立体专一性地合成（Z）-α-氟-β-三氟甲基乙烯基碘化物和应用于合成多氟噻吩基双烯烃

The direct iodination of polyfluorinated vinyl stannanes by tin-iodine exchange methodology was achieved giving （Z）-α-fluoro-β-trifluoromethyl vinyl iodides stereospecifically. Changing the substituent in R group from the electron-withdrawing group to electron-donating group led to an increase in the yield from 78% to 90%, while it was moved from para to meta position the reaction did not afford a dramatic change in the yield （90% to 95%）. In addition, this reaction also can be applied to the vinyl stannane with heterocyclic group. The further coupling reaction of prepared vinyl iodide containing heterocyclic moiety with （Z）-α-fluoro-β-trifluoromethylstannanes gave polyfluorinated heterocyclic alkadienes with 2E,4E-selectivity.     

Reaction of Grignard Reagents with Diethyl Perfluoroacyl (1-Cyanoethyl)phosphonates. Synthesis of Perfluoroalkylated α,β-Unsaturated Nitriles with Predominant Z-Selectivity

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ω－芳氧乙酰氧基－ω－（1H－1，2，4－三唑－1－基）苯乙酮衍生物的研究

报道了１５种含三唑取代的芳氧乙酸苯甲谈甲酯类新化合物；产物的结构经ＩＲ、１ＨＮＭＲ、ＭＳ及元素分析证实。生物活性测定结果表明：部分化合物表现出良好的除草或杀菌及植物生长调节活性。     

甲氧羰基亚甲基三苯基胂和苯甲酰基亚甲基三苯基胂与α,β-不饱和酮的反应

本文得到环丙烷衍生物或类似于正常的Wittig反应产物,视α,β-不饱和酮中相邻于羰基的取代基而异.当取代基是空间位阻较大的基因,如苯基,则胂试剂进攻双键,得到环丙烷衍生物;反之,胂试剂进攻羰基,得到类似于正常的Wittig反应产物.前者是合成1,2,3-三取代环丙烷较好的方法,其中Ⅲ_BA,Ⅳ_AB,Ⅳ_AC,Ⅲ_BC是立体专一性的.文中根据构象分析,讨论了反应的机理;并从¹H核磁共振谱,确定了环丙烷衍生物的构型.     

新型含芳氧乙酸酯基三唑酮类化合物的合成及生物活性研究

通过芳氧乙酸与2-溴-4,4-二甲基-1-(1H-1,2,4-三唑-1-基)-3-戊酮反应, 合成了14个新型含芳氧乙酸酯基三唑酮类化合物. 所有化合物均经核磁、元素分析确证, 部分化合物进行了红外和质谱的测定. 生物活性测试表明部分化合物具有良好的生物活性.     

黄芩素磺酸根与钙离子的自组装作用

黄芩素磺酸根与钙离子在水溶液中自组装得到黄芩素-8-磺酸钙[Ca(H2O)6(C15H9O5SO3)][C15H9O5SO3].8H2O单晶,采用单晶X射线衍射对其组成和结构进行了研究。单晶衍射分析表明:黄芩素-8-磺酸钙属三斜晶系,空间群P1;结构中包含2个黄芩素-8-磺酸根阴离子、1个钙离子、6分子配位水和8分子结晶水。配位水、结晶水和黄酮骨架上的磺酸根、酚羟基、羰基之间以多种氢键相连,黄酮骨架之间存在π…π芳香堆积作用。配位作用、π…π芳香堆积、氢键以及阴阳离子间的静电引力将黄芩素-8-磺酸钙自组装成具有三维结构的超分子。     

The crystal and molecular structure of pentafluoropropionylbenzoylmethylene triphenylphosphorane

The crystals of pentafluoropropionylbenzoylmethylene triphenylphosphorane that bears two strongly electron-withdrawing groups in alkylidene moiety are monoclinic and its space group is C2/c, with a = 11.271(3)Å, b = 18.253(6)Å, c =23.938(7)Å, β = 91.09(2)°, z = 8. The X-ray diffraction intensity data were collected on a four-circle diffractometer. The structure has been solved by direct method and refined by block-diagonal least-squares method. The final R- index was 0.075 for 3146 independent observed reflexions. In this paper the structure of this ylide is compared with that of corresponding arsonium ylide previously reported. Both ylidic skeleton structures are planar with sp² hybridization. The bond length of P-C(1) is 1.748 (5)Å with bond order. 1.60 while the bond order of As-C(1) in the corresponding arsonium ylide is 1.46, indicating that the phosphonium ylide has a greater contribution of “ylene” structure to the overall structure. As a result the phosphonium ylide should be less reactive than the corresponding arsonium ylide. In both ylides, (he major delocalized canonical forms of negative charge are shown to be 3.     

碳-碳重键的新合成方法学研究

本研究工作包括下列8方面:(1)一种不同于Wittig反应的新的烯化方法,含氟β-酮基磷盐在有机合成中的应用。(2)"一锅"法的碳-碳双键形成反应。(3)一种新的叶立德阴离子的形成方法。(4)消去三苯基胂形成碳-碳双键的合成方法学。(5)立体选择性地控制合成(Z)或(E)-碳-碳双键化合物的新方法。(6)亲核试剂对全氟酰基膦酸酯进攻为基础的新合成方法学。(7)还原烯化反应的合成方法学。(8)含氟碳-碳叁键的合成方法学。     

全氟-[2]-炔酸乙酯的合成和炔酯-烯醚重排的立体化学

本文报道了三氟丁-[2]-炔酸乙酯(2a)和七氟己-[2]炔酸乙酯(2b)的合成。产物在水溶液中用氢氧化钠皂化,和相应的甲酯一样,也发生特殊的炔酯-烯醚重排,乙氧基迁移到β碳上,酸化后,分别得到3-乙氧基-4,4,4-三氟丁-[2]-烯酸(3a)和3-乙氧基-4,4,5,5,6,6,6-七氟己-[2]-烯酸(3b)。其结构经元素分析,红外吸收光谱和核磁共振谱证明。文中还研究了炔酯-烯醚重排反应的立体化学。根据重排产物的~1H NMR数据,确定重排是高度立体选择性的,所有产物中Z异构体占94％以上。根据构象分析,得到合理的解释。NMR的溶剂效应和NOE增强,也进一步确证了重排产物的构型。     

Homocoupling of Polyfluorovinylstannanes Mediated by a Novel Combination of CuCl/2,2''''-Dipyridyl. Stereospecific Syn-thesis of Polyfluorinated Alka-2,4-dienes

Introduction Stille reaction, which is known as the cross-coupling reaction between organostannanes and organic electro-philes, has become a widely employed synthetic tool in organic synthesis for the construction of carbon-carbon single bond,1 particularly in the synthesis of naturally occurring compounds.2 But the homocoupling reaction of vinylstannanes is still limited. Intramolecular CuCl mediated oxidative coupling of alkenyltrimethylstan-nane has been reported3 and applied to the synthe…