REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

2－戊酮、芳香醛与芳香胺的Mannich反应

２－戊酮、芳香醛与芳香胺的Ｍａｎｎｉｃｈ反应邹君华，易林（西南师范大学化学系，重庆６３０７１５）关键词Ｍａｎｎｉｃｈ反应，芳香醛，芳香胺，２－戊酮８０年代以前，一般认为芳香胺与甲醛及含有α－氢的酮不能发生Ｍａｎｎｉｃｈ反应￣［１，２，３］，相应的Ｍａ...     

龙脑烯醛同单重态氧反应的立体选择性

用竹红菌甲素匹配高压钠灯光敏氧化龙脑烯醛,高产率并有立体选择性地获得反应主产物,α-(2,2-二甲基-3-亚甲基-4-羟基-1-环戊烷基)乙醛。反应具有协同的“ene”反应特性。反应的立体选择性被龙脑烯醛的分子构象,取代基的空间位阻效应和烯丙基氢的轴向定位所控制。羰基同环戊烯基的相互隐蔽的分子构象对反应的立体选择性起关键作用。     

ON SOME INCORRECTNESS IN THE INTERPRETATION OF RESULTS OF THE REACTION OF SULPHINYLAMINES WITH ALDEHYDES

Abstract

In contradiction to reports by others, it was shown that sulphinylamines do not give products of cycloaddition on reaction with aldehydes in aprotic solvents. However, in the presence of a protonogenic agent, crystalline products were precipitated for which an ammonium α-aminosulphonate salt structure was confirmed. These salts are formed as a result of consecutive hydrolysis of sulphinylamines, condensation of aldehydes with the resulting amines, and bisulphite anion addition to Schiff bases.     

二氯甲基膦酸二乙酯与醛、酮的反应——1,1-二氯代烯烃的制备

本文报导了以二氯甲基膦酸二乙酯作试剂,在正丁基锂作用下与醛、酮化合物反应制备1,1-二氯代烯烃的合成方法。该试剂在相近条件下与醛、酮反应无显著差别,均得到了较满意的结果。二氯甲基膦酸二乙酯由络合物[Cl₂CHPCl₃]⁺AlCl₄^-与无水乙醇反应制得。     

CONDENSATION OF SOME AROMATIC ALDEHYDES WITH DIMETHYL SULFONE

Abstract

Condensation of some aromatic aldehydes with dimethyl sulfone using sodium amide has been studied. Majority of the aldehydes afforded cis-2,6-diaryl-1,4-oxathian-4,4-dioxides as the exclusive product. 4-Methoxybenzaldehyde, in addition, provided the bis α,β-unsaturated sulfone as the major product while 4-nitrobenzaldehyde yielded only the Tischenko product by self-condensation. The products have been characterised by elemental analysis and spectral data.     

THE KNOEVENAGEL CONDENSATION REACTION OF AROMATIC ALDEHYDES WITH MALONONITRILE BY GRINDING IN THE ABSENCE OF SOLVENTS AND CATALYSTS

ABSTRACT

An improved Knoevenagel condensation reaction of aldehydes and malononitrile can be achieved by grinding at room temperature in the absence of solvents and catalysts. This process is simple, efficient, economical, and environmentally benign. Compared to reactions carried out by microwave irradiation, this procedure is completely free from organic solvents during both the reaction and separation of the product.     

REACTION OF SUGAR PHOSPHONATES WITH SUCROSE ALDEHYDES. SYNTHESIS OF HIGHER ANALOGS OF SUCROSE

The Horner-Emmons reaction between sugar phosphonates Sug-C(O)CH₂P(O)(OMe)₂ and aldehydes derived from sucrose afforded precursors of higher analogs of the general formula Sug-C(O)CH═CH-Suc. An example of the functionalization of the internal three-carbon saccharide connecting unit is provided.     

强酸性阳离子交换树脂催化醛与乙酸酐的反应

强酸性阳离子交换树脂能有效地催化醛与乙酸酐的反应合成1，1二酯，获得较好的收率，产物的熔点、红外光谱及元素分析数据均与标准数据相吻合。     

压力和温度对4-甲基二苯并噻吩和二苯并噻吩加氢脱硫反应的影响

研究了4-甲基二苯并噻吩(4-MDBT)和二苯并噻吩(DBT)在CoMo/γ-Al2O3上的加氢脱硫反应产物分布及其可能的反应网络,通过反应压力和温度对产物分布影响的研究,揭示了加氢脱硫反应的可能机理。研究发现4-MDBT在CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径和加氢路径进行,且两者反应速率相当；DBT在 CoMo/γ-Al2O3上的加氢脱硫反应主要通过直接氢解路径进行。4-MDBT分子位于4位的甲基阻碍其在催化剂表面通过硫原子的端连吸附,从而降低了其直接氢解脱硫路径的反应速率,因而也降低了其总的加氢脱硫转化率。反应压力降低,DBT和4-MDBT加氢脱硫反应中加氢路径反应速率明显下降,而其对氢解路径影响较小,但效果却与加氢路径相反,反应压力对4-MDBT转化率的影响大于DBT。反应温度对DBT和4-MDBT加氢脱硫反应中加氢路径和氢解路径都有明显影响,但是对DBT加氢脱硫反应中氢解路径的影响小于加氢路径,而对4-MDBT加氢脱硫反应中氢解路径的影响稍高于加氢路径,4-MDBT分子中甲基的供电子作用有利于相连苯环的加氢反应。     

阿奇霉素和茜素在甲醇中的荷移反应

研究了阿奇霉素和茜素在甲醇中的电荷转移反应,两者在甲醇中生成摩尔比为2∶1的荷移络合物,此络合物的λmax=536 nm,表观摩尔吸光系数为1.50×103L.mol-1.cm-1,药物浓度在25~250 mg.L-1范围内符合比耳定律。据此提出阿奇霉素的简单,快速而准确的测定方法。     

AN APPROACH TO THE REACTION MECHANISM OF GEM-DIHALOCYCLOPROPANES WITH METALS UNDER ULTRASONIC IRRADIATION

The reactive intermediate cyclopropylidene, generated quickly by the reactions of dihalocyclopropanes with lithium or magnesium under ultrasonic irradiation, can be trapped by olefins and the corresponding spriopentane derivatives are obtained, Based on the identification of the intermediate and the products of the reaction, a mechanism is proposed that the radical intermediate should be generated at first via a single electron transfer process, sequentially it gains another electron from the metals to form the carbenoid intermediate which then leads to the main products by insertion, addition or rearrangement. On the other hand, it can also abstract the hydrogen atom from the solvent to form the corresponding monohalide which then converts into the cyclopropane derivatives. Discussions on and verifications for the reaction mechanism are given in this paper.     

PC/EAA共混体系在加工过程中的反应

采用差示扫描量热法(DSC)和核磁共振氢谱法(1H-NMR)研究了不同聚碳酸酯(PC)/乙烯-丙烯酸共聚物(EAA)共混体系在加工过程中的大分子反应,考察了有机金属催化剂二丁基锡DBTO)含量和反应时间对体系的影响.采用哈克(Haake)转矩流变仪的混合器作反应釜,索氏抽提器分离产物.结果表明,PC和EAA在加工中反应剧烈,在共混体系的界面原位形成接枝或交联的PC-EAA共聚物,随催化剂用量增大、反应时间延长易生成共交联的PC-EAA共聚物.但混合时间过长,体系的断链反应会加剧,生成产物不稳定.     

二溴对甲基偶氮溴羧与钡显色反应的研究与应用

研究了新显色剂二溴对甲基偶氮溴羧与钡显色反应的条件。在磷酸介质中,试剂与钡形成2:1的络合物,最大吸收波长为610nm,摩尔吸光系数为2.13×10~4L·mol~(-1)·cm~(-1),钡量在0～20μg/25ml范围内符合比耳定律。两倍的锶和五倍的钛不干扰,钙的允许量较大,方法用于直接测定钛酸钡烧结物中微量钡,结果满意。     

离子分子反应装置的建立及应用

本文报导离子分子反应装置的建成并测量了O~++N_2反应的速率常数k.O~+离子由微波放电和电极电离产生,经快速流动,用四极质谱仪检测到.中性分子N_2经支管进入流动管,并与O~+离子反应,在温度为298 K 时,测得该反应速率常数为k=(2.50±0.52)×10~(-12)cm~3·molec~(-1)·s~(-1)(T=298 K)     

稀土氧化物上COS还原SO_2脱硫反应及机理

设计了两级干法脱硫系统，在第一级脱硫器中用ＣＯ还原烟道气中的ＳＯ２，在第二级脱硫器中，让在第一级脱硫器中产生的副产物ＣＯＳ与未完全脱除的ＳＯ２进一步进行二级脱硫反应。考察了稀土氧化物对ＣＯＳ还原ＳＯ２脱硫反应的催化活性，发现氧化铈具有最高的脱硫活性，并且具有较大的反应物配比适用范围。对氧化铈催化ＣＯＳ还原ＳＯ２反应提出了ｒｅｄｏｘ还原氧化机理。     

四水氯化锰与对甲基苯胺配位反应的热化学研究

用溶解量热法测定聚凝相反应的焓变,并进一步得到指定物质未见报道的标准生成焓数据,是一种较准确的研究手段。所得到结果可完善物质的标准热力学性质,满足化学研究与应用的需要。本文选择氯化锰（NnCl2.4H2O)与对甲基苯胺（CH3C6H4NH2,简称p-tol)进行反应,合成了配合物Mn(p-tol)2Cl2。用新型的具有恒定温度环境的反应热量计^[1],以溶解量热法^[2,3],用一定比例的HCl(3.0mol.L^-1)与无水乙醇的合溶液作为量热溶剂,分别测定了反应物,产物的溶解熔,设计了一个新的热化学循环,得到了配位反应的反应焓,并计算出了配合物Mn(p-tol)2Cl2的标准生成焓。     

尾式缬氨酸四苯基卟啉锌(Ⅱ)与咪唑轴配反应的光谱和热力学

用金属卟啉化合物来模拟血红素、细胞色素等天然卟啉化合物的生理过程一直是配位化学重要的研究课题。人们发现 ,血红蛋白中的血红素是通过铁与组氨酸残基的侧链咪唑配位于蛋白质上 ,因此 ,人们对金属卟啉与咪唑类配体的轴向配位反应研究产生了极大兴趣 [1] 。有关取代四苯基卟啉金属配合物的合成和轴配反应热力学研究已有很多报道 ,但人们的研究尚处在对称且苯环上连有较小取代基的四苯基卟啉锌、钴、铁等模拟化合物的合成、结构表征及光谱和配位反应热力学的研究阶段 [2 -4 ]。对于结构不对称且卟啉中苯环上连有氨基酸的四苯基卟啉配合物…     

用NH4Cl氯化Li2CO3的研究

近年来利用熔盐电解法制备Al-Li合金已开始受到重视。但由于LiCl具有强烈的吸水性给工艺及其电解质溶液物化性质的研究带来很大的困难。因此本文利用热分析手段研究了NH_4Cl氯化Li_2CO_3的反应,为今后在电解工艺及其基础研究中用NH_4Cl定量氯化Li_2CO_3取代直接使用LiCl提供依据。