1,1,1-三氯-2-取代肼基-3-硝基丙烷及其衍生物的合成

叙述了以1,1,1-三氯-2-乙酰氧基-3-硝基丙烷和1,1,1-三氯-2-肼基-3-硝基丙烷为原料,合成脂肪和芳香肼类、酰肼类、偶氮类以及腙类等四十三个新化合物的方法,将N-芳基-N'-[2-(1,1,1-三氯-3-硝基)丙基]肼用N-溴代丁二酰亚胺氧化成1,1-二氯-2-芳偶氮基-3-硝基丙烯后,不经分离直接加入过量的醇和定量的水继续反应,可方便地获得β-硝基丙酮酸酯腙类化合物,收率达60%以上。初步抑菌活性测定结果表明,大多数化合物呈现不同程度的抑菌活性,其中以肼类和偶氮类化合物的活性最高,丙酮酸酯腙类化合物次之。     

偶氮二甲酸二异丙酯的合成

以氯甲酸异丙酯、水合肼为主要原料,制备肼-1,2-二甲酸二异丙酯,然后用双氧水氧化制得偶氮二甲酸二异丙酯(DIAD)。 研究确定了最佳的反应条件:在0 ℃以下乙醚溶剂中,水合肼和氯甲酸异丙酯反应2 h,制备肼-1,2-二甲酸二异丙酯;n(肼-1,2-二甲酸二异丙酯)∶n(双氧水)=1:1.1,在-5~5 ℃下反应2 h,双氧水氧化得到偶氮二甲酸二异丙酯,总收率为90.7%,采用红外光谱、核磁共振等技术手段验证了中间体及目标产物结构。     

芳酰基芳基偶氮化合物的合成

芳酰基芳基偶氮化合物的合成;芳酰基芳基偶氮化合物;哌啶氮氧自由基;芳酰基芳肼;相转移催化     

二取代苯基卡巴腙的合成新方法

二苯基卡巴腙是一种重要的有机分析试剂,常用于测定和检出多种金属离子.¹文献报道的合成方法一般是用氧化剂对二苯基卡巴肼进行氧化脱氢制得,但产率偏低,操作较烦.^2,3 近来,我们用相转移催化法对二取代苯基卡巴肼脱氢,高产率地制得双(取代苯基)羰基二偶氮化合物.⁴ 但是相转移催化法不能得到单侧脱氢产物. 本文首次用价廉易得的三氯化铁为氧化剂,控制其与二取代苯基卡巴肼的摩尔比, 在酸性介质中反应,高产率地制备出8个二取代苯基卡巴腙化合物.该方法反应时间短, 条件温和,现象明显,操作简便.产物结构已经元素分析,IR, NMR,谱证实.     

低价钛盐还原反应的研究——Ⅱ.低价钛盐与芳基三卤甲烷的反应

用LiAlH_4或Zn、Mg等与四氯化钛作用得到的低价钛盐能使芳基三卤甲烷还原偶联为1,1,2,2-四卤-1,2-二芳基乙烷、1,2-—二卤-1,2-二芳基乙烯或二芳基乙炔,反应可能生成ArCX_2·自由基,然后偶联为二芳基四卤代乙烷,后者能脱去卤素生成二芳基二卤代乙烯。TiCl_3和Ti°与三氯甲苯作用能得到相似的后果。     

钯催化芳基偶氮的氧化羰基化反应

采用TBHP作为氧化剂,发展了钯催化芳基偶氮化合物N＝N双键断裂的氧化羰基化反应.芳基偶氮的羰基化反应在Pd(OAc)2(5％),MeO-BIPHEP (5％),芳基偶氮(0.2 mmol),TBHP(2 equiv),H2O(1 equiv),DCE(1 mL),CO (3.0 MPa)的条件下110℃反应12h后,经柱层析纯化分离得到31％-91％的芳基脲.初步的机理研究表明,芳基偶氮化合物的N＝N双键断裂原位产生芳基胺,再进一步氧化羰基化生成芳基脲.     

N,2-二芳基二氮亚烯甲酰胺合成的新方法

偶氮化合物可用作非线性光学材料、激光盘信息存贮材料和现代科技中的油溶性染料［１］．传统偶氮化合物的制备有重氮盐偶合和取代肼氧化等许多方法［２～４］,其偶氮基两端一般联有烃基或芳环,而联有羰基的偶氮类化合物用通常方法难以制备．本文首次用Ｎ－溴代丁二酰亚...     

镍催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃与格氏试剂偶联反应制备多取代烯烃

以5.0 mol%NiCl_2(dppe)作为催化剂,催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂偶联反应,高选择性制备了一系列多取代烯烃化合物.有机硫基团经水解、氧化后生成二芳基二硫醚,实现了硫资源的循环利用,符合绿色化学要求.同时,此方法对不同取代的(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂均具有较好的适用性,以较高的产率获得相应的目标产物,为多取代烯烃的制备提供了有效的路径.     

2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉类化合物的合成

在冰醋酸存在下, 4-取代苯乙酮和溴素容易进行溴代反应, 得到α-溴-4-取代苯乙酮; 将其和1,2,4-三唑在丙酮中反应, 得到α-(1,2,4-三唑-1-基)-4-取代苯乙酮2; 在冰醋酸催化下, 2和4-取代苯甲酰肼1进行缩合, 得到相应酰腙衍生物3; 化合物3在乙酸酐的作用下环化生成一系列2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉4. 化合物4的结构经IR, 1H NMR, MS, 元素分析和单晶衍射确证.     

一步法合成取代-1, 2-苯醌类化合物

应用固定化多酚氧化酶催化的氧化-迈克尔加成反应,一步合成了4,5-二取代-1,2-苯醌类化合物:4,5-N,N-二(苯胺基)-1,2-苯醌,4,5-N,N-二(对甲苯胺基)-1,2-苯醌,4,5-N,N-二(间氯苯胺基)-1,2-苯醌,4,5-N,N-二(对溴苯胺基)-1,2-苯醌。用化学法(I~2-KI)进行氧化-迈克尔加成反应也成功地合成了4,5-二取代-1,2-苯醌类化合物。应用紫外光谱方法证明了氧化-迈克尔加成反应的机制。     

Fragmentation and rearrangement processes in the mass spectra of perhalogeno-aromatic compounds—VII. Pentafluorophenyl derivatives of nitrogen

The mass spectra of several perfluoroaromatic nitrogen compounds, including primary and secondary amines, diamines, nitriles, hydrazines, azines and azo compounds, are presented. Fragmentation patterns of these compounds are described and the data are discussed in terms of comparisons amongst perfluoroaromatic nitrogen compounds, and with reference to the hydrogen substituted analogs, or to oxygen and sulfur analogs of a particular compound.     

Active nickel-based reduction of organic compounds

The reducing system NiCl₂·2H₂O—Li—arene_cat (cat is catalyst) was proposed for use to reduce a wide range of organic compounds, including alkenes, alkynes, carbonyl compounds, imines, halogenated derivatives, sulfonates, aromatic compounds, hydrazines, azo and azoxy compounds, N-oxides, and nitrones. The degree of reduction can be controlled for some substrates. Deuterium can be incorporated in the reaction products using nickel chloride deuteriohydrate. Nitrones, N-alkoxyamides, and acyl azides are also reduced with the Li—arene_cat system containing no nickel salt.     

相转移催化合成偶氮脲

取代氨基脲的两相转移催化脱氢合成偶氮脲是一种新反应, 本文报道了用2, 4, 6-三叔丁基苯酚两相转移催化取代氨基脲脱氢形成偶氮化合物, 在温和的条件下合成了10个新偶氮脲, 均获得较好的产率(88-99%), 并对其反应机理作了合理的解释。     

Organic azo complexes of molybdenum and their reactions with electrophiles

Organic azo(1) and N,N-disubstituted hydrazido-N'(2) complexes of molybdenum have been prepared by the reactions of certain molybdenum-oxo complexes with hydrazines.     

新型N-[cis-3-(2-氯-3,3,3-三氟丙烯基)-2,2-二甲基环丙烷基羰基]-N'-芳氧乙酰肼的合成与生物活性

为了寻找高效、低毒的农药先导化合物,利用cis-3-(2-氯-3,3,3-三氟丙烯基)-2,2-二甲基环丙烷酰氯(1)与芳氧乙酰肼的缩合反应,合成了12种未见文献报道的目标化合物,其结构经IR,1H NMR,MS和元素分析测试技术确证.初步的生物活性测定结果表明,部分目标化合物在100 mg/L浓度下对双子叶植物(油菜)显示出良好的除草活性;同时,部分化合物在200 mg/L浓度下对蚕豆蚜虫(Aphis fabas)显示出较好的杀虫活性.     

3-取代酚酮5位偶联产物的溴氧化成环反应

报道了采用溴氧化3-异丙烯基(艹卓)酚酮和3-肉桂酰基(艹卓)酚酮合成杂环并(艹卓)酮化合物的新方法。3-异丙烯基(艹卓)酚酮5位偶联产物1a～1f和3-肉桂酰基(艹卓)酚酮5位偶联产物3a～3d分别在吡啶介质中与过量溴作用生成5-取代苯偶氮基-7-溴-3-甲基-8-氢环庚并呋喃-8-酮2a～2f和6-取代苯偶氮基-2-苯基-8-溴-4,9-二氢环庚并吡喃-4,9-二酮4a～4d。     

Impurities within carbon nanotubes govern the electrochemical oxidation of substituted hydrazines

Electrochemistry and electrocatalysis on carbon nanomaterials is at the forefront of research. The presence of carbonaceous and metallic impurities within carbon nanotubes (CNTs) is a persistent problem. Here we show that the electrochemistry of the entire group of hydrazine compounds is governed by impurities within single-walled, double-walled and few-walled CNTs. The oxidation of organic substituted hydrazines at CNTs is driven by nanographitic impurities, in contrast to unsubstituted hydrazine, for which the electrochemistry is driven by metallic impurities within CNTs. This finding is unexpected, as one would assume that a whole group of compounds would be susceptible to "electrocatalysis" by only one type of impurity. This discovery should be taken into account when predicting the susceptibility of whole groups of compounds to electrocatalysis by metallic or nanographitic impurities. Our findings have strong implications on the electrochemical sensing of hydrazines and on the use of hydrazines as fuels for nanomotors.     

Application of aza-transfer to organic compounds : Reactions between heterocyclic diazo compounds and hydrazines

Aza-transfer reactions between heterocyclic hydrazines and diazonium salts or between heterocyclic diazo compounds and substituted hydrazines have been investigated. The reaction proceeds via intermediate tetrazenes and labelled compounds have been used to elucidate the reaction mechanism.     

The Reaction of 5-Aryl(hetaryl)-2-aroylmethylthio-1,3,4-oxadiazoles with Aryldiazonium Tetrafluoroborates

5-Aryl(hetaryl)-2-aroylmethylthio-1,3,4-oxadiazoles behave as CH acids and readily react with aryldiazonium tetrafluoroborates at the active methylene group to give azo coupling products. The spectroscopic properties of the compounds synthesized have been studied.     

Convenient Methodology for the Synthesis of Trialkylhydrazines

A convenient methodology, based on the addition of organolithium compounds to N-nitrosamines, was developed for the synthesis of substituted hydrazones and trialkyl hydrazines. The reaction is very sensitive to the reaction conditions, particularly the [RLi]–[nitrosamine] ratio. For molar ratios of 1–1.2, an almost quantitative conversion to the N = O bond addition products (i.e., alkylhydrazones) can be obtained in very good yields, with any remaining nitrosamine. Using greater molar ratios (in the range of 3–5), a second addition occurs, and branched trialkyl hydrazines are obtained, in good yields, with variable amounts of hydrazone remaining. Substituted hydrazines are known to have useful commercial applications and remarkable biological activities. A wide diversity of trialkyl hydrazines could be synthesized by using two different organolithiums.