氯化π-单取代环戊二烯基镍(Ⅱ)的双齿膦配合物合成和催化

合成了化学式为[(η~5一RC_5H_4)NiPh_2P(CH_2).PPh_2]Cl的六个配合物(式中R=Me,Et;n=2(dppe ).n=3(dppp),n=4(dppb).并用IR和~1H NMR对其进行了表征.考察并讨论了它们对苯基溴化镁与氯化苄和反式-均二氯乙烯交叉偶联反应的催化活性.     

2-(1,11-十一亚甲基)-5-取代亚氨基-△~3-1,3,4-噻二唑啉的合成及杀菌活性

通过环十二酮与 N -取代氨基硫脲的缩合反应 ,合成了一系列 N -取代环十二酮缩氨基硫脲 ,经Mn O2 氧化关环 ,得到 1 5种未见文献报道的标题化合物 ,其结构经 IR,1 3C NMR,元素分析的确证 .初步实验表明 ,部分化合物具有一定的杀菌活性     

α，α-二取代环十二酮的构象

利用分子力学计算，1~H NMR和单晶X射线衍射分析技术研究了α，α-二取代 环十二酮的构象．结果势构象骨架仍是[3333]-2-酮，在晶体和溶液中，它们的优 势构象均为α-角顺、α-角反-二取代[3333于α-角反位，后上基团处于α-角顺位.     

α-单取代环十二酮肟及缩氨基硫脲的合成及晶体结构

单晶X射线衍射分析表明, α-单取代环十二酮与氨衍生物羟胺和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α-单取代环十二酮肟或缩氨基硫脲. 利用底物的“角位羰基参与反应”原理, “记忆效应”及进攻试剂与底物是否形成氢键解释了这一实验结果. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α-角反取代环十二酮肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α-边外取代环十二酮肟或缩氨基硫脲.     

Alkylation of cyclododecanone with α,ω-dibromoalkanes under conditions of phase-transfer catalysis

Alkylation of cyclododecanone with ,-dibromoalkanes Br(CH) _n Br (n=3, 4, 5) under conditions of phase-transfer catalysis in the presence of KOH results in the formation of either bicyclic ketones forn=3 and 5 or a mixture of bicyclic and spirocyclic ketones forn=4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1436–1438, August, 1994.     

Graphs to chemical structures. 4: Combinatorial enumeration of planted three-dimensional trees as stereochemical models of monosubstituted alkanes

Planted three-dimensional (3D) trees, which are defined as a 3D version of planted trees, are enumerated by means of Fujita’s proligand method formulated in Parts 1–3 of this series [Fujita in Theor Chem Acc 113:73–79, 80–86, 2005; Fujita in Theor Chem Acc 115:37–53, 2006]. By starting from the concepts of proligand and promolecule introduced previously [Fujita in Tetrahedron 47:31–46, 1991], a planted promolecule is defined as a 3D object in which the substitution positions of a given 3D skeleton are occupied by a root and proligands. Then, such planted promolecules are introduced as models of planted 3D-trees. Because each of the proligands in a given planted promolecule is regarded as another intermediate planted promolecule in a nested fashion, the given planted promolecule is recursively constructed by a set of such intermediates planted promolecules. The recursive nature of such intermediate planted promolecules is used to derive generating functions for enumerating planted promolecules or planted 3D-trees. The generating functions are based on cycle indices with chirality fittingness (CI-CFs), which are composed of three kinds of sphericity indices (SIs), i.e., a _d for homospheric cycles, c _d for enantiospheric cycles, and b _d for hemispheric cycles. For the purpose of evaluating c _d recursively, the concept of diploid is proposed, where the nested nature of c _d is demonstrated clearly. The SIs are applied to derive functional equations for recursive calculations, i.e., a(x), c(x ²), and b(x). Thereby, planted 3D-trees or equivalently monosubstituted alkanes as stereoisomers are enumerated recursively by counting planted promolecules. The resulting values are collected up to 20 carbon content in a tabular form. Now, the enumeration problem initiated by mathematician Cayley [Philos Mag 47(4):444–446, 1874] has been solved in such a systematic and integrated manner as satisfying both mathematical and chemical requirements.     

Reaction of octafluorocyclopentene with various carbon nucleophiles

The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields.     

单取代芳烃对位选择性碳氢活化反应研究

以单取代芳烃为芳基化试剂,以羰基为导向定位基团,研究了单取代芳烃对位选择性与芳香酮的交叉脱氢偶联反应。该方法的高选择性一方面体现在用作芳基化试剂的单取代芳烃能够单一选择性地发生对位碳氢活化,并生成对位取代产物;另一方面,作为弱导向基团的羰基具有优异的邻位导向定位作用,高选择性地发生羰基邻位碳氢键活化。此外,该方法还具有反应条件温和、反应效率高、底物范围广、氧化剂廉价易得等优点,为对位取代联芳基化合物的合成提供了一条切实可行的途径。     

2-胺甲基环十二烷酮酯类化合物的合成及其生物活性研究

环十二烷酮衍生物;Mannich碱;反应;2-胺甲基环十二烷酮酯类化合物的合成及其生物活性研究     

N-取代环十二酮缩氨基硫脲的氧化环合反应

以环十二酮为起始物合成的一系列N-取代环十二酮缩氨基硫脲(Ⅰ)经二氧化锰氧化环合为2-(1,11-十一亚甲基)-5-取代亚氨基-△^3-1,3,4-噻二唑啉(Ⅱ)。Ⅱ的结构得到IR,13^CNMR和元素分析的确证。反应中同时分离到一个副产物,经IR,13^CNMR,EIMS和元素分析确定其结构为2-(1,11-十一亚甲基)-5-亚氨基△^3-1,3,4-噻二唑啉(Ⅲ)。据此提出了Ⅰ经二氧化锰氧化环合为Ⅱ的两步反应机制,此机制可以合理地解释Ⅱ和Ⅲ的生成。