α-乙酰基二硫缩烯酮α碳原子的酰化反应

进行了α-乙酰基二硫缩烯酮与酰氯的酰化反应. 以干燥的二氯甲烷为溶剂, 在四氯化钛催化下, α-乙酰基环二硫缩烯酮(1)可与脂肪及芳酰氯(2)反应, 在化合物1的α-碳原子上发生酰化反应, 以较高的产率生成各种α-乙酰基-α-酰基二硫缩烯酮(3).     

乙酰基硫代甲酰芳胺合成二氢吡嗪的研究

报道了一种合成乙酰基硫代甲酰芳胺的方法. 合成的乙酰基硫代甲酰芳胺与1,2-乙二胺缩合生成5-(4'-取代苯胺基)-6-甲基-2,3-二氢吡嗪类杂环化合物.     

2-(芳氧基苯基硫代膦酰基)-1,2,3σ^2-二氮磷杂环戊二烯的合成

研究了芳氧基苯基硫代膦酰基酮腙与三氯化磷的环化反应, 成功地合成了2-N上带有硫代膦酰基的3-氯1,2,3-二氮磷杂环戊烯(3)及二配位磷化物2-硫代膦酰基1,2,3σ^2-二氮磷杂环戊二烯(4)。     

α-氧代烯酮环二硫代缩酮化学——α,α-二氧代烯酮环二硫代缩酮与乙二胺反应

由α，α－二氧代烯酮环二硫代缩酮与乙二胺反应制得五种α，α－二氧代烯酮环二氮代缩酮化合物，所有产物均经元素分析、ＩＲ、１ＨＮＭＲ和１３ＣＮＭＲ确证。     

α—氧代烯酮环二硫代缩酮化学：α,α—二氧代烯酮环二硫代缩酮与乙二…

由α，α－二氧代烯酮环二硫代缩酮与乙二胺反应制得五种α，α－二氧代烯酮环二氮代缩酮化合物，所有产物均经元素分析，ＩＲ＾１ＨＮＭＲ和＾１３ＣＮＭＲ确证。     

(反)-肉桂酰基二茂铁缩二硫代碳酰腙及其Cu(Ⅱ)、Zn(Ⅱ)配合物的合成与表征

合成了两种未见文献报道的Schiff碱HCFM[(反)-肉桂酰基二茂铁-(S)-甲基二硫代碳酰腙]及HCFB[(反)-肉桂酰基二茂铁-(S)-苄基二硫代碳酰腙]及其铜(Ⅱ)、锌(Ⅱ)的六个配合物Cu(CFM)2@H2O、Cu(CFM)OAc@H20、Cu(CFB)2@H20、zn(CFM)2@2H20、Zn(CFM)0Ac@H20、Zn(CFB)2,考察了它们的物理性质,并利用元素分析、IR、1H NMR谱及摩尔电导表征了它们的组成、可能结构及配位过程.实验结果表明:这两种Schiff碱都是反式双齿配体,烯硫醇化失去质子后以负硫离子与过度金属离子形成共价键,氮原子与中心金属离子形成配位键.     

Grignard试剂与α-肉桂酰基环二硫缩烯酮的区域选择性加成反 应

乙基、丙基、丁基、苯基和苄基卤化镁等Grignard试剂与具有三个亲电中心的α-肉桂酰基环二硫缩烯酮类化合物2反应,加成反应发生在2中与芳基相邻的碳原子上,生成共轭加成产物3,反应具区域选择性。     

(反)-肉桂酰基二茂铁缩二硫代碳酰腙及其Cu(ⅡI)、Zn(Ⅱ) 配合物的合成与表 征

合成了两种未见文献报道的Schiff碱HCFM[(反)-肉桂酰基二茂铁-(S)-甲基二硫代碳酰腙]及HCFB[(反)-肉桂酰基二茂铁-(S)-苄基二硫代碳酰脘]及基铜(Ⅱ)、锌(Ⅱ)的六个配合物Cu(CFM)2·H2O、Cu(CFM)OAc·H2O、Cu(CFB)2·H2O、Zn(CFM)2·2H2O、Zn(CFM)OAc·H2O、Zn(CFB)2,考虑了它们的物理性质,并利用元素分析、IR、1^HNMR谱及摩尔电导表征了它们的组成、可能结构及配位过程。实验结果表明：这两种Schiff碱都是反式双齿配体,烯硫醇化失去质子后以负硫离子与过度金属离子形成共价键,氮原子与中心金属离子形成配位键。     

N,N′-双(2-羟基-3-甲氧基-5-甲基苯甲叉基)乙二胺合钴(Ⅱ)类似物的合成及其对氧分子的加合性能

2-羟基-3-甲氧基-5-甲基苯甲醛分别与乙二胺、1,2-丙二胺、1,3-丙二胺、2,3-二甲基-2,3-丁二胺及邻苯二胺反应,合成出一系列二元Schiff碱型化合物.测定Schiff碱与钴(Ⅱ)离子配合后的配合物对氧分子的加合常数,讨论了结构与加合性能之间的关系.配合物中二胺-钴螯合环的刚性对配合物的氧加合性有重要影响.     

一种合成α-硫代-β-氨基酸酯的新方法

以β-烯胺酯和N-硫代-丁二酰亚胺为原料,溴化铜为催化剂,经氧化偶联反应制得5个新型α-硫代-β-脱氢氨基酸酯(3a~3e);3经氢化硅烷化反应,合成了5个α-硫代-β-氨基酸衍生物(4a~4e),其结构由1H NMR表征。在最佳反应条件(3 0.1 mmol,三氯硅烷2.0 eq.,DCE 1 m L,于室温反应12 h)下,4a收率97%。     

Synthesis of bicyclic N,N-enaminals by cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH

A cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH was found to lead to bicyclic N,N-enaminals. The studies of this reaction showed that 1,3-diaminopropane and N-methyl-1,3-diaminopropane gave (E)-6-(arylmethylidene)octahydropyrrolo[1,2-a]pyrimidines in 45—78% yields, whereas 1,2-diaminoethane gave 5-(arylmethylidene)hexahydropyrrolo[1,2-a]imidazoles as mixtures of E- and Z-isomers in up to 75% total yield. The mechanism of these new cascade cyclization reactions includes formation of the equilibrium mixtures of imines and cyclic aminals with subsequent intramolecular hydroamination of the triple bond having considerable ionic character.     

N，N＇－二取代一硫代草酰胺的合成及其与二元胺反应的研究

Ｎ，Ｎ＇－二取代一硫代草酰胺的合成及其与二元胺反应的研究陆忠娥，邹建平，袁于人，陈克潜（苏州大学化学系，苏州，２１５００６）关键词Ｎ，Ｎ＇－二取代一硫代草酰胺，咪唑啉，四氢嘧啶Ｎ，Ｎ＇－二硫代草酰胺可与多种金属络合，而Ｎ，Ｎ＇－二取代一硫代草酰胺的合...     

Investigation of energetic materials prepared by reactions of diamines with picryl chloride

Five compounds containing picryl group(s) were synthesized from reactions of hydrazine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane and 1,7-diaminoheptane with picryl chloride under hydrothermal conditions in methanol. Hydrazine reaction yielded N-2,4,6-trinitrophenylhydrazine which has a single picryl group, whereas the other reactants formed symmetric products with both amine groups connected to picryl groups. These compounds are N,N′-di-2,4,6-trinitrophenyl-1,2-diaminoethane, bis-N,N′-di-2,4,6-trinitrophenyl-1,3-diaminopropane, bis-N,N′-di-2,4,6-trinitrophenyl-1,4-diaminobutane and bis-N,N′-di-2,4,6-trinitrophenyl-1,7-diaminoheptane. Molecular structures of two of these compounds, N-2,4,6-trinitrophenylhydrazine and bis-N,N′-di-2,4,6-trinitrophenyl-1,3-diaminopropane, were revealed by XRD methods. All compounds were investigated by TG and DSC methods. The thermal behaviour of N-2,4,6-trinitrophenylhydrazine was explosive, undergoing a strong explosion in a very short temperature interval, 180–185 °C. In cases of the other compounds, it was found out that the carbon chain between two picryl groups reduced the explosion enthalpy. In addition, the theoretical formation enthalpy of N-2,4,6-trinitrophenylhydrazine was calculated by running CBS-4 M energy calculations under Gaussian 09 software package. From the calculated value, reaction enthalpy values for the possible explosion pathways were investigated in accordance with the experiment. The path with reaction enthalpy closest to the experimental value was proposed as the explosion mechanism.     

Diastereo‐ and Regioselective Addition of Thioamide Dianions to Imines and Aziridines: Synthesis of N‐Thioacyl‐1,2‐diamines and N‐Thioacyl‐1,3‐diamines

Addition reactions of thioamide dianions that were derived from N‐arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N‐thioacyl‐1,2‐diamines in a highly diastereoselective manner in good‐to‐excellent yields. The diastereomeric purity of these N‐thioacyl‐1,2‐diamines could be enriched by simple recrystallization. The reduction of N‐thioacyl‐1,2‐diamines with LiAlH₄ gave their corresponding 1,2‐diamines in moderate‐to‐good yields with retention of their stereochemistry. The oxidative‐desulfurization/cyclization of an N‐thioacyl‐1,2‐diamine in CuCl₂/O₂ and I₂/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N‐tosylaziridines gave the addition products of N‐thioacyl‐1,3‐diamines with low diastereoselectivity but high regioselectivity and in good‐to‐excellent yields. The use of AlMe₃ as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X‐ray diffraction.     

Novel syntheses of hexahydropyrimidines and tetrahydroquinazolines

1-Benzotriazolylmethyl-3-propylhexahydropyrimidine (1) and 1,3-bis(1H-1,2,3-benzotriazol-1-ylmethyl)-1,2,3,4-tetrahydroquinazoline (3) were readily prepared by reactions of N-propyl-1,3-propanediamine or 2-aminobenzylamine with benzotriazole and formaldehyde, respectively. Intermediate 1 reacted with alkyl and aryl Grignard reagents to produce N,N'-unsymmetrically substituted hexahydropyrimidines 2a,b in 90 and 92% yields, respectively. Nucleophilic substitutions of 3 with Grignard reagents, allylsilane, and triethyl phosphite gave N,N'-disubstituted 1,2,3,4-tetrahydroquinazolines 4a-f, 5, and 6 in good to excellent yields. Successive treatment of 3 with two different Grignard reagents in one-pot reaction led regiospecifically to N,N'-unsymmetrically substituted tetrahydroquinazoline derivatives 8a,b.     

Base-catalyzed cyclization reactions of 2-[2-(2,4-dimethyl-3-oxopentyl)]benzimidazoles with acetic anhydride and its homologs

2-[2-(2,4-Dimethyl-3-oxopentyl)]benz, imidazoles ( 2-10 ) were obtained by allowing o-phenyl-enediamines to react with 2,2,4,4-tetramethyl-1,3-cyclobutanedione ( 1 ). When refluxed with acetic anhydride (or sterically unhindered homologs) they cyclize in the presence of base to yield the pyrido[1,2-α]benzimidazoles ( 16-21 and 24, 25 ). The 2-[2-(2,4-dimethyl-3-oxo-pentyl) ]imidazolines ( 12 and 14 ) were obtained by reaction of 1,2-diaminoethane and 1,2-diaminopropane, respectively, with 1 . When allowed to react with acetic anhydride/base, they gave only N-acylated products.     

SYNTHESIS,CHARACTERIZATION AND SOLUTION CHEMISTRY OF NEW Re(V) DIOXO COMPLEXES

Abstract

In this work, we report the synthesis, characterization and potentiometric studies of new Re(V) complexes of general formula [ReO₂(amine)₂]⁺ (amine = 1,2-diaminopropane, 1,4-diaminobutane, N,N′-diethylethylenediamine, diethylenetriamine, triethylenetetramine and N-tris(2-aminoethyl)amine). Compounds were prepared starting from [ReO₂I(PPh₃)₂] and characterized by several techniques. The presence of different substituent groups in the diamines (including alkyl and amine groups) allows the presence of pendant arms. When these groups are free amino groups, they can react with acids such as H⁺ and M²⁺ cations and studied by potentiometry. The formation of very stable binuclear species was demonstrated.     

锰(Ⅱ)呋喃甲醛Schiff碱催化苯乙烯环氧化的研究

自1979年Groves首先以金属卟啉模拟细胞色素P－450,实现烯烃的环氧化^[1]以来,仿单加氧酶催化环氧化烯烃就成为仿酶催化领域里的一个非常活跃的研究课题^[2-5],但在这些报道中所用的模型化合物均为金属卟啉及其衍生物或Mn-Salen及其衍生物,这些化合物高昂的价格极大地限制了其应用前景。呋喃甲醛（俗称糠醛）取之于米糠或玉米芯,价格便宜且非石化产品,用它取代水杨醛不仅可降低成本,而且符合绿色化学要求。为此,本文选取了五种锰呋喃甲醛Schiff碱配合物作为模型化合物,以NaOCI为氧化剂,催化苯乙烯环氧化。讨论了配体结构、氧化物的pH值、轴配体、反应时间对催化环氧化反应的影响。     

A facile synthesis of unsymmetrical heterocyclic azines by cyclodesulfurization: Reaction of methyl arylalkylidenehydrazinecarbodithioates with diamines

A new and facile synthesis of unsymmetrical heterocyclic azines is described. Methyl arylalkylidenehydraz-inecarbodithioates, prepared by the condensation of ketones or aldehydes with methyl hydrazinecarbodithioate, were heated under reflux with various diamines in ethanol. Secondary diamines, such as N,N′-dimethyl-ethylenediamine, N,N′-dimethyl-1,3-diaminopropane or N,N′-dimethyl-o-phenylenediamine, reacted smoothly with loss of hydrogen sulfide to give good yields of unsymmetrical azines. However, primary diamines, such as ethylenediamine or o-phenylenediamine, and primary/secondary diamines, such as N-methylethyl-enediamine and N-methyl-1,3-diaminopropane gave, instead, only the corresponding uncyclized thiosemi-carbazones. A cyclodesulfurization mechanism for azine formation is discussed.     

Synthesis and Reactions of 1,1-Dimethyl-3-oxobutyl-isothiocyanate (DMO-ITC)

In this review an attempt has been made to compile all the existing comprehensive literature for the synthesis of 1,1-Dimethyl-3-oxobutyl-isothiocyanate (DMO-ITC) and its reactions with the compounds having different functional groups, such as amines, diamines, amino alcohols, amino phenols, amino thiophenols, amino nitriles, amino acids, and hydrazines. The peculiar behavior of the DMO-ITC is due to its sensitivity toward acids and gives different products when the reaction occurs in the absence and presence of an acid. The pH of the reaction condition also plays an important role. Normally, DMO-ITC gives pyrimidinethione derivatives when treated with amines, but reactions become interesting when the compounds have an amino group as well as the other functional group (NH 2 , OH, SH, CN, COOH) at ortho position, providing condensed bicyclic, tricyclic, or poly heterocycles with ring nitrogen and/or sulfur is of biological importance. The reaction of DMO-ITC with ethylene diamine, o -phenylenediamines, 1,2-diaminoanthraquinone, o -diaminonaphthalenes, N -aminoethyladenosine, 2-amino ethanol, o -aminophenols, o -aminothiophenols, o -aminobenzonitriles, and o -aminobenzoic acids gave imidazopyrimidinethione, pyrimidobenzimidazolethiones, pyrimidoanthraquinonimidazolethione, pyrimidonaphthoimidazolethiones, furanopurinimidazopyrimidinethione, oxazolopyrimidinethione, oxafluorenethiones, thiafluorenethiones, thioxophenanthreneones, and thiaphenanthreneones derivatives respectively. But similar reactions were not seen with o -diaminoheterocycles. Hydrazines derivatives gave seven-membered heterocycles, that is, triazepinethiones derivatives. The synthesis of the heterocycles are well defined in separate sections according to the update references.