1-[(Z)-2-(-苯基二溴化锡基)乙烯基]环戊醇的合成及晶体结构

通过１［（Ｚ）２（三苯基锡基）乙烯基］环戊醇与Ｂｒ２反应制得了新化合物１［（Ｚ）２（苯基二溴化锡基）乙烯基］环戊醇．通过元素分析、锡含量测定、ＩＲ、１ＨＮＭＲ对其进行了表征并用Ｘ射线衍射法测得了所合成化合物的晶体结构．该化合物属正交晶系，Ｐ２１２１２１空间群，晶胞参数：ａ＝０８６７５（４）ｎｍ，ｂ＝１２５２３（７）ｎｍ，ｃ＝１４００９（８）ｎｍ；Ｚ＝４，Ｖ＝１５２１９ｎｍ３，Ｄｃ＝２．３９ｃｍ３，ｕ＝２３．７２ｃｍ－１．结构分析表明，标题化合物分子为畸变的三角双锥构架，双键的两个氢取顺式结构，分子中Ｏ与Ｓｎ配位，形成五元螯合环结构     

α-外式-7-氧双环[2.2.1]庚-5-烯-2,3-二甲酰亚氨基-α-取代苯基膦酸二苯酯的合成

以去甲 去氢斑 蝥素为原 料合 成了 α外式７氧双 环［２２１］ 庚５烯２ ，３二 甲酰 亚氨 基α取代苯 基膦酸二 苯酯共 ８ 种化合 物． 所 合成化合 物结构 经１ Ｈ Ｎ Ｍ Ｒ、３１ Ｐ Ｎ Ｍ Ｒ 、 Ｍ Ｓ、 Ｉ Ｒ 及 元素 分析所确证 ．     

钛开环夹心羰基化合物的构象分析

合成了３个钛开环夹心羰基化合物．用１ＨＮＭＲ方法对３个钛开环夹心羰基化合物进行了研究实验结果表明,钛开环夹心羰基化合物的分子构象与开环配体的取代状况有关．由对称取代戊稀基配体形成的化合物只有１种构象,由非对称取代戊二稀基［２ＣＨ３Ｃ５Ｈ６］－形成的化合物具有２种构象（ｃｉｓ和ｔｒａｎｓ）．     

4 氨基4′ 氰基联苯的合成

４氨基４′氰基联苯,不仅是制备烷氧基联苯的原料,而且可以制备高正介电各向异性液晶及系列酯类液晶材料．但通常要经过酰化、氧化、酰氯化、氨解、脱水、硝化和还原［１］等多步反应,步骤长、收率低,本文用联苯为原料,经过硝化、碘代、氰代和还原反应合成４氨基４′氰基联苯．反应步骤及时间比原路线减少近一半,而且反应条件温和,收率高．联苯（ＣＰ,上海化学试剂一厂）;Ｎ,Ｎ二甲基甲酰胺（ＡＲ,临平化工试剂厂）;氯仿（ＡＲ,沈阳试剂一厂）;亚硫酸氢钠（ＡＲ,大连辽南化学品厂）;碘酸（ＡＲ,北京化工厂）…     

侧链液晶聚合物相转变点的分子动力学模拟

液晶基本上可分为３类：向列型液晶、近晶型液晶和胆甾型液晶［１］．液晶材料的相转变温度的预测对选择和设计液晶材料具有非常重要的作用．本文用分子动力学模拟法对聚［ω－（４′－甲氧基联苯－４－氧基）己基］甲基丙烯酸酯（ＰＭ６ＭＰＰ）单链分子进行了研究,模拟...     

夹心化合物［C_5HMe_4］_2TiCl_2的合成及谱学表征

用四甲基环戊二烯基［Ｃ_５ＨＭｅ_４］~－为配体合成了夹心化合物［Ｃ_５ＨＭｅ_４］_２ＴｉＣｌ_２，通过核磁共振、质谱、红外光谱、拉曼光谱等多种谱学方法对该化合物进行了结构表征，实验结果表明［Ｃ_５ＨＭｅ_４］_２ＴｉＣｌ_２中两个［Ｃ_５ＨＭｅ_４］~－配体对称分布在Ｔｉ（Ⅳ）两侧，整个分子具有Ｃ_２ｖ对称性，呈覆盖型结构。     

化学修饰环糊精在醇/水混合溶剂中的包结行为

环糊精 (ＣＤ)及其衍生物在主客体化学中占有重要位置［１］．在环糊精母体上引入一个荧光发色团,可使ＣＤ变为在光谱上有响应的主体化合物,如引入一个丹酰基,在水溶液中由于疏水相互作用,该荧光团易于进入ＣＤ内腔形成“自包结”配合物［２ -３］．我们曾合成了以氮氧杂 十一烷基链相连接的单个Ｎ,Ｎ二甲氨基查尔酮 (ＤＭＡＣ)修饰的 β ＣＤ衍生物 (ＤＭＡＣ ＣＤ),也表现出良好的自包结特征［４］．前人曾有吖啶／ＣＤ配合物体系与低浓度醇分子形成三元包结物的报导［５,７］,而在醇水混合溶剂中主客体配合物的稳定性研究较少．…     

聚醚砜的磺化及表征

磺化是芳环聚合物改性的有效方法．引入的磺酸基以酸型、盐型和酯型存在,且可以继续制备其它衍生物．有关聚苯醚［１,２］、聚苯硫醚［３］、聚醚醚酮［４,５］和聚砜［６～８］的磺化研究和表征已有很多报道,这些聚合物引入磺酸基后亲水性增强,广泛用于制备反渗透膜...     

N,2-二芳基二氮亚烯甲酰胺合成的新方法

偶氮化合物可用作非线性光学材料、激光盘信息存贮材料和现代科技中的油溶性染料［１］．传统偶氮化合物的制备有重氮盐偶合和取代肼氧化等许多方法［２～４］,其偶氮基两端一般联有烃基或芳环,而联有羰基的偶氮类化合物用通常方法难以制备．本文首次用Ｎ－溴代丁二酰亚...     

(R)-N-酰基四氢噻唑-2-硫酮-4-羧酸在DCC存在下与胺的反应

由Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１０９．８３°），及Ｎ－苯甲酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１１２．２２°），在Ｎ，Ｎ′－二环己基二亚胺（ＤＣＣ）存在下分别与环己胺、苯胺反应得到光学活性产物（Ｒ）－Ｎ－乙酰四氢噻唑－２－硫酮－４－甲酰环己胺（［α］１７Ｄ－７４．５°），及（Ｒ）－Ｎ－苯甲酰四氢噻唑－２－硫酮－４－甲酰苯胺（［α］１９Ｄ－７．０４°）。用量子化学ＰＭ３方法研究了反应物和产物的电子结构。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.