烷基亚磺酰氯与格氏试剂反应：用于方便的合成烷基亚砜

在氯化锌存在下，利用烷基亚磺酰氯与格氏试剂反应，以良好的产率合成了相应的烷基亚砜。     

ω-氟砜基氟烷基格氏试剂的制备及其反应

合成氟烷基酮的通用方法是将全氟烷基金属试剂与羰基类化合物反应。但对于ω位带有官能团的全氟烷基金属试剂的研究,唯一的例子是:     

ω-氟砜基氟烷基格氏试剂的制备及其反应

本文研究了5-碘-5-氧杂八氟戊磺酰氟与乙基格氏试剂的反应, 发现只有乙基格氏试剂与碘离子发生交换后的产物而没有得到格氏试剂与磺酰氟反应的产物砜。     

格氏试剂的形成及某些单电子转移反应

本文介绍了格氏试剂的形成机理、组成、结构以及某些经由单电子转移的反应,对于深入了解这方面内容具有一定意义。     

有机硼酸盐的化学 Ⅲ.三烷基炔基硼酸锂与CO_2反应中烷基转移的难易顺序及反应温度的影响

我们曾报道在合适的条件下三烷基炔基硼酸锂可以与CO_2反应,当亲电试剂CO_2进攻三烷基炔基硼酸锂中炔基上的β-碳原子时,硼原子上的一个烷基即向炔基的α-碳上转移.而且转移烷基在反应前后其构型保持不变.反应式为     

三苯基丙烯腈衍生物的定量结构-活性关系研究

应用半经验量子化学AMl方法得到了24种三苯基丙烯腈衍生物的优势构象，利用AMl方法和分子图形学技术获得其电子结构、几何结构及拓扑结构参数，并将这些参数与三苯基丙烯腈衍生物对乳腺癌细胞(MCF-7)的生物活性相关联．结果表明，三苯基丙烯腈衍生物对MCF-7的活性与羟基指示数、分子表面积和B环上原子净电荷之和之间存在良好的多元线性相关性，成功地建立了三苯基丙烯腈衍生物的构效关系式．     

单质硒促进的格氏试剂自偶联反应

通过探讨镁屑和单质硒的量、催化剂及配体等对反应的影响,获得制备对称偶联产物的较佳实验条件,成功得到较高分离产率(65%～92%)的15个对称芳烃或烷烃偶联目标产物,在实验结果基础上,提出了硒可在反应中循环的合理机理.     

电荷转移聚合研究——三苯基磷引发丙烯腈光聚合

研究了三苯基磷(TPP)引发丙烯腈(AN)光聚合。测定了光聚合速率 R_p与单体浓度、引发剂浓度的关系为:R_p=K[AN]~(1.49)[TPP]~(0.47)以及光聚合反应活化能E_α=6.16千卡/摩尔,从激发态电荷转移机制,讨论了引发聚合机理。     

格氏试剂与酮反应的一个重要途径: 单电子转移

本文着重阐述了格氏试剂和酮的性质影响反应的一般规律,介绍了普遍接受的格氏试剂与酮反应的机理。讨论了溶剂及微量过渡金属对反应的影响。     

金属有机配合物对格氏试剂与酰氯交叉偶联反应的催化活性

本文采用镍-膦配合物、有机钛化合物、氯化钕、乙酰丙酮希土配合物、含二茂铁基羰基三氟丙酮希土配合物(HL)_3Ln·xH_2O共十余种,作为苯甲酰氯与正丁基格氏试剂的交叉偶联反应的催化剂,发现各种有机钛化合物都具有和经典镍膦配合物类同或略好些的催化活性,而(HL)_3Ln,当Ln为Ce、Pr、Nd、Sm、Ho、Er时,均表现良好催化活性,反应产率高,反应选择性很好(～100％),本文同时讨论了反应的催化作用过程。     

NEW PRODUCTS OF REACTION OF LAWESSON'S REAGENT WITH DIOLS

Reaction of the Lawesson's reagent (LR) with aliphatic 1,2- and 1,3-diols as well as with aromatic 2,2′-dihydroxybiphenyl led to new products. Stable di-tert-butylammonium salts of bis-anisyldithiophosphonic acids 6 were isolated and were then converted into unique 9-, 9-, and 10-membered cyclic disulfides 7 and into S,S-dimethyl esters 8. The salts of bis-anisyldithiophosphonic acids 6 were shown to be capable of splitting the disulfide bond of Ellman's reagent.     

IN-SITU SYNTHESES OF ALKYLLITHIUM COMPOUNDS UNDER ULTRASONIC IRRADIATION

Abstract

The syntheses of organometallics such as alkyllithium compounds are performed. Furan and thiophene derivatives were prepared. Parameters which influence the yield have been optimized. The more important were the physical states of lithium and its sodium content and the nature of the substrate.     

POLYMER-SUPPORTED GRIGNARD REAGENT AND ITS USE IN THE FUNCTIONALIZATION OF POLYMER

Polymeric Grignard Reagent (PGR) based on the chloromethylated poly(ST-co-DVB) resinhas been prepared by means of anthracene-magnesium complex in THF (Anth-Mg-THF), andpolymer matrix with long polymethylene spacer was synthesized via the coupling reaction betweenPGR and α, ω-dibromoalkanes. Based on the studies of factors affecting the coupling, such ascatalyst,reaction time,the length of spacer etc.,this paper offers the optimal reaction conditionsand three typical experiment procedures. The mechanism for the formation and coupling reactionof PGR are also discussed.     

新树型配体TTBA与铜配合物的研究

研究了新配体TTBA与二阶铜离子生成配合物的光度特征和电化学 特征。在较宽的PH范围内，新试剂和铜离子形成1：2的棕黄色配合物，并且在一定范围内具有良好的线性关系。通过电化学方法和光度法都可以证明，文中合成的新试剂氮三没食子酸三乙胺测定Cu^2 具有很高的灵敏度和选择性，在实际生产中具有一定的应用价值。     

新试剂对羧基苯基荧光酮与铀(Ⅵ)显色反应的研究

研究了对羧基苯基荧光酮与铀(Ⅵ)的显色反应。在pH6.5氨水-乙酸缓冲溶液和阳离子表面活性剂溴化十六烷基三甲铵存在下,铀(Ⅵ)与对羧基苯基荧光酮发生灵敏的显色反应,其配合物最大吸收峰位于570nm,表观摩尔吸光系数为7.52×104L.mol-1.cm-1。铀(Ⅵ)浓度在0~100μg/25mL符合比耳定律。在室温下,试剂与铀(Ⅵ)的显色反应立即完成,配合物吸光度至少可以稳定12h。体系具有较好的选择性,绝大多数金属离子有较高的允许量,铀(Ⅵ)的伴生元素钍和稀土允许量达10mg,方法已应用于水样中痕量铀的测定,结果满意。     

LIGAND COUPLING AND PSEUDOROTATION IN THE REACTION OF ALKYL 2-PYRIDYL SULFOXIDE WITH GRIGNARD REAGENTS

Abstract

In the reaction of benzyl 2-pyridyl sulfoxide (1) with C₆H₅CH₂MgCl, the incoming Grignard reagent tends to couple preferentially with 2-pyridyl group at lower temperatures, whereas, at higher temperatures, coupling between benzyl and 2-pyridyl groups with 1 tends to increase due presumably to the relatively more facile pseudorotation² at higher temperatures.     

D-葡萄糖D-果糖与硼的有机物形成配合物的稳定性研究

葡萄糖异构酶加速葡萄糖与果糖的平衡,平衡时果糖含量为42％左右,体系中加入一些硼酸盐,果糖的含量提高到80％左右,究其原因可能是由于葡萄糖和果糖与硼酸盐形成不同稳定性的配合物。虽然Roy,Conner,Daris,Belcher,Lorand等都已报导了这些配合物的稳定常数,概括结果分歧较大。Belcher曾首次报导了硼酸与D-果糖的配位数为     

ORGANOPHOSPHORUS COMPOUNDS,XXXIII THE REACTION OF PHOSPHITE ESTERS WITH QUINISATIN

Abstract

Trialkyl phosphites react with quinisatin (1) and its monohydrate 3 to give the corresponding phosphate derivatives 2a-c. The same compounds are obtained upon reacting 1 and/or 3 with the proper dialkyl phosphite. Structural reasonings based on IR, MS and NMR spectral data, are presented.     

ORGANOPHOSPHORUS COMPOUNDS,XXVIII. THE REACTION OF TRIPHENYLPHOSPHINE SULFIDE WITH TETRACHLOROBENZOQUINONES

Abstract

The reaction of triphenylphosphine sulfide with tetrachloro-o-benzoquinone gives a complex of the corresponding hydroquinone and triphenylphosphine oxide. Elemental sulfur is the other product. The tetrachloro-p benzoquinone does not react to any noticeable extent under similar conditions. Several mechanisms are proposed to explain the results.