细胞色素P—450单加氧酶的模拟—在锰卟啉催化环己烷加氧反应中不同…

以ＭｎＴＰＰＣｌ为催化剂研究了不同氧原子供体ＰｈＩＯ，ＮａＯＣｌ和Ｈ２Ｏ２在环己烷加氧反应中的作用。根据动力学考察和ＵＶ－Ｖ１Ｓ，ＩＲ，ＥＳＲ分析认为，ＰｈＩＯ和ＮａＯＣｌ可能分别与ＮｔＰＰＣｌ形成具有转移氧原子能力的单核或双核的高氧化态氧化锰卟啉配合物，而Ｈ２Ｏ２与ＭｎＴＰＰＣｌ作用同形成非活性物种。     

2,4,6—三氧—1,3,5,2—三氮磷杂环己烷衍生物的合成及其生物活性

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，ＭＳ和元素分析所证实．初步生测结果表明，部分化合物具有一定的抗肿瘤活性．     

2—氯／2—甲磺酰基—5—（2—苯基—4—喹啉基）—1,3,4—恶二唑…

借处理２－羟基－５－（２－苯基－４－喹啉基）－１，３，４－恶二唑同ＰＣｌ５／ＰＯＣｌ３之间的反应合成了２－氯－５－（２－苯基－４－喹啉基）－１，３，４－恶二唑（３）和通过２－Ｙｕ基－５－（２－苯基－４－喹啉基）－１，３，４－恶二唑的甲基化，然后氧化制得２－甲磺酰基－５－（２－苯基－４－喹啉基）－１，３，４－恶二唑（６）。并分别研究了３和６同胺、叠氮及肼的反应，得到２，５－二取代的恶二唑新衍生物。初     

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。     

（3—苄基—4—芳酰基—1,2,4—三唑—5—基）（5—苯基—1,3,4—E…

通过３－苄基－４－芳酰基－１，２，４－三唑－５－巯基负离子在２－甲磺酰基－５－苯基－１，３，４－Ｅ二唑环２－位上的亲核取代反应，制得１３个新的（３－苄基－４－芳酰基－１，２，４－三唑－５－基）（５－苯基－１，３，４－Ｅ二唑－２－基）硫醚衍生物。经元素分析、ＩＲ、＾１Ｈ ＮＭＲ和ＭＳ裂解碎片分析确认结构。初步观察了它们在０．０１％浓度时对大肠杆菌繁殖的抑制作用。     

分子设计合成高折光指数的光学树脂（Ⅲ）：MMDMA的合成及？…

采用盐酸／硫脲法合成了２－巯基甲基－１，４－二硫杂环己烷，利用反滴碱液的低温相转移催化技术合成了２－甲基丙烯酰硫基甲基－１，４－二硫杂环己烷，讨论了ＭＭＤ合成过程中的结构变化，研究了ＭＭＤＭＡ的共聚性能，合成了折光指数高，色散能力低的新型光学树脂。     

1—甲苯磺酰基—3—芳基—4—苯基—1,4,2—二氮磷杂环戊—5—酮的合成及除草…

通过１－苯基－３－对甲苯磺酰基脲与亚磷酸三苯酯和取代苯甲苯在甲苯中进行的类Ｍａｎｎｉｃｈ反应合成１－对甲苯磺酰基－２－苯氧基－２－氧代－３－芳基－４－苯基－１，４，２－二氮磷杂环戊－５－酮。生物测定实验表明，某些产物具有良好的选择性除草活性。     

铽与4—酰代吡唑啉酮—5的三元配合物的合成与荧光性质

合成并表征了一系列铽与含不同４－酰代的１－苯基－３－甲基－吡唑啉酮－５的三元配合物Ｔｂ９Ｌ）３．２Ｈ２Ｏ和Ｔｂ（Ｌ）３．Ｄｉｐｙ「Ｌ＝１－苯基－３－甲基－４－乙酰基吡啥林酮－５（ＰＭＡＰ），１－苯基－３－甲基－４－丙酰基吡唑啉酮－５（ＰＭＰＰ），１－苯基－３－甲基－４－异丁酰基吡唑啉酮－５（ＰＭＩＢＰ），１－苯基－３－甲基－４－特戊酰基吡唑啉酮－５（ＰＭＰＶＰ），１－苯基－３－甲基－４－苯甲酰基吡     

合成2—芳基—3—烷基—7—硝基—1,4—氧硫杂萘—4,4—二氧化物的新…

在Ｋ２ＣＯ３－ＴＥＢＡ－ＤＭＦ体系中，２－（２－氯－４－硝基苯磺酰基）－１－芳基乙酮与各种灶基化试剂发生烷基化－环化反应，得到一系列３－位取代的１，４－氧硫要萘－４，４－二氧化物，并讨论了反应机理和反应条件。     

1—对甲苯磺酰基—2—氧代—2—苯氧基—3—芳基—1,4,2—二氮…

通过１－苯基本磺酰基硫脲（１）与亚磷酸三苯酯和取代苯甲醛在甲苯中进行的类Ｍａｎｎｉｃｈ反应合成１－对甲苯磺酰基－２－氧代－２－苯氧基－３－芳基－１，４，２－二氮磷杂环戊－５－硫酮（２）。本文对合成过程中所涉及到的副反应进行了初步探讨。     

Theoretical prediction of the p53 gene mutagenic mechanism induced by trans-4-hydroxy-2-nonenal

The reaction mechanism of guanine with trans-4-hydroxyl-2-nonenal (4-HNE) and the mutagenic mechanism induced by adducts have been theoretically predicted at a molecular level from the energy point of view. 4-HNE directly reacts with guanine via three steps, yielding eventually four main diastereoisomers: trans-4-HNE-dG adducts. A concerted six-atom-centered transition state is proposed for the first step, while the last two steps are involved in four-membered-ring transition states. The third step is the rate-determining step. The studies of base pairing properties of trans-4-HNE-dG adducts with A, T, C, A*, and T* together with the relationship between the mutation and structure of trans-4-HNE-dG indicate that syn- and anti-conformations of trans-4-HNE-dG around the glycosidic bond are favorable for pairing with A* and T*, respectively, in the parental generation. As a result, the GC --> CG or GC --> TA mutation may be generated from the syn-4-HNE-dGA* during replication. Nevertheless, anti-4-HNE-dGT* creates GC --> TA mutation or nonmutagenesis. Moreover, syn-4-HNE-dGA* has a slightly higher probability to be generated than anti-4-HNE-dGT* in the parental generation; therefore, the GC to TA transversion is predominant among the mutations. In addition, no correlation between the mutations and the stereochemistry of C6 and C8 of trans-4-HNE-dG adducts was found in this work. Our mutational results have interpreted well a part of the discrete experimental observations, but the mutagenic process itself has not previously been characterized, through either computation or experiment.     

一步法高压合成硫化异丁烯产物分析及反应机理

以正辛胺为催化剂,硫磺和异丁烯为原料在160~190 ℃条件下通过一步法高压合成硫化异丁烯。 采用气相色谱、红外光谱和¹H NMR谱等技术手段分析了产物硫化异丁烯的化学组成。 分析结果表明,产物中含有链状和环状的叔丁基多硫醚,其中链状多硫醚是主产物,同时伴有副产物4-甲基-3H-1,2-二硫杂茂-3-硫酮(MDTT)、叔丁基硫醇和少量的尾气如H₂S产生。 硫化过程中主要的副反应是碱催化下硫磺与异丁烯的脱氢反应,生成MDTT和H₂S,H₂S与异丁烯进行马氏加成反应生成叔丁基硫醇,叔丁基硫醇与硫磺反应生成链状的叔丁基多硫醚。     

Pyridazine Derivatives and Related Compounds,Part 1. Some Reactions with 4-Cyano-5,6-Diphenyl-2,3-Dihydropyridazine-3-One

4-Cyano-5,6-diphenyl-2,3-dihydropyridazine-3-onc 1 reacts with phosphorous oxychloride to give 70% of the corresponding 3-chloro derivative 2. Treating 2 with anthranilic acid in butanol, 4-cyano-2,3-diphenyl-10H-pyridazino[6,1-b]quinoxaline-10-one, 3 was obtained. Compound 1 reacts with phosphorous pentasulphide to give 3-mercapto derivative 4, which was converted by acrylonitrile to S-(2-cyanoethyl)pyridazine derivative 5. Compound 4 reacts with ethyl bromoacetate and with phenacyl bromide gave the corresponding thieno[2,3-c] pyridazine derivatives 8, 9, Alkylation of 1 with ethyl chloroacetate afforded 3-0-carbethoxymethyl derivative 10. Compound 10 reacts with amines (aniline, hydrazine) to give the corresponding amide and acid hydrazide 13, 12 respectively. Hydrolysis of 10 with sodium hydroxide gave the corresponding acid derivative 11. Treating 1 with methyl iodide, 3-0-methyl derivative 14 was obtained, which was converted by ammonium acetate/acetic acid to 3-amino-4-cyano-5,6-diphenyl pyridazine 15. Compound 1 reacts with methyl magnesium iodide gave 4-acetyl derivative 16, which was reacted with hydrazine, phenyl hydrazine and with hydroxylamine to give the substituted I H pyrazolo [3,4-c] pyridazine 17 a,b and isoxazolo [5,4-c] pyridazine 18 derivatives respectively.     

Studies with Polyfunctionally Substituted Heteroaromatics: The Reaction of Heterocyclic Enaminonitriles with α‐β‐Unsaturated Nitriles

5‐Amino‐4‐cyano‐3‐phenylpyrazole ( 1 ) reacts with cinnamonitriles ( 2 ) to yield the pyrazolo[1,5‐a]pyrimidines ( 3 ). Also, 5‐amino‐4‐cyano‐1‐phenylpyrazole ( 4 ) reacts with cinnamonitriles ( 2 ) to yield the pyrazolo[3,4‐b]pyridine derivatives ( 5 ). In contrast to this reaction, enaminothiophene ( 6 ) reacts with cinnamonitriles ( 2 ) to yield compound ( 7 ) not ( 8 ). The enaminopyrane ( 9 ) reacts with cinnamonitriles ( 2 ) to yield ( 10 ). Finally we have attempted to add cinnamonitriles ( 2 ) to thiopyrane ( 13 ); only rearrangement and aromatization product ( 14 ) was isolated.     

Anodization in oligo(ethylene glycol) as an initial derivatization tool for preparing glassy carbon electrodes covalently modified with amino compounds: effective access to a 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-modified glassy carbon electrode

Anodization in HO(CH2CH2O)nH (1a, n=2; 1b, n=3; 1c, n=4) as an initial derivatization tool for preparing glassy carbon (GC) electrodes covalently modified with amino compounds was explored. As an amino compound to be immobilized, 4-amino-2,2,6,6-tetramethylpiperidinyl-1-oxyl (4-amino-TEMPO) was selected. When GC electrodes anodized at 2.0 V vs. Ag wire coated with AgCl in 1 containing RCH2CH2SO3Na (2a, R=H; 2b, R=OH) were treated with a N,N-dimethylformamide (DMF) or CH2Cl2 solution of 4-amino-TEMPO and 1,3-dicyclohexylcarbodiimide (DCC), TEMPO-modified GC electrodes were afforded. Coverage (gammaTEMPO) of the electrode surfaces by TEMPO was estimated by cyclic voltammetry in CH3CN containing NaClO4. A TEMPO-modified GC electrode with the best gammaTEMPO (1.36 x 10(-10) mol/cm2) was obtained by anodization in 1b containing 2a at the expense of 3.0 C followed by amidization in DMF for 7 d. On cyclic voltammetry, the TEMPO-modified GC electrode showed good and stable electrocatalytic ability for oxidation of allyl alcohol in the presence of 2,6-lutidine.     

Synthesis and reactivity of 3-(trichlorogermyl)propanoic acid and 3-(triphenylgermyl) propanoic acid

3-(Trichlorogermyl)propanoic acid (la) reacts with phenylmagnesium bromide in malar ratio 1:4 to give 3-(triphenylgermyl)propanoic acid (2a).In the compounds la and 2a theβ-carboxylic functional group shows some unusual properties when they react with excess of phenylmagnesium bromide.The compound la reacts with phenylmagnesium bromide in molar ratio 1:5 to give phenyl 2-(triphenylgermyl)ethylketone (3a) and in molar ratio 1:6 to give l,l-diphenyl-3-(triphenylgermyl)propanol (4a).The compound 2a reacts with phenylmagnesium bromide in molar ratio 1:2 to give 3a and in molar ratio 1:3 to give 4a also.Dehydration of the compound 4a with dilute hydrochloric acid seems especially easy.Moreover,the compound la reacted with phenylmagnsium bromide in molar ratio 1:6,then the mixture was treated with dilute hydrochloric acid to give 1,1-diphenyl-3-(triphenylgermyl)-1-propene (5a) in one pot reaction.Alkyl Ge-C bond in the compound 5a can be cleaved selectively by lithium aluminium hydride ( LiAlH4) in good yiel     

Heterodiene synthesis. Synthesis of fused thiopyrano [2,3-d]thiazole,Benzopyrano[3′,4′:4,5]thiopyrano[2,3-d]thiazole and thiazolo[3,4-c]triazine derivative

5-Salicylidenethiazolidine-2,4-dithione ( 1 ) reacts with acrylonitrile, N-phenylmaleimide and dimethyl acet-ylenedicarboxylate to afford the fused thiopyrano[2,3-d]thiazolidinethione derivatives 2, 4 and 6 , respectively. The salicylidene derivative 1 reacts with ethyl acrylate and malononitrile to afford the fused [1]benzopyrano[3′,4′:4,5]thiopyrano[2,3-d]thiazoles 3 and 9 , respectively. 4-Phenylhydrazono-2-thiazolidinethione ( 11 ) reacts with ethyl bromoacetate and/or phenacyl bromide to yield the fused thiazolo[3,4-c]triazines 13 and 14.     

CO_2和丙三醇直接合成碳酸甘油酯的新方法

报道了一种以CO_2和丙三醇为原料,Cs_2CO_3为碱,DMF为溶剂,bmimBF_4为增溶剂,直接合成碳酸甘油酯(GC)的新方法。在最优反应条件[丙三醇5 mmol,Cs_2CO_310 mmol,CH_2Cl_25 m L,bmimBF_41 m L,DMF 5 m L,P(CO_2)1 MPa,于100℃反应24 h]下,GC收率76%,其结构经1H NMR和ESI-MS确证。在最优条件下进行50倍放大实验,GC收率72%。     

Interaction of 1-Benzyl-4-benzoyl-5-phenyl-2,3-dihydro-2,3-pyrroledione with Ketene Diethylacetal: Synthesis and Crystal and Molecular Structure of 1-Benzyl-4-benzoyl-3-hydroxy-5-phenyl-5-ethoxycarbonylmethyl-2,5-dihydro-2-pyrrolone

1-Benzyl-4-benzoyl-5-phenyl-2,3-dihydro-2,3-pyrroledione reacts with ketene diethylacetal, forming 1-benzyl-4-benzoyl-3-hydroxy-5-phenyl-5-ethoxycarbonylmethyl-2,5-dihydro-2-pyrrolone, whose crystal and molecular structure was studied by XRD.