     

N-丙烯酰吩噻嗪异构体的量子化学研究

用量子化学从头算方法 ,在RHF/ 6_31G 的水平上 ,对N_丙烯酰吩噻嗪分子两种异构体进行了理论计算 ,优化得到了它们的平衡几何构型 ,并计算了它们的谐振动频率 .结果表明 :N_丙烯酰吩噻嗪分子两种异构体的稳定性不同 .用PM3/CIS和AM1/CIS方法计算了它们的电子光谱 ,得到了由基态到各激发态的垂直跃迁能和相应的振子强度 .这些结果对探讨N_丙烯酰吩噻嗪引发丙烯腈聚合的机理是有益的     

<Emphasis Type="Italic">N</Emphasis>-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/<Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A simple method for N-alkylation of 1,2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/γ-Al₂O₃ as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of 1,2-diaminoethane with both primary and secondary alcohols. Mono-N-alkylation of 1,2-diaminoethane with low-carbon alcohols resulted in high yields; the yields of tetra-N-alkylation of 1,2-diaminoethane with low-carbon alcohols declined markedly with the increase of the molecular volume of alcohols.     

Electronic properties of n-type carbon nanotubes prepared by CF4 plasma fluorination and amino functionalization

Single-walled carbon nanotubes (SWNTs) have been fluorinated by CF4 plasma exposure and further functionalized with 1,2-diaminoethane. The degree of amino functionalization is dependent on the degree of initial fluorination rather than oxygen or carbon defects. Reaction at both ends of 1,2-diaminoethane was observed to increase with fluorine content. Back-gated SWNT devices have shown p-type semiconducting behavior for CF4-functionalized SWNTs and n-type semiconducting behavior for amino-functionalized SWNTs. The degree of n-type behavior increases with the amount of nitrogen attached to the SWNTs.     

超支化聚酰胺-胺破乳剂的合成及应用

以N-丙烯酰-1,2-乙二胺盐酸盐(ADE)合成为基础,通过ADE的Michael加成反应制备阳离子超支化聚合物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),并对其结构进行了表征。研究表明,50℃下,HADE破乳剂(质量浓度为200 mg/L)对含煤油质量分数5%的水包油(O/W)煤油乳液的除油率可高达95.6%,显示了产品在乳液破乳除油方面良好的发展前景。     

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3-(1-Hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines with Dinucleophilic Reagents

The reaction of 3-(1-hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was inves-tigated.7-Fluoroalkyl-2,3-dihydro-1,4-diazepine[1,2-d]quinazolin-11-ones 2,2-fluoroalkylisoxazolo[3,2-b]quin-azolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane,hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.     

手性1,2-二苯基-1,2-乙二胺及其衍生物在不对称合成中的应用

含有C2 对称轴的1,2-二胺在不对称合成中得到了广泛的应用.综述了手性1,2-二苯基-1,2-乙二胺及其衍生物的合成,以及作为手性辅助基和手性配体在不对称合成中的应用.     

1,2-Diisophthalimidoethane. X-ray diffraction evidence for the structure of the product of acylation of 1,2-diaminoethane with phthaloyl chloride

It was demonstrated by x-ray diffraction investigation of the product of the reaction of 1,2-diaminoethane with phthalic acid dichloride that the resulting compound has the 1,2-diisophthalimidoethane structure. An improved method for its synthesis is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1320–1323, October, 1987.     

Reactions of allenylphosphonates with 1,2-diaminoethane

The reactions of dialkyl 3-methylbuta-1,2-dien-1-ylphosphonates with 1,2-diaminoethane lead to the formation of symmetrical N,N′-bis(1-dialkoxyphosphoryl-3-methylbut-1-en-2-yl)-1,2-diaminoethanes.     

乙酰基硫代甲酰芳胺合成二氢吡嗪的研究

报道了一种合成乙酰基硫代甲酰芳胺的方法. 合成的乙酰基硫代甲酰芳胺与1,2-乙二胺缩合生成5-(4'-取代苯胺基)-6-甲基-2,3-二氢吡嗪类杂环化合物.     

Synthetic studies on isoschizogamine: construction of [3.3.1] bicyclic aminal core by using oxidative skeletal rearrangement

The tetracyclic core structure of isoschizogamine containing aminal functionality was constructed by oxidative skeletal rearrangement of a 1,2-diaminoethene derivative. The 1,2-diaminoethane was prepared by palladium-catalyzed allylation at the 4a position of a 1,2,3,4-tetrahydro-β-carboline derivative and subsequent lactam formation. After the oxidative skeletal rearrangement using dimethyldioxirane, the allyl group was removed by a three-step sequence to provide the tetracyclic core skeleton of isoschizogamine with aminal functionality.     

Long-lived reactive intermediate photogenerated from N-(5-azido-2-nitrobenzoyl)-N'-(D-biotinyl)-1,2-diaminoethane as an affinity reagent to streptavidin

Irradiation of a complex between N-(5-azido-2-nitrobenzoyl)-N'-(D-biotinyl)-1,2-diaminoethane (I) and streptavidin with light of 313 nm led to the covalent attachment of the photobiotin analogue I to the protein. Streptavidin could also be labelled in the dark with prephotolyzed I. These results indicate that a long-lived reactive intermediate was formed upon irradiation. Moreover, after cleavage of labelled streptavidin with proteinase K this intermediate appears to be covalently attached to the same peptide as the one obtained by direct photoaffinity labelling. An iminosulfurane II derived from the reaction of biotin sulfur atom with aryl nitrene is responsible for the dark-labelling reaction. The photoproduct II converts in an aqueous solution almost completely into N-(5-amino-2-nitrobenzoyl)-N'-(D-(S-oxo)biotinyl)-1,2-diaminoethane (the half-life of II is 10 days).