Synthesis, Chemistry, and Applications of Heterocyclic Cage Compounds (V)

The synthesis and chemistry of polycyclic of cage compounds have attracted considerable attention in recent years. The vast majority of the work reported in this area has dealt with carbocylic cage compounds. On the other hand, the synthesis and chemistry of heterocyclic cage compounds have received less attention. Recently, we envisioned that studies on the synthesis and chemistry of heterocyclic cage compounds can greatly expand the scopes and utilities of cage compounds.1 As part of a program that involves the synthesis, chemistry, and application of heterocyclic cage compounds, we report here the synthesis of new thia-oxa-cage compounds and the chemical nature of these thia-cages.     

高张力笼形氮杂环化合物的合成

以六苄基六氮杂异伍兹烷(HBIW)为母体,Pd(OH)₂/C为催化剂,在温和条件下,通过选择性催化氢解脱苄,使部分或全部苄基被其它官能团(如CH₃O-,C₂H₅-,CHO-)取代,合成了4种N-取代六氮杂异伍兹烷,并鉴定了它们的结构.这些化合物都是高张力的笼形氮杂环化合物,且均可作为合成六硝基六氮杂异伍兹烷(HNIW)的前体,而HNIW是当今最引人注目和最有军用前景的高能量密度化合物(HEDC).     

Synthesis of Heterocyclic Compounds from Metallated Unsaturated Compounds and Isothiocyanates. (Review)

Novel syntheses of heterocyclic compounds resulting from reactions of metallated acetylenes, allenes, and conjugated dienes with isothiocyanates and from reactions of the latter with strong bases are reviewed.     

N-Cyanoimines in the Synthesis of Heterocyclic Compounds. (Review)

Methods for the synthesis of N-cyanoimines in the period between 1959 and 2003 and their chemical properties are examined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–973, July, 2005.     

Catalytic Synthesis of Some Sulfur-containing Heterocyclic Compounds. (Review)

Researches on the synthesis of sulfur-containing heterocyclic compounds at the G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, are reviewed. They include the synthesis of thiolane by the recyclization of THF in hydrogen sulfide; the synthesis thiacycloalkanes by the hydrogenation of thiophenes; the synthesis of 4-methylthiazole by the reaction of SO₂ with methylisopropylideneamine; the synthesis of thiophenes by the heterocyclization of aliphatic compounds of sulfur and dehydrogenation of thiacycloalkanes; the synthesis of thiolane 1,1-dioxide by the hydrogenation of 2- and 3-thiolene 1,1-dioxides and 3-alkoxythiolane 1,1-dioxides; the synthesis of sulfoxides by the oxidation of thiacycloalkanes with atmospheric oxygen.     

缩杂环酮化合物的合成

酮(troponoid)是自然界中某些抗菌素和毒菌的基本骨架组成。近年来,人们合成了许多具有各种生理活性的酮类化合物,而     

Synthesis and Structural Chemistry of Tungstoarsenates(V)

An overview of the synthesis and of the structural chemistry of tungstoarsenates(V) of the 1:12 and 2:21 families is presented with special emphasis on the 2:20 species. The molecular structure of [As₂W₂₀O₇₁(H₂O)₃]¹²⁻ has been determined by single-crystal X-ray diffraction of K₁₂[As₂W₂₀O₇₁(H₂O)₃]·23H₂O and that of [As₂W₂₀O₇₀(H₂O)₂]¹⁰⁻ has been inferred from a ¹⁸³W NMR study in aqueous solution.This paper is dedicated to Professor Michael Pope in recognition of his invaluable contribution to polyoxometalate chemistry.     

Ball Milling for Heterocyclic Compounds Synthesis in Green Chemistry: A Review

This review aims to present the application of ball milling for the synthesis ofdifferent heterocyclic compounds in very good yields. The method is a simple, economical, and ecofriendly process for synthesizing heterocycles, which is a large family of organic compounds. They are extremely important and have wide-ranging pharmaceutical and industrial applications.     

(Chloromethyl)alkoxysilanes,Silethanes, and Silethenes in the Synthesis of Linear and Heterocyclic Compounds

The use of N,N-dimethylhydrazine or its trimethylsilyl derivatives in silylation, silamethylation, silethenation, and transsilylation allows synthesis of previously unknown linear and heterocyclic compounds.     

零价铜催化含氮杂环的N-芳基化合物的合成

由于氮的负性基团的亲核性低,使得在芳香卤代物的环上引入含氮基团的反应(或者说在含氮杂环化合物的亚氨基上进行 N-芳基化)不易进行,因而需要强烈的反应条件或加入催化剂促使反应的发生。曾有人用一价铜盐作为催化剂研究了芳香卤代物的亲核取代反应。本文用零价铜催化的方法,合成了 N-芳基含氮杂环化合物(3 a～h)。反应机理可能是芳香肉代物与铜首     

Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.