Synthesis of 3,6,10,13-tetrathia[6.6.2]propellanes from 1,1,2,2-Tetrakis-(bromomethyl)cyclobutane

Summary A synthesis of two new tetrathia[6.6.2]propellane systems, each containing one cyclobutane ring, is described. On the basis of¹HNMR, UV/Vis and mass spectra, the possibility of the formation of an isomeric bispirane is discussed.

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Synthese von 3,6,10,13-Tetrathia[6.6.2]propellanen aus 1,1,2,2-Tetrakis(brommethyl)cyclobutan

Zusammenfassung Es werden die Synthesen zweier neuer Tetrathia[6.6.2]propellansysteme beschrieben, die jeweils einen Cyclobutanring enthalten. Auf der Grundlage von NMR-, UV/Vis- und Massenspektroskopie wird die Möglichkeit der Bildung isomerer Bispirane diskutiert.

     

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).     

芳香偶氮化合物的合成研究进展

综述了芳香偶氮化合物的主要合成方法,包括重氮偶联反应、米尔斯反应、胺的氧化、芳肼的的氧化、硝基化合物的还原偶联反应、重氮盐的二聚反应、叠氮化合物的热解等,并对各方法的优缺点进行了简要评述。     

芳酰基芳基偶氮化合物的合成

芳酰基芳基偶氮化合物的合成;芳酰基芳基偶氮化合物;哌啶氮氧自由基;芳酰基芳肼;相转移催化     

Studies on Organophosphorus Compounds: The Synthesis of [1,3,2]-Diazaphospholes and [1,3,2]-Oxaazaphospholes

A number of spiro[cyclopentane (cyclohexane, and cycloheptane)-1,4′-perhydro-[1,3,2]diazaphosphole] derivatives (3a–c, 5a–c, 11a–c, and 12a–c) and spiro-[cyclopentane (cyclohexane, and cycloheptane)-1,4′-perhydro[1,3,2]oxaazaphos-phole] derivatives (7a–c) were prepared via an interaction of 2,4-bis-(4-methoxy-phenyl)-1,3,2,4-dithiaphosphetane-2,4-disulphide (1) with substances containing two functional groups.     

Synthesis and Properties of Novel Aromatic Azo Compounds from Hydroxyazobenzene and Cyanuric Chloride

A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p‐hydroxyazobenzene, 4,4′‐dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV‐vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV‐vis absorption ability of the synthesized compounds greatly improved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.     

氰基亚胺与亚甲基二氢苯并呋喃二酮类化合物的[3+2]环加成反应:螺吡唑类化合物的合成

采用具有环外双键的二氢苯并呋喃二酮类化合物和氰基亚胺的[3+2]环加成反应,在温和条件下,以高产率(78%~94%)和高非对映选择性(>20∶1dr)构建了一系列具有螺环结构的吡唑类化合物.     

Zn-Al-Ce三元类水滑石的制备及性质研究

采用共沉淀法，水热合成层状化合物一硝酸根柱撑锌铝铈三元类水滑石，分别测定了各种单一金属盐溶液及M^2 ／M^3 摩尔比为2，Ce^3 ／Al^3 摩尔比为0．25的混合金属盐的NaOH滴定曲线，并利用XRD对不同条件下合成产物进行物相分析。实验结果表明：在M^2 ／M^2 =2，Ce^3 ／Al^3 =0．07～0．50，pH=5．8～6．5条件下进行多种离子共沉淀，并经120℃、6h水热处理后，均能合成结构单一的ZnAlCe—HTLLcs，利用TG—DTlA、FT—IR、ICP对合成物进行了表征，筛选出适宜的合成条件，并对HTLcs层状结构的热行为进行初步研究，结果表明ZnAlCe—HTLcs热稳定性较差，层间结合水、层板羟基及层间客体物种(NO3^-)失去温度在240℃左右，易于转化为复合氧化物，将此复合氧化物应用于NO的催化?肖除反应，680℃下NO的转化率高达近100％。     

Diastereoselective Access to Polyoxygenated Polycyclic Spirolactones through a Rhodium‐Catalyzed [3+2] Cycloaddition Reaction: Experimental and Theoretical Studies

The synthetic utility of γ‐alkylidenebutenolides is demonstrated as highly competent dipolarophile partners in both intra‐ and intermolecular rhodium(II)‐catalyzed 1,3‐dipolar cycloaddition reactions. The strength of this approach lies in the formation of spiro[6,4]lactone moieties with the concomitant construction of quaternary spiro stereocenters. Typically, the construction of spirolactones involves an esterification step, which has often been reported as a “biosynthetic pathway”, and often occurs either as or near to the final step of a total synthesis. Furthermore, a convergent and versatile route is reported for the formation of the (5,7) skeleton of molecules that were isolated from the Schisandra genus. Computational studies were performed to provide an overall picture of the mechanism of the intermolecular [3+2] cycloaddition between 2‐diazo‐1,3‐ketoester and protoanemonin and to rationalize the empirical observations. In particular, we have demonstrated for the first time that the rhodium center plays an important role during the cyclization step itself and reacts with the dipolarophile as a complex with the ylide.     

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.     

Propellanes. Part LXXX. Baeyer-Villiger Oxidation of [4.3.3]Propellane-8,11-dione

Oxidation of the title compound with m-chloroperbenzoic acid affords a keto-lactone, two bis-lactones and a bis-spirolactone, in varying amounts depending upon the reaction conditions. The structures were established by means of X-ray diffraction, ¹H- and ¹³C-NMR spectroscopy.     

Chiral Self‐Sorting of [2+3] Salicylimine Cage Compounds

An inherently chiral C₃‐symmetric triaminotribenzotriquinacene was condensed in racemic and enantiomerically pure form with a bis(salicylaldehyde) to form [2+3] salicylimine cage compounds. Investigations on the chiral self‐sorting revealed that while entropy favors narcissistic self‐sorting in solution, selective social self‐sorting can be achieved by exploiting the difference in solubility between the homochiral and heterochiral cages. Gas sorption measurements further showed that seemingly small structural differences can have a significant impact on the surface area of microporous covalent cage compounds.     

Studies on the chemistry of 2,3,5,6-tetrahydro-6-phenylimidazo[2,1-b]-thiazole II. Reaction with nucleophiles

The title compound behaves as an ambident electrophile which reacts with alkylthiols, thio-phenols, and sodium diethyldithiocarbamate to give 1-(2-substituted ethyl)-4-phenylimidazolidine-2-thiones by attack at C-2. In contrast, the reaction with pyrrolidine involves attack at the bridgehead carbon atom, followed by elimination of thiirane, to give 4-phenyl-2-(1-pyrrolidino)-imidazoline.     

新型六氢吡啶-2,3-并吲哚化合物的合成及其抗肿瘤活性

以3-取代氧化吲哚与丙烯酸酯为原料,经Michael加成反应制得中间体--3-丙酸酯取代氧化吲哚（3a~3d）; 3a~3d与甲胺发生酰胺化反应制得3 丙酰胺取代氧化吲哚（4a~4d）; 4a~4d用氢化铝锂还原-环化,合成了4个六氢吡啶-2,3-并吲哚化合物(5a~5d）; 5a和5b用氢化铝锂还原合成了2个六氢吡啶-2,3-并吲哚化合物（6a和6b）, 5a～5d, 6a和6b均为新化合物,总产率42%～61%,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。采用MTT法研究了5a～5d, 6a和6b对人肺癌细胞（A549）,人前列腺（PC-3）和人白血病细胞（K562）的体外抗肿瘤活性。结果表明：5b对A549, PC 3和K562的抑制活性均较好,其IC₅₀分别为27.2μmol·L^-1, 37.5 μmol·L^-1和21.7 μmol·L^-1。     

Efficient synthesis of 8,11-dimethylene-bicyclo[5.3.1]undecan-2-one

We report here, an effective methodology for the preparation of 8,11-dimethylene-bicyclo[5.3.1]undecan-2-one. The key steps in these reactions were chloromethylation, cationic-alkyne cyclization and anionic fragmentation sequence.     

Synthesis of 2,3,5,6-tetrahydroimidazo[1,2-c]quinazoline derivatives as potential narcotic antagonists

The synthesis of a series of N₆-alkyl derivatives of the 2,3,5,6-tetrahydroimidazo[1,2-c]quinazoline as potential narcotic antagonists is reported.     

A Convenient Synthesis of Novel Pentacyclo [5.4. 0.02,6 .03,10 .05,9] Undecane-8,11-dione-4-spiro-1-cyclopropane

An efficient synthesis of the title compound by Diels-Alder cycloaddition of spiro(4.2) heptadiene with p-benzoquinone followed by photochemical ring closure is described.     

Synthesis, Characterisation and UV-Vis Properties of Azocalix[4]crowns

This article describes the synthesis, structure andUV properties of azocalixcrowns in which the photoresponsivetrans-cis azo benzene unit has been introduced in the glycolicchains of the calix[4]crowns. The synthesis proceeded via the selective-1,3O-dialkylation of calix[4]arene with glycolic chains terminated bynitrophenyl residues. After reduction of thenitro groups into amino functions,intramolecular oxidative coupling produced thecapping of the calixarene. Thesynthetic approaches and the cis-transstructure of these new ligandsare discussed and full details on synthesesand structural data are given. Apreliminary example of cesium complexation byone of the ligands is proposed.