新型苯并噁唑(噻唑)衍生物的合成与表征

通过N-氯乙酰或N、N＇-二氯乙酰取代的含氮杂环中间体，4，5-二氯-2-苯基-3-哒嗪酮分别与2-巯基苯并噁唑和2-巯基苯并噻唑反应，合成了8个未见文献报道的苯并噁唑和苯并噻唑衍生物，其结构经^1H NMR，IR，MS及元素分析确认。     

2-巯基苯并噻唑稀土配合物的合成、表征及橡胶硫化促进性能研究

在无水乙醇溶剂中,以稀土氯化物与2-巯基苯并噻唑钠盐反应,合成了8种稀土含硫有机配合物.通过元素分析、红外光谱和热重分析,确定了配合物的组成为RELCl2*RE(OH)3*xH2O(L=2-巯基苯并噻唑, RE= La～Gd, Y, 除Pm外,x=0,2～4 );并对合成的镧配合物进行了橡胶硫化促进性能研究,结果表明,该类配合物具有较好的硫化促进性能和改善硫化胶物理机械性能的特性.     

新型二茂铁噻唑和咪唑衍生物的合成及其对Fe~(3+)的选择性识别

设计合成了5个新型二茂铁噻唑和咪唑衍生物,其特点是二茂铁共轭单元与杂环共轭单元之间用羰基亚甲基(COCH_2)相连.以二茂铁为原料,经氯乙酰化反应生成氯乙酰基二茂铁(1a),1a分别与不同的杂环化合物(2-巯基苯并噻唑、2-巯基苯并咪唑、咪唑和苯并咪唑)反应生成相应的四种新化合物;二茂铁经乙酰化、溴代反应生成1,1'-二(溴乙酰基)二茂铁(1b),1b与2-巯基苯并噻唑反应生成1,1'-二茂铁二[(2-苯并噻唑-2-硫基)-1-乙酮](2e).五种新化合物的结构都经~1HNMR,~(13)CNMR,ESI-MS,HRMS和IR确认,并得到3个化合物的X射线单晶结构.利用紫外-可见光谱研究了5个新化合物对14种金属离子的识别性质,发现这5个化合物只对Fe~(3+)离子具有离子识别作用,其中2a具有最大的吸收光谱响应.     

含苯并噻唑基的硫桥杯芳烃衍生物的合成及结构

在碳酸钾存在下, 对叔丁基硫桥杯芳烃(1)分别与端基二溴代烷和碘甲烷反应, 生成硫桥杯芳烃衍生物2 和3, 它们分别与过量的2-巯基苯并噻唑在碳酸钾存在下反应, 生成含苯并噻唑基的硫桥杯芳烃衍生物5a～5d. 通过 1H NMR, 13C NMR, IR, MS和元素分析等手段对产物进行了表征. 同时, 采用X射线衍射分析确定了硫桥杯芳烃5b的晶体结构.     

2-位官能团化合成2-取代苯并噻唑的研究进展

2-取代苯并噻唑类衍生物在化工、医药、农业等领域具有广泛的应用价值.2-位官能团化是合成2-取代苯并噻唑化合物的一种便捷、有效的合成方法.综述了苯并噻唑2-位的烷基化、酰基化、芳基化、胺基化以及磷酸化等产物的合成方法并进行了归类和分析,同时对其发展进行了展望.     

苯并噻唑螺萘并噁嗪类化合物的微波合成与性质

以苯并噻唑衍生物、1-亚硝基-2-萘酚为原料,三乙胺为催化剂,无水乙醇为溶剂,采用微波辐射法合成了苯并噻唑螺萘并噁嗪光致变色化合物.通过元素分析,IR,MS,1H NMR对结构进行了表征,并用紫外分光仪研究了溶剂效应和荧光分光光度计研究了荧光效应,结果表明该类化合物具有较好的荧光性能,其开环体的λmax与溶剂的极性常数呈较好的线形相关性.     

5-(1-苯基-3-取代苯基-吡唑基)-1-苯并噻唑基吡唑啉衍生物的合成及其荧光性能

含吡唑基查尔酮与2-肼基苯并噻唑反应,直接成环得到一系列新的含吡唑基、苯并噻唑基的吡唑啉衍生物。目标化合物结构通过IR、~1H NMR谱和元素分析进行了确证,并用UV-Vis和荧光光谱研究了其光学性能。结果表明其最大激发波长在350 nm左右,其最大发射波长在434~452 nm之间。此类化合物具有良好的荧光性,其荧光强度的大小与衍生物中不同的取代基有关。     

含酯基苯并噻唑衍生物的摩擦膜及热膜化学结构

制备了两种苯并噻唑衍生物2-苯并噻唑基-巯基硫代乙酸正辛酯(MBTT)和2-苯并噻唑基-巯基乙酸正辛酯(MBTA), 并用元素分析和核磁共振谱表征其分子结构. 用X光吸收近边结构谱(X-ray absorption near edge structure, XANES)全面地分析了杂环化合物在矿物油和菜籽油中所形成的摩擦膜和热膜的化学态. 分析结果表明, 在矿物油中, 添加剂MBTT和MBTA摩擦反应生成的摩擦膜主要由FeS2组成, 而菜籽油中, 两种添加剂摩擦反应生成的摩擦膜由FeSO4组成; 在两种基础油中, 两种添加剂生成的热膜都是由FeSO4组成的.     

苯并噻唑类化合物在银上的吸附机理研究

本文利用线性电势扫描的方法研究了几种苯并噻唑类化合物及巯基苯基四氮唑在银上的吸附机理。结果表明:2.巯基苯并噻唑和巯基苯基四氮唑以化学吸附方式,通过分子上巯基与银表面的作用形成分子紧密排列的吸附层。25℃下,PMT可以在银表面形成紧密单层。这种吸附在较高吸附温度下可以转化为多层,且完全覆盖银表面。在含Br^-的溶液中,它可以阻碍Br^-与表面的接触。在较大的浓度下,2-甲基苯并噻唑和苯并噻唑也可以在银表面的某些位置,通过杂环上的S原子(或N原子)形成松散的吸附,但这种吸附层不能完全覆盖银表面。电镜实验也表明以上物质在银表面发生了作用。     

Selectfluor氧化合成2-芳基苯并噻唑的新方法

开发了一种以芳基甲基酮或脂肪酮和2-氨基苯硫酚为原料,正丁醇为溶剂, 120℃条件下经Selectfluor氧化合成2-取代苯并噻唑类衍生物的方法.通过改变底物芳基甲基酮上的取代基可以获得具有生物活性的药物中间体.     

Nucleophilic substitution reactions of pyranose polytosylates

The 2,3,4-tri-toluenesulfonate ester derivatives of the methyl pyranosides of l-arabinose, d-ribose, d-lyxose, and d-xylose have been prepared, and their substitution reactions with various nucleophiles have been examined. For arabinose, xylose, and ribose, highly regioselective monosubstitutions were observed with benzoate, nitrite, and azide anions. These reactions have led to short and simple routes from d-xylose to l-arabinose derivatives, from l-arabinose to d-xylose derivatives, and from d-ribose to l-lyxose derivatives. The tritosylate derived from methyl alpha-d-lyxopyranoside was unreactive toward nucleophilic substitution reactions, giving instead a dihydropyran product arising from an initial E2 elimination reaction of the 2-tosylate.     

2,4,6—三氧—1,3,5,2—三氮磷杂环己烷衍生物的合成及其抗肿瘤活性

利用Ｎ，Ｎ－二（２－氯乙基）氨基磷酰二异氰酸酯和胺的加成反应，合成了２，４，６三氧－１，３，５，２三氮磷杂环己烷衍生物，它们的结构经＾１ＨＮＭＲ，ＩＲ和元素分析所证实。初步生物活性测试结果表明，部分化合物具有一定的抗肿瘤活性。     

Selective functionalization of 2-oxoallobetulin derivatives

A new series of 2-oxoallobetulin derivatives has been synthesized by using various unique reactions. Site-specific or regio-selective functionalization of those compounds has been investigated. In all cases, the reactions only happened at C-3 position except the synthesis of lactam happened at C-1 position. The intermediates leading to the novel allobetulin derivatives have also been described.     

二氧化碳作为羧化试剂用于羧酸及其衍生物的合成(英文)

二氧化碳是储量丰富、廉价易得且可再生的C1资源,将其催化转化成高附加值精细化学品的研究已经引起了人们的广泛关注.目前,虽然二氧化碳用作初始原料的反应已经工业化的很少,但过去几十年中仍有二十多个具有实际应用前景的二氧化碳参与的新反应被发现,其中以二氧化碳作为羧化试剂合成各种羧酸及其衍生物的反应为突出代表.本文综述了过渡金属催化合成羧酸及其衍生物的二氧化碳与多种碳亲核试剂、碳氢键以及碳碳多重键化合物的反应,并总结了无过渡金属参与或有机小分子催化条件下将二氧化碳转化成羧酸及其衍生物的反应.     

Cycloaddition of keteniminium with terminal alkynes toward cyclobuteniminium and their use in Diels–Alder reactions

An efficient access to cyclobutanone derivatives has been developed via a ‘one-pot’ [2+2]/[4+2] sequence involving keteniminium and cyclobuteniminium salts as key intermediates. A broad range of novel cyclobuteniminium salts have been prepared via [2+2] cycloaddition of keteniminium salts and alkynes. The resulting [2+2] adducts were then further transformed by Diels–Alder reaction with various dienes to afford cyclobutanone derivatives in good yields. A density functional theory (DFT) based computational study has been performed to obtain insight into the nature of the cycloaddition reactions and to investigate the difference in reactivity of cyclobuteniminium salts. Finally, the usefulness of cyclobutanone derivatives has been demonstrated by ring expansion reactions affording lactone, lactame, and cyclopentanone derivatives.     

1-(2-羟甲基-1,3-氧硫杂环戊基)吡啶酮类化合物的合成

研究了1,3-氧硫杂环戊烷核苷类似物的合成. 以吡啶酮为碱基, 利用三甲基硅基三氟甲磺酸酯(TMSOTf)催化, 与1,3-氧硫杂环戊烷发生Vorbruggen缩合反应, 合成了一系列的保护的核苷类似物, 经过进一步脱保护或者还原得到目标产物. 并测试了合成化合物的抗菌活性, 发现该类化合物对革兰氏阳性菌具有中等抑制活性.     

Reactions of 4-hydrazinoquinazoline with derivatives of 1,3-cyclanediones

In reactions of 4-hydrazinoquinazoline with 2 formyl- and 2-acetyldimedones, 2 formyl-1,3-indandione, dehydroacetic acid, and 2, 2-dimethyl-5-ethoxymethylene-1, 3-dioxane-4, 6-dione, the corresponding hydrazinomethylene and 1-hydrazinoethylidene derivatives have been obtained. Attempts to convert the 2-hydrazinomethylene- and 2-(1-hydrazinoethylidene)dimedones to indazole derivatives were unsuccessful. In reactions of 4-hydrazinoquinazoline with 2-cyano-3-ethoxy-5,5-dimethylcyclohex-2-en-1-one, 3-hydrazino derivatives were obtained; with 2-amino-5-oxo-7, 7-dimethyl-5, 6, 7, 8-tetrahydroquinazoline and 1 phenyl-4,5-dioxo-6, 6-dimethyl-4, 5, 6, 7-tetrahydroindazole, the corresponding 5(4-quinazolylhydrazino) derivatives were obtained.     

Spectral studies of the newly synthesized azomethine derivatives of zirconium(IV)

Equimolar and bimolar reactions of zirconium isopropoxide with bibasic tridentate azomethine (AZH₂) having the donor system ONO have been carried out and derivatives of the type Zr(OPr¹)₂(AZ) and Zr(AZ)₂ [Where AZ²⁻ is the anion of the azomethine molecule] have been isolated. The labile nature of the isopropoxy groups in 1∶1 derivatives has been shown by carrying out exchange reactions with equimolar amount of 2-methylpentane-2,4-diol. All the newly synthesized derivatives have been characterized on the basis of elemental analysis, conductance measurements, molecular weight determinations and infrared, ultraviolet, visible and proton magnetic resonance spectral studies.     

Synthesis of Guanine Derivatives Substituted in the O6-Position by Mitomycin C

Although adducts resulting from the reaction of mitomycin C (MC) and DNA have been characterized as guanine derivatives covalently linked to MC at the guanine N²-and/or O⁶-positions, lack of material and of protons on the quanine nucleus had led to difficulties in product characterization. Authentic O⁶-MC guanosine derivatives have been synthesized and comparison shows that N²-adducts and not O⁶-adducts are the major products from reactions of reduced MC with DNA.     

Effect of metal ions in organic synthesis : Part XXXIII. 2-hydroxy-4-pyrrolines as stable intermediates in the synthesis of 1-aminopyrrole derivatives

The reactions of conjugated aroylazoalkenes with β-diketones and β-ketoesters in the presence and in the absence of copper(II) chloride as catalyst have been studied. In the first case, 1-aminopyrrole derivatives have been obtained, while in the second case the formation of 2-hydroxy-4-pyrrolines as stable intermediates has been frequently detected. The observations on the conditions of the formation of either or both products, as well as the proof of the easy conversion of 2-hydroxy-4-pyrrolines into pyrrole derivatives elucidate the much debated behaviour of these reactions.