二碘化钐还原硫代碳酸酯

在ＳｍＩ＿２－ＨＭＰＡ－ＴＨＦ－ｔ－ＢｕＯＨ体系中，硫代碳酸酯的酰硫键发生还原断裂反应，得到相应的二硫醚产物。     

钐－二氯二茂钛体系促进的碳－硫键的还原断裂－二烷基二硫醚的合成

A mild and rapid method was found for the reductive cleavage of the carbon-sulfur bond in the alkylthiocyanates by samarium/Cp2TiC12 system to give the corresponding dialkyl disulfides in moderate to good yields.     

三苯基锗二硫代氨基甲酸酯的合成及表征

近年来 ,人们相继合成了有机锗倍半硫化物、有机锗硫杂环戊酮、含硫的螺环有机锗等化合Scheme1　 Synthetic route of compound物[1,2 ] .但烃基锗二硫代氨基甲酸酯类化合物尚未见报道 .我们 [3,4 ] 发现 ,有机锡二硫代氨基甲酸酯类化合物有很强的生物活性 .鉴于有机锗化合物比有机锡化合物毒性低得多 ,且副作用小 ,我们以三苯基氯化锗和二硫代氨基甲酸盐为原料 ,合成了一系列新型的有机锗含硫衍生物 (反应式如Scheme1所示 ) ,并对其结构进行了表征 ,初步生物活性测试结果表明 ,部分化合物显示出较强的抗癌活性 .1　实　　验1 .1　仪器与…     

二正丁基二硫代氨基甲酸锌配合物的量子化学研究

The geometric configurations of binuclear Zinc(Ⅱ) complex Zn₂[(n-Bu)₂NCSS]₄ and the ligand Na[(n-Bu)₂ NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G^* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π^* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π^* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS₂ and to increase the energy needed for the π → π^* and n → π^* transitions, and results in the absorption bands shifting towards the short wavelength direction.     

三丁基锡二硫代氨基甲酸酯的合成及表征

通过三丁基氯化锡与二硫代氨基甲酸盐反应,合成了１０个 三丁基锡二硫代氨基甲酸酯,利用元素分析,ＩＲ、ＨＮＭＲ、ＵＶ和ＴＧ－ＤＴＡ表征了这些化合物结构,测定了部分化合物的生物活性。     

无溶剂无催化剂条件下二硫代氨基甲酸酯衍生物的合成研究

主要研究了二硫代氨基甲酸酯衍生物的合成,将脂肪胺、CS2与α,β-不饱和羰基化合物或卤代烃在无溶剂无催化剂室温条件下,"一锅法"进行了Michael-type的加成反应,合成了二硫代氨基甲酸酯衍生物.该方法产率高,操作简单,是一种原子经济的合成方法,并可大规模地用于制药及农药方面.     

三苄基锡二硫代氨基甲酸酯的合成

三苄基锡二硫代氨基甲酸酯的合成尹汉东马春林＊张如芬（聊城师范学院化学系聊城２５２０５９）关键词三苄基氯化锡，二硫代氨基甲酸盐，合成１９９７－０７－１０收稿，１９９７－０９－０９修回山东省自然科学基金资助项目三烃基锡衍生物是一类具有较强生物活性的有机锡...     

二苯基锗二硫代氨基甲酸酯的合成及表征

合成了10种二苯基锗二硫代氨基甲酸酯Ph2Ge(S2CNR2)2,用元素分析、IR、^1H NMR和MS表征了这些化合物的结构,体外实验表明,这些化合物对MCF－7,WiDr和EC癌细胞具有较的抑制活性。     

SmI_2-promoted imino-Reformatsky reaction for facile synthesis of enantioenriched β-amino acid esters

A facile and efficient method for the stereoselective synthesis of β-amino acid esters via SmI2-promoted imino-Reformatsky reaction is described.Asymmetric addition of tert-butyl bromoacetate to N-tert-butanesulfinyl aldimines afforded β-amino acid esters in moderate to high yields with excellent diastereoselectivities.The synthetic utilities of the tert-butyl β-amino acid esters were expanded by the preparation of β-lactams and 3-aminoindan-1-ones derivatives.     

α-羰基硫代甲酰胺与溴的反应研究

报道了α 羰基硫代甲酰胺与溴在三乙胺存在下的反应 ,合成了二 [( 1 芳基亚胺基 1 苯甲酰基 )甲基 ]二硫醚类化合物 ,产率为 60 %～ 65 %.它们的结构经元素分析、红外光谱、核磁共振光谱和质谱分析得到确证     

二碘化钐促进的硒代酯的合成

用SmI2/THF/HMPA体系在室温下使二芳基二硒醚中的Se-Se键还原断裂成硒负离子物种, 继而与酸酐作用得到硒代酯, 该反应条件温和中性, 产率良好, 提供了合成硒代酯的一个新途径。     

二硫代乙二酰胺合镍在硫化镉纳米晶表面的逐层配位组装

CdS nanocrystals, which were surface modified by poly (nickel dithioxamide) [Ni(DTO)]_n, were prepared and characterized. TEM image showed that the shape and the outward aspect of the modified CdS sample were essentially the same as those of the original material and no impurities were found. The characteristic IR peaks at 1 513cm^-1 and 870 cm^-1 confirmed the success in assembling [Ni(DTO)]_n on the surface of CdS. For XPS spectra, the characteristic bands of Ni2p3/2 and Ni2p1/2 appeared at 856 eV and 877 eV indicating the nickel in Ni(Ⅱ) oxidation state. The solid state electronic spectra showed the improvement in surface energy gap, which was changed from 2.38 eV to below 1.91 eV.     

α-氧代烯酮环二硫代缩酮化学(ⅩⅫ) ——硫醇(酚)为亲核体的α-氧代烯酮环二硫代缩酮与2-甲基烯丙基氯化镁加成物的取代-环合芳构化反应

缩酮基为五元和六元环的α-氧代烯酮环二硫代缩酮与2-甲基烯丙基氯化镁反应得1,2-加成产物。所得加成产物在酸催化条件下以乙硫醇为亲核体时生成芳基乙基硫醚;苯硫酚为亲核体时,产物为芳基苯基硫醚。同样实验条件下,缩酮基为甲硫基的α-氧代烯酮二硫代缩酮与2-甲基烯丙基氯化镁的1,2-加成则生成芳构化产物芳基甲基硫醚。本实验从亲核体的选用上进一步拓展了所述取代-环合芳构化反应,并进一步验证了缩酮基结构对反应活性的影响。     

Chiral Borated Esters in Asymmetric Synthesis： 1. The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.     

3-硫代甲酰基中氮茚与三丁基膦的反应

2-Phenyl-3-thioformylindolizine and 1,2-dimethyl-3-thioformylindolizine undergo a novel desulfur coupling reaction in the presence of tributylphosphine to give （E）-1,2-bis（3-indolizinyl）ethenes in high yields. The structures of products were confirmed by IR, ^1H NMR, MS, elemental analysis and single crystal X-ray diffraction analysis. The mechanisms involved in various stages of the reaction were discussed.     

硒作用下苯胺和硫醇羰基化合成硫代氨基甲酸酯

报道了一种新颖且简易的合成硫代氨基甲酸酯的方法. 在硒作用下, 苯胺和硫醇的羰基化反应在室温常压条件下顺利进行, 大多数目标产物硫代氨基甲酸酯的收率从中等到较高. 硒在反应结束后可方便地回收并能循环使用.     

聚2,2′-二硫代二苯胺的化学合成与表征

从2-氨基苯硫酚出发制备二硫代二苯胺,以此为原料与重铬酸钠在低温溶液中合成聚二硫代二苯胺,并对产物进行了红外光谱、热重、X射线、光电子能谱和扫描电镜分析表征.     

二硫代二乙二醇水基抗磨剂的合成及性能研究

以硫磺、硫化钠、2-氯乙醇为起始原料合成了二硫代二乙二醇。以乙醇为溶剂,硫化钠187mmol,n(2-氯乙醇)：n(硫磺)：n(硫化钠)=1．8：1．2：1．0,回流反应30min,二硫代二乙二醇(其中硫醚硫含量为39．54％)产率达88．5％。含二硫代二乙二醇85．7％的水基抗磨剂具有优良的极压性(PB=804N),但抗磨性不理想(D30min^196N=0．72mm)。     

二硫代酯的单晶结构及荧光性能的研究(英文)

合成了两种单晶化合物二硫代酯1 和2,并对其经行了表征.二硫代酯1属于单斜晶系,空间群是P21/n; 二硫代酯2属于正交晶系,空间群是Pbca.此外,分别研究了两种二硫代酯在液态和固态中的荧光性能,发现二硫代酯1和2在乙腈溶剂中有很强的荧光,而在固体状态下没有荧光.这可能是由于在固态下分子间的堆积造成了荧光团发生迅速的π-π碰撞,从而导致荧光的自身淬灭.     

Theoretical Study on the Hetero-Diels-Alder Reactions between 3-Pyridinedithioesters and 1-Phenylsulfanylbutadiene

The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reac- tions between 3-pyridinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT) at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C bond and the opposite results are found in other reactions. The BF3 catalyst may lower the activation barriers by changing the energies of LUMO for 3-pyridine- dithioester. THF solvent has trivial influence on the potential energy surface of these reactions. With the BF3-catalyzed reactions, regioselectivity and stereoselectivity observed experimentally were predicted correctly by calculations and these results originate probably from C-H···F interaction in two transition states.