1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂（艹/卓）化合物的合成

苯并二氢吡喃－４－酮的芳腙（１）衍生的偶氮基碳正离子（３）与腈发生１,３－偶极环加成反应,加成产物（４）通过「１,２」－迁移扩环重反应,形成新颖的三环系杂环化合物１,２,４－三唑并「３,２－ｄ」「１,５」－苯并氧氮杂Ｚｈｕｏ化合物５ａ－５ｋ。     

BDTAN与铜显色反应的研究及应用

研究了新合成的双噻唑偶氮类试剂２,６－二偶氮－「１,１‘－（２,２’－二萘酚）」苯骈「１,２－ｄ：４,５－ｄ‘」二噻唑（ＢＤＴＡＮ）与Ｃｕ＾２＋的显色反应。在Ｔｒｉｔｏｎ Ｘ－１００存在下,ｐＨ６－ｐＨ７的范围内,该试剂与Ｃｕ＾２＋形成物质的量比为２：１的络合物,络合物对试剂空白的最大吸收波长λｍａｘ＝６２５ｎｍ,ε为３．８×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１,Ｃｕ＾２＋的质量浓度在０－３０μｇ     

杂多核配位荧光增敏法测定痕量铍

研究了新荧光试剂２－「５－羧基－２－胂酸基苯偶氮」－１,８－二羟基－３,６－萘二碘酸与铍络合的荧光性能。铍与试剂形成荧光络全物,在硼砂介质啼生增敏效应,据此建立了测定痕量铍的新方法。Ｂｅ（Ⅱ）浓度在０－０．１２ｍｇ／Ｌ范围内一荧光哟度呈良好线性关系,方法检测限为０．０７６μｇ／ＬＢｅ（Ⅱ）,用于水及铜基合金样中的痕量铍的测定,结果满意。     

甲基、磺酸基取代的9,9'-双吖啶衍生物的化学发光研究

研究了１０,１０’－二甲基－９,９－双吖啶（ＤＭＢＡ）,２,２‘－二磺酸基－９,９－双吖啶二硝酸盐（ＤＳＢＡＤＮ）,１０,１０’－二甲基－２,２‘－二磺酸基－９,９’－双吖啶（ＤＭＤＳＢＡ）,及１０,１０‘－二甲基－９,９’－双吖啶二硝酸盐９ＤＭＢＡＤＮ,谷称光泽精）等４种９、９‘－双吖啶衍生物的化学发性质,发现１０,１０’－二 磺酸基－９,９‘－双吖啶的化学发光强度是光泽精的２２倍,是迄今为止发     

水溶性[5-邻(乙氧羰基甲氧基苯基)-10,15,20-Tri(4-N-甲基吡啶基)]卟啉铜(Ⅱ)配合物的合成、表征及其和单核苷酸的相互作用

合成并表征了「５－ｏ（乙氧羰基甲氧基苯基）－１０,１５,２０－Ｔｒｉ（４－Ｎ－甲基吡啶基」卟啉Ｈ２「５－ｏ－（Ｅｍｏｐｈ）－Ｔｒｉ（４－Ｎ－Ｍｅｐｙ）」ＰＰ（１）及其铜配合物Ｃｕ「５－ｏ－（Ｅｍｏｐｈ）－Ｔｒｉ（４－Ｎ－Ｍｅｐｙ）」ＰＰ（２）,用紫外－可见光谱滴定法测定配合物（２）与单核苷酸的配位平衡常数,研究了它作为主体分子和单核苷酸的相互作用。研究结果表明,各配体结合常数按Ｋ（ｄＧＭＰ）〉Ｋ（ｄＡＭＰ）〉Ｋ（ｄＴＭＰ）〉Ｋ（ｄＣＭＰ）≥Ｋ（ｄＵＭＰ）的顺序依次减小。测定了π－π配合反应的△,Ｇ,△ｒＨ,△ｒＳ,发现该反应是放热,熵减小的过程,该反就体系存在焓熵补偿关系。     

酰胺型杯[4]聚硅氧烷用作气相色谱固定相的研究

将合成的两种酰胺型杯「４」聚硅氧烷（ＰＳＯ－Ｃ「４」Ａ和Ｍ－Ｃ「４」Ａ－ＰＳＯ）用作毛细管柱气相色谱固定液,考察了产的色谱特性,柱效、极性及选择性,相变温度和稳定性。结果表明,两种酰胺型杯「４」聚硅氧烷固定液具有优良的色谱性能、多环芳主一些芳香族位置异构体得到较好的分离。     

1-[(2,3,4-三羟基苯)偶氮]-4-苯甲酸的合成及光度法测定锡青铜中的锡

合成了新试剂１「２,３,４－三羟基苯）偶氮」－４－苯甲酸并将其应用于锡青铜中锡中测定。发现该度剂与锡形成的棕红色络合物在４８５ｎｍ处有最在吸收,表观摩尔吸光系数为２．５２×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,并且锡的质量浓度在０－７０μｇ／２５ｍｌ范围内符合比耳定律。大量铅对测定无影响,可不经分离,直接分光光度法测定锡青铜合金中的锡。     

（二噻吩[3,2—b：3‘,2’—d]环戊烷—4—亚基）C60中的分子轨 …

在ＺＩＮＤＯ方法基础上，按完全态求和公式编制了计算分子二阶非线性光学系数β的程序。研究了（二噻吩「３，２－ｂ：３‘，２’－ｄ」环戊烷－４－亚基）Ｃ６０中的分子轨道相互作用，计算了该分子的电子光谱和二阶非线性光学系数β，前者与实验结果吻合较好，后者属于理论预测性质。     

用新试剂2[—5‘—氟—2’—砷酸基苯）偶氮]—1,8—二羟基—3,6—萘二磺酸荧光法

研究了试剂２－」５’－氟－２’－－砷酸基苯）偶氮「－１，８－二羟基－３，６－萘二磺酸与硼的荧光性能。硼与试剂形成１：２的强荧光配合物，其λｅｘ／λｅｍ＝２３４ｎｍ／３８０ｎｍ，Ｂ（Ⅲ）含量在０－３６０μｇ／Ｌ范围内呈良好线性关系，检测限为２．０６μｇ／Ｌ，据此建立了测定微量硼的新方法。     

用新试剂2-[(5’-氟-2’-砷酸基苯)偶氮]-1,8-二羟基-3,6-萘二磺酸荧光法测定硼

研究了试剂２－［（５’－氟２’－砷酸基苯）偶氮］－１，８－二羟基－３，６－萘二磺酸与硼的荧光性能．硼与试剂形成１：２的强荧光配合物，其λｅｘ／λｅｍ＝２３４ ｎｍ／３８０ ｎｍ， Ｂ（Ⅱ）含量在 ０～３６０μｇ／Ｌ范围内呈良好线性关系，检测限为２．０６μｇ／Ｌ，据此建立了测定微量硼的新方法。该方法应用于茶叶、铝合金及粮食等样品中微量硼的测定，结果满意．     

One-Pot Synthesis of Hydroxybenzo[d]-oxazole-2-aliphatic Acid Derivatives by Meerwein's Reagent

A general one-pot synthesis of hydroxylbenzo[d]oxazole-2-aliphatic acid esters and hydroxylbenzo[d]oxazole-2-amino acid esters was successfully achieved in good yield by using Meerwein's reagent.     

[60]富勒烯[2＋2]环加成反应的研究进展

[2＋2]环加成反应是对C₆₀进行化学修饰的重要反应之一, 重点从[2＋2]环加成的典型反应、主要试剂及反应机理等方面进行了综述.     

Synthesis and Crystal Structure of 1,3-Trans-1,4-cis- 3,4-di(4-bromophenyl)-1',2',3'-trihydro-1-hydroxy- benzo[g]bicyclo[3.3]octane-2-spiro-2'-indene-1'-one

1 INTRODUCTION Low-valent titanium reagents have exceedinglyhigh abilities to promote reductive coupling of car-bonyl compounds and they are attracting increasinginterest in organic synthesis[1]. Many other func-tional groups can also be coupled[2~8]. Recently, wehave reported some intermolecular reductive cou-pling reactions[9~12] and some new intramolecular re-ductive coupling reactions[13~16] induced by low-va-lent titanium reagents. The spiro[4.4]nonane skeleton has been found inmany…     

由N-苯基[1,3]苯并噁嗪正离子与烯烃[4+2]反应合成喹啉并[1,2-c][1,3]苯并噁嗪-6-酮衍生物

以BF3·OEt2 为催化剂, 在室温下通过4-羟基-N-苯基[1,3]苯并噁嗪-2-酮的脱羟基产生N-苯基[1,3]苯并噁嗪正离子, 然后与富电子烯烃发生Diels-Alder反应, 合成出了一系列喹啉并[1,2-c][1,3]苯并噁嗪-6-酮和喹啉并[1,2-c][1,3]萘并噁嗪-6-酮衍生物.     

3-对甲氧基苯基-和3-对羟基苯基-1-氨基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈的合成和晶体结构

用低价钛试剂(TiCl₄-Zn)与2-氰基-3-对甲氧基苯基-3-(1-四氢萘酮-2-基)丙腈反应合成了3-对甲氧基苯基-1-氨 基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈和3-对羟基苯基-1-氨基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈, 并用X射线衍射分析确定了这两个产物的结构.     

Some reactions of 2H-[1]benzothieno[3,2-b]pyran-2-ones and related compounds

The conversion of 2H-[1]benzothieno[3,2-b]pyran-2-ones into mono- and dithio-derivatives and the preparation of some dibenzothiophenes, sulphines and pyridones are described.

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Einige Reaktionen von 2H-[1]Benzothieno[3,2-b]pyran-2-onen und verwandten Verbindungen

Zusammenfassung Es wird die Umsetzung von 2H-[1]benzothieno[3,2-b]pyran-2-onen zu Monound Dithio-Derivaten und die Darstellung einiger Dibenzothiophene, Sulfine, und Pyridone beschrieben.

     

Helic[6]arene-Based Chiral Pseudo[1]rotaxanes and [1]Rotaxanes

Chiral pseudo[1]rotaxanes and [1]rotaxanes constructed from macrocyclic arenes still remain a big challenge mainly owing to the lack of such chiral macrocycles. In this work, a new system of chiral pseudo[1]rotaxanes formed by self-inclusion of helic[6]arene containing amide linked with the terminal tertiary amines was first discovered. Based on an atom-economic stopping strategy, a pair of chiral [1]rotaxanes were conveniently obtained in almost quantitative yields by blocking the pseudo[1]rotaxanes with monobenzyl bromide of tetraphenylethene. The structures of pseudo[1]rotaxanes and [1]rotaxanes were characterized by 2D NMR spectra in solution, combined with DFT calculations. The photophysical properties further revealed the efficient chirality transfer of helic[6]arene to the tetraphenylethene moiety, compared to their unthreaded chiral isomers. The discovery of the chiral pseudo[1]rotaxanes allows for a wide and available synthesis of chiral [1]rotaxanes, and also opening a new avenue to the design of chiral supramolecular materials.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

低价钛促进的苯并咪唑并[1,2-c]喹唑啉衍生物的合成

利用低价钛试剂促进的2-邻硝基苯基苯并咪唑与原甲酸酯或丙酮或固体光气的反应, 合成了一系列苯并咪唑并[1,2-c]喹唑啉衍生物, 化合物的结构经IR, 1H NMR, MS和元素分析确定, 化合物4c的结构经单晶X射线衍射分析进一步确证. 该方法具有原料易得、操作简便和产率高等优点.     

Formylation of Furyl-substituted Imidazo[1,2-a]pyridine, Imidazo[1,2-a]pyrimidine and Imidazo[2,1-b]thiazole

Vilsmeier formylation of 2-(2-furyl)-substituted imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrimidine, and also 6-(2-furyl)imidazo[2,1-b]thiazole with 1 mole of reagent occurs at the free position of the imidazole ring, while with an excess of the reagent it also occurs at the position 5 of the furyl group.