3-芳基-5-巯基-1,2,4-三唑的亲核取代反应研究

以3-芳基-5-巯基-1,2,4-三唑为原料合成了20个3-芳基-1,2,4-三唑-5-巯基乙酸乙酯(2a～e)、3-芳基-1,2,4-三唑-5-巯基乙酸(3a～e)、3-芳基-5,6-二氢噻唑并[2,3-c]均三唑(5a～e)和3-芳基-6,7-二氢均三唑并[3,4-b][1,3]噻嗪(6a～e)。研究了3a～e在微波辐射下的环化反应，合成了5个3-芳基-5-氧代-6H-噻唑[2,3-c]均三唑(4a～e)。产物经元素分析、红外、核磁共振以及质谱方法确定了结构。初步研究了代表化合物的生物活性。     

1-氯-3-硝基-2-丁烯与2-硝基丙烷钠盐的SRN1反应

本文研究了1-氯-3-硝基-2-丁烯与2-硝基丙烷钠盐的SRN1反应, 结果表明这种开链状纯脂肪族烯丙基型化合物发生了不重排的SRN1反应.     

电化学和石英晶体微天平研究2-巯基苯并咪唑的电化学氧化反应

应用循环伏安研究水相中２－巯基苯并咪唑的电化学氧化过程,考察了ｐＨ值、浓度等的影响,并应用电化学石英晶体天平（ＥＱＣＭ）监测了此氧化成膜的过程。结果表明此反应为一电子过程。结合表面光电子能谱（ＸＰＳ）对此氧化膜进行了初步表征。     

2-巯基苯并咪唑及其类似物互变异构的理论研究

采用B3LYP/6-311G**方法, 计算了2-巯基苯并咪唑及其类似物(2-巯基苯并噁唑、2-巯基苯并噻唑、2-羟基苯并咪唑、2-羟基苯并噁唑、2-羟基苯并噻唑以及2-巯基咪唑、2-巯基噁唑、2-巯基噻唑、2-羟基咪唑、2-羟基噁唑、2-羟基噻唑)的(硫)醇式与(硫)酮式结构进行质子迁移的3种可能途径: (a)分子内质子迁移; (b)水助质子迁移; (c)甲醇助质子迁移．结果表明, 途经b和c所需要的活化能较小, 氢键在降低反应活化能方面起重要作用．采用PCM方法研究了反应体系的溶剂化效应．结果表明孤立分子、一水合物和一甲醇合物的最稳定异构体相同, 都为(硫)酮式, 与气相结论一致．溶剂化效应对异构化能垒的影响较小.     

微波辐射下2-取代苯并咪唑衍生物库的平行合成

以邻苯二胺及相应羧酸为原料,于多聚磷酸存在下,由微波辐射平行合成了一个小型2-取代苯并咪唑衍生物库,反应时间由常规加热的几小时到几天缩短为20min,且产率较高。经元素分析和1H NMR确证了产物结构。     

3-氯-2-烃基四氢吡喃的镁开环反应

研究了用镁对3-氯-2-烃基四氢吡喃(1)的开环反应,制得一系列5-烃基-4-戊烯-1-醇(2),上述反应产率高,立体选择性强,无论顺式或反式的(1)开环时都得到反式(2).     

2-巯基苯并咪唑与溶菌酶作用机理的研究

在生理条件下利用光谱法和分子模拟技术研究了2-巯基苯并咪唑对溶菌酶的毒性作用机理,分析了二者的结合特性,探讨了溶菌酶空间结构和酶活性的变化,模拟了二者的具体结合位置,结果表明2-巯基苯并咪唑可以通过静态猝灭的方式显著地猝灭溶菌酶的内源荧光。通过测量不同温度下的结合位点数、结合常数以及热力学常数,显示2-巯基苯并咪唑与溶菌酶主要通过氢键和范德华力相结合。分子模拟结果显示2-巯基苯并咪唑结合在溶菌酶的活性位点处,并最终导致溶菌酶空间结构和酶活性的变化。该研究为从分子水平上考察2-巯基苯并咪唑的毒性作用机理提供了参考。     

无溶剂微波照射下2－取代苯并咪唑的合成

用PPA作催化剂，在无溶剂微波照射下合成了10种2－取代苯并咪唑，为该类化 合物的合成提供了一种新方法。与常规方法相比，反应时间大大缩短，产率与传统 合成方法相当。     

A simple and efficient approach for the synthesis of a novel class aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives via intramolecular nucleophilic substitution reaction

In this study, we synthesized a new series of substituted aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives (6-24) in yields ranging from 42 to 70% with an interesting mechanism that involves internal nucleophilic substitution followed by an S_N2-type nucleophilic substitution. First, 1-(4-chlorophenyl)-2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethanone (3) was synthesized from the reaction of 5-methyl-1,3,4-thiadiazole-2-thiol (1) with 2-bromo-1-(4-chlorophenyl)ethanone (2) in the presence of potassium hydroxide. Then, 1-(4-chlorophenyl)-2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethanol (4) was synthesized by a reduction reaction of this compound using NaBH₄. Finally, 5-methyl-3-alkyl-1,3,4-thiadiazol-2(3H)-one derivatives (6-24), which are the target compounds, were synthesized from the reaction of this compound (4), which is a secondary alcohol with various alkyl halides (5a-n) in the presence of sodium hydride (NaH). This study presents an interesting reaction mechanism related to the synthesis of aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives that is not recorded in the literature.     

One-pot three-component reaction for the synthesis of novel series of fully substituted 1,3,4-oxadiazole derivatives bearing pyridine moiety

(N-isocyanimino)triphenylphosphorane, 2-pyridinecarbaldehyde, and aromatic carboxylic acids (benzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 3-methoxybenzoic acid, 1-naphthoic acid, and 2-naphthoic acid) undergo a 1:1:1 addition reaction under mild conditions in a one-pot reaction to afford novel series of fully substituted 1,3,4-oxadiazole derivatives in good yields.     

一种高亲核怀长链咪唑肟的合成与反应

报道了一种新的高亲核长链咪唑肟N-十四烷基咪唑-2-甲醛肟的设计与合成， 并比较了它及其他长链咪唑肟与有机磷酸酯二苯基、对硝基苯基磷酸酯（PNPDPP） 、对硫磷及V_x的反应活性。结果表明，该肟对PNPDPP、对硫磷等磷酸酯反应活性 很高，超过目前已报道的反应活性最强的肟基试剂5～10倍，可用于毒性高且难以 分解的磷酸酯消毒与防护。     

Formation of an organolithium derivative of 2-(α-aminobenzyl)-1-methylbenzimidazole in the reaction of 2-benzoyl-1-methylbenzimidazole oxime with lithium naphthalenide

It was shown with the reaction of 2-benzoyl-1-methylbenzimidazole oxime with lithium naphthalenide that ketoximes can be used to obtain difficultly accessible organolithium derivatives of primary nonaromatic amines.     

Synthesis and Antifungal Bioactivity of Methyl 2-Methoxyimino-2-{2-[(substituted benzylidene)aminooxymethyl]phenyl}acetate and 2-Methoxyimino-2-{2-[(substituted benzylidene)aminooxy-methyl]phenyl}-N-methylacetamide Derivatives

Ten methyl 2‐methoxyimino‐2‐{2‐[(substituted benzylidene)aminooxymethyl]phenyl}acetate and 2‐methoxy‐ imino‐2‐{2‐[(substituted benzylidene)aminooxymethyl]phenyl}‐N‐methylacetamide derivatives were synthesized. Structures of the new compounds were characterized by IR, ¹H NMR and GC‐MS data. These compounds at 10 µg/mL were tested in vitro against five pathogenic fungi, namely, Sclerotonia, Botrytis cinerea Pers, Gibberella zeae, Rhizoctorua solani and Pyricularia oryzae. Compounds G₅ , G₆ , G₇ and G₈ showed potent antifungal activities against Botrytis cinerea Pers, G₇ against Gibberella zeae and G₇ , G₈ against Rhizoctorua solani, respectively.     

2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4- 噻唑啉酮的合成

以2-氨基-5-取代苯氧甲基-1,3,4-噻二唑(1)为起始原料, 合成了中间体2-氯乙酰氨基-5-取代苯氧甲基-1,3,4-噻二唑)-2-乙酰亚胺(2)和2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-4-噻唑啉酮(3), 化合物3进一步与取代苯甲醛发生类Knoevenagle缩合反应, 得到了一系列2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4-噻唑啉酮类化合物4a～4p. 目标化合物4a～4p的结构经IR, ¹H NMR和元素分析确证.     

3-Phenoxy- and 3-phenylthio-1-propynyl substituted derivatives of silicon and germanium

Reactions of bromomagnesiopropargyl phenyl ethers and their isostmctural sulfides BrMgCCCH₂XPh (X = O, S) with MeVinSiCl₂, Me(CH₂Cl)SiCl₂, EtSiHCl₂, and Me₂SiHCl afforded the corresponding 3-phenoxy- and 3-phenylthio-1-propynyl substituted derivatives of silicon (PhXCH₂CC)₂SiRR¹ and PhXCH₂CCSiHMe₂ (X = O, S). Reactions of the above-mentioned Iotsitch reagents with GeCl₄ led to the corresponding germanium derivatives (PhXCH₂CC)₄Ge (X = O, S).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 511–513, March, 1994.     

Multicomponent reaction of amine,carbon disulfide,and fluoronitrobenzene via nucleophilic attack on the fluorinated carbon for the synthesis of nitrophenyl methylcarbamodithioates

In this paper, multicomponent reaction of amine, carbon disulfide and fluoronitrobenzene is reported for the synthesis of nitrophenyl methylcarbamodithioate derivatives. The method is based on the nucleophilic attack of the activated methylcarbamodithioate salt to fluoronitrobenzene. Several starting materials are tested and successfully produced the corresponding nitrophenyl methylcarbamodithioate. A possible mechanism for the reaction is suggested.     

密度泛函理论研究香草醛与氨基硫脲的加成-缩合反应

针对氨基硫脲和香草醛亲核加成-缩合反应的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何优化,通过Mulliken电荷分析推测出香草醛具有较高的亲核加成反应活性.对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算出相应温度下的反应焓变、吉布斯自由能变和平衡常数.实验表明,在298K～1000K内,氨基硫脲与香草醛的亲核加成-缩合反应是一个放热反应,吉布斯自由能变成负值,平衡常数很大,说明反应在温和条件下即能自发进行.在此基础上采用含时密度泛函方法(TD-DFT)计算了分子激发态的电子跃迁能,得到对应激发态的吸收波长,所得结果与文献值基本吻合.     

Theoretical study of bimolecular elimination (E2) reactions. Possibility ofsyn E2 elimination in the series of 2-R-2-R'-1-halocyclopropanes

Reactions of the methoxide ion with substituted halocyclopropanes, which result in E2 elimination, have been studied by the semiempirical quantum-chemical AM1 method. The transition states corresponding totrans andcis routes have been localized. The energetic predominance of thetrans route over thecis route is reduced by 2.6 kcal mol^–1 on going from 1-chloropropane to chlorocyclopropane because of the features of cyclopropane geometry. It has been demonstrated that, in the gas phase,cis elimination may predominate overtrans elimination for a particular stereoisomer of 2-cyano-2-methyl-1-halocyclopropanes due to weakening of orbital interactions and Coulomb repulsion between the cyano group and the MeO^– anion in thetrans E2 transition state.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 620–623, April, 1995.