稠杂环化合物的研究（XV）──6－取代－3－（1H－苯并三唑－1－亚甲基）－1，2，4－三唑并［3，4－b］－1，3，4－噻二唑的合成

研究了３－（１Ｈ－苯并三唑－１－亚甲基）－４－氨基－５－巯基－１，２，４－三唑与取代苯甲酸在三氯氧磷催化下的反应，制得１０种新的３－（１Ｈ－苯并三唑－１－亚甲基）－１，２，４．三唑并［３，４－ｂ］－１，３，４－噻二唑，通过元素分析、ＩＲ、￣１ＮＭＲ和ＭＳ确证了它们的结构并讨论了其波谱性质。     

1－（取代异噁唑基）－1，2，4．三唑和1－（取代嘧啶基）－1，2，4－三唑的合成及生物活性

合成了１５个新的１－（取代异噁唑基）－１，２，４－三唑和１－（取代嘧啶基）－１，２，４－三唑化合物，经元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ证实其结构，并对其代表化合物进行了抑菌及植物生长调节活性的初步观察     

稠杂环化合物的研究（X）──3－芳基－6－苯甲酰氨基均三唑并［3，4－b］－1，3，4－噻二唑类化合物的合成及生物活性

本文利用３－芳基－４－氨基－５－巯基－１，２，４－均三唑和苯甲酰异硫氰酸酯在无水丙酮中反应，得到一系列３－芳基－６－苯甲酰氨基均三唑并［３，４－ｂ］－１，３，４－噻二唑，用元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ确定了其结构，提出了可能的反应机制。并对其代表产物２ｈ进行了初步的抗菌和除草实验。     

稠杂环化合物的研究（Ⅸ）──3－芳基－6－（2，4－二氯苯氧乙酰胺基）均三唑并［3，4－b］－1，3，4－噻二唑的合成

３－芳基－４－氨基－１，２，４－均三唑－５－硫酮和２．４－二氯苯氧乙酰异硫氰酸酯在丙酮中于６０℃回流，制得１０个新的均三唑并［３，４－ｂ］－１，３，４－噻二唑（３ａ－ｊ）化合物，用元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ确证了结构，并讨论了反应机制。     

2，4－二羟基－3－芳氨基甲基苯乙酮和8－乙酰基－3－芳基－3，4－二氢－5－羟基－2H－1，3－苯并■嗪的合成及其相互转化

研究了在氯化氢－乙醇溶液或乙醇溶液中，２，４－二羟基苯乙酮与甲醛和芳胺的Ｍａｎｎｉｃｈ反应，分别得到了５个２，４－二羟基－３－芳氨基甲基苯乙酮和５个８－乙酰基－３－芳基－３，４－二氢－５－羟基－２Ｈ－１，３－苯并嗪新化合物。用元素分析、ＩＲ、１ＨＮＭＲ、ＭＳ、ＵＶ确定了它们的结构，并成功地实现了２，４－二羟基－３－芳氨基甲基苯乙酮和８－乙酰基－３－芳基－３，４．二氢－５－羟基－２Ｈ－１，３－苯并嗪二类化合物的转化。     

1，2，4－三嗪类化合物的研究（ⅩⅫ）──咪唑并－（5，4－e）－1，2，4－三嗪衍生物的合成

１，２，４－三嗪类化合物的研究（ⅩⅫ）──咪唑并－（５，４－ｅ）－１，２，４－三嗪衍生物的合成沙耀武，蔡孟深（北京医科大学药学院，北京，１０００８３）关键词乙二脒腙，原甲酸三乙酯，１，２，４－三嗪，咪唑并－（５，４－ｅ）－１，２，４－三嗪天然碱基拮抗...     

1，2，4－三嗪类化合物研究（XXIV）──吡唑并－（5，4－e）－1，2，4－三嗪衍生物的合成

先合成１，２，４－三嗪环，然后并接吡唑环，对标题化合物进行了合成研究。对１，２，４－三嗪环上的硫化反应进行了改进，解决了３个反应活性相近部位的选择性肼解问题；并发现了肼基与乙酸乙酯于室温下反应生成１，３，４－　二唑环的新反应。     

酰氨基硫脲及相关杂环衍生物研究（XXV）──1－［5′－氨基－1′－（4″－氯苯基）－1′，2′，3′－三唑－4′－甲酰基］－4－芳基氨基硫脲的合成和波谱研究

通过５－氨基－１－（４′－氯苯基）－４－甲酰肼基－１，２，３－三唑与芳基异硫氰酸酯的反应，合成了１３种新的１－［５′－氨基－１′－４″－氯苯基）－１′，２′，３′－三唑－４′－甲酰基］－４－芳基氨基硫脲类化合物３ａ－１，经元素分析、ＩＲ、１ＨＮＭＲ以及ＭＳ确证其结构。     

1－N－（苯并咪唑－1－乙酰基）－4－苯基－3－氨基硫脲金属配合物的合成及结构表征

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物。所有化合物均经元素分析、ＩＲ、１ＨＮＭＲ和热重分析等表征。红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子、烯醇式硫羰基硫原子以及Ｃ＝Ｎ１和Ｃ＝Ｎ２的氮原子与金属配位     

2－芳酰氨基－5－（5－苯基－2H－四唑2－甲基）－1，3，4－噻二唑类化合物的合成

在浓硫酸作用下，由５－（５－苯基－２Ｈ四唑－２－乙酰基）－４－芳酰氨基硫脲１ａ～ｎ制得了一系列新的２－芳酰氨基－５－（５－苯基－２Ｈ－四唑－２－甲基）－１，３，４－噻二唑化合物（２ａ～ｎ）。所有化合物的结构均经元素分析、ＭＳ分析，部分代表化合物经ＩＲ、￣ＨＮＭＲ分析确证；初步观察了２ａ～ｎ在１％浓度下对大肠杆菌（Ｇ￣－）的抑制作用，发现２ｄ，２ｅ，２ｆ，２ｎ显示出较强的活性。     

3-间硝基苯基/对硝基苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物的合成

报道了以3-间硝基苯基/对硝基苯基-4-氨基-5-巯基-1,2,4-三唑与芳酸在磷酰氯的作用下,合成了16个标题化合物,并研究了合成反应的条件。观察了部分标题化合物对金黄色葡萄球菌和大肠杆菌有明显的抑菌作用。     

ON THE ANIONS OF DIPHENYL 1-(4-NITROPHENYLAMINO)-1-ARYLMETHANE PHOSPHONATES1

Abstract

By means of UV spectroscopy it is shown that the anions derived of diphenyl 1-(4-nitrophenylamino)-1-arylmethane phosphonates are carbanions and not nitranions. This spectroscopical finding is corroborated by alkylation of the anions to give almost quantitatively the C-alkylated products.     

Synthesis, Crystal Structure and Fluorescent Properties of 1-（4-（Dimethylamino）benzylidene）- 4-（naphthalen- 1-yl） Thiosemicarbazide

1 INTRODUCTION Recently, for the fluorescent properties, Schiff base has been more and more important and widely studied in density optical memories, nonlinear op- tics (NLO), organic light-emitting diodes (OLED), polymer LED and electrogenerated chemilumines- cence (ECL)[1~5]. Thiosemicarbazones are a kind of Schiff bases with thiourea and good ligands easily chelating with transition metal ions. Although they have been studied extensively for a long time due to their chemical and b…     

手性2-(2-吡啶基)-4-羧乙基-1,3-噻唑烷的合成及应用研究

以分级结晶和柱层析法对手性配体2-(2-吡啶基)-4-羧乙基-1,3-噻唑烷(A)进行了异构体分离提纯。将其与[Rh(COD)Cl]_2制备的原位催化剂用于催化苯乙酮及其它几种芳香酮的不对称硅氢化反应,化学收率达90％左右,光学纯度达80％e.e.左右,噻唑烷环上的C_2构型对催化反应结果无影响,C_4位上酯基的影响也不大。     

Solvent Extraction of Alkaline Earths with 1-Phenyl -3-Methyl 4 Stearoylpyrazol - 5 - One and Topo

Abstract

The synergic extraction of Ca, Sr, and Ba ions from aqueous solutions into cyclohexane or benzene containing 1- pheny 1 - 3 - methyl - 4 - stearoylpyrazol - 5 - one (HPMSP) and TOPO has been studied. Quantitative extraction (log D>2) was attained at pH>5.4 for Ca, pH>6.5 for Sr, and pH>7.3 for Ba when cyclohexane containing 0.05 M HPMSP and 0.01 M TOPO was used, and the corresoponding values for benzene were 6.5, 7.8, and 8.4. Extracted species were M(PMSP)₂(TOPO)₃ (M=Ca, Sr, Ba) for cyclohexane and Ca(PMSP)₂(TOPO)₃ and Sr (or Ba) (PMSP)₂(TOPO)₂ for benzene.     

Metabolic study of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone to the enantiomers of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol in vitro in human bronchial epithelial cells using chiral capillary electrophoresis

4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) with one chiral center at the carbinol is a major metabolite of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK). As tobacco specific N-nitrosamines (TSNAs), NNK and NNAL are the most pulmonary carcinogens in tobacco products and smoke. In this paper, a chiral CE method modified with highly sulfated β-cyclodextrin (S-β-CD) was developed to investigate the stereoselective formation of NNAL from NNK in vitro in normal human bronchial epithelial (NHBE) cells. Combined with solid phase extraction (SPE) of the cell samples, NNK and NNAL enantiomers were baseline separated under the proposed CE conditions, with satisfactory recoveries (72.5-113% for NNK and (±)-NNAL) and low limits of detection (LOD, 2.5-3 μg/mL for NNK and (±)-NNAL). The cytotoxicity of NNK in NHBE cells was investigated through the cell counting kit (CCK) assay and proved to be highly dependent on the NNK's concentration. The metabolic results obtained from CE analysis demonstrated that NNK was preferentially metabolized to (+)-NNAL through carbonyl reduction. Meanwhile, the ratio of [(+)-NNAL]/[(-)-NNAL] was independent of NHBE cells' incubation time with NNK, but could be changed according to the original incubation concentration of NNK. This chiral CE method could be useful for the study on toxicology and metabolic transformations of related TSNAs.     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮的合成

异氰酸苯醇和N-[2-(4,6-二甲基)-嘧啶基]-羟胺(5)反应生成1-[2-(4,6-二甲基)-嘧啶基]-1-羟基-3-苯基脲(6)。化合物(6)在三乙胺存在下和氯甲酸乙醇反应生成2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮(1)。     

1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲的另一个手性对映体晶体结构

对-二甲氨基苯甲醛和苯基氨基硫脲缩合反应生成1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲(DMB), 产物能从溶液中析出单一手性对映体晶体. 用单晶X射线衍射技术测定了它的绝对构型, 晶体属正交晶系, P2₁2₁2₁空间群, a＝0.7870(2) nm, b＝1.1560(2) nm, c＝1.6668(3) nm, V＝1.5164(5) nm³, Z＝4, D_c＝1.307 g/cm³, F(000)＝632, μ＝0.213 mm^－1, 2557个可观测点[I＞2s(I)]精修的最终残差因子: R＝0.0409, wR＝0.1061, Flack参数为0.00(9), 能够确定绝对构型. 化合物的晶体结构和大宗粉末样品的固体圆二色谱表明化合物在结晶过程中发生单一对映体的手性堆积.     

Synthesis and Crystal Structure of Tert-butyl 4-[(E)-4-(1,3 -Dioxo-1,3-dihydro-2H-isoindol-2-yl)-1-butenyl] Benzoate

1 INTRODUCTION Phthalimide and its derivatives are synthetic mate- rials, which are widely used as important chemical intermediates of biosensors[1] and many drugs such as Citalopran[2], luminal[3], Beta-Lactam[4] and the No. three generation quinolones[5], and they have been identified as active groups of some drugs and chemical luminescence reagents[6, 7]. Tert-butyl 4- [(E)-4-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-1- butenyl] benzoate is an intermediate of a new type of insulin sen…