二氢和四氢-2,4-二取代-1,5-苯并二氮杂的光谱和立体化学

本文制备了一系列2,4-二取代-1,5-苯并二氮杂草,研究了它们的光谱和立体结构。二氢化物具有船式构象,而且2位取代基可以朝向“船头”的下方,处于与4位取代基近似地为五原子重叠的地位,但分子仍然是稳定的,这种现象较少见。二氢化物用硼氢化钠还原,生成含量相近的两种四氢化物,其中高熔点异构体确定为顺式椅式构象而低熔点异构体具有反式扭船式构象。这一结果纠正了福岛清吾等关于这两种异构体的不正确的指认。     

二碘化钐催化合成1,5-苯并二氮杂草

Samarium diiodide （SmI2） was found to be an efficient catalyst for the condensation of o-phenylenediamine and ketones to afford the corresponding 2,3-dihydro-1H-benzo[b][1,4]-diazepines in moderate to excellent yields under very mild and solvent-free conditions. The real active species here was suggested to be a Sin（Ⅲ） intermediate formed in situ and the mechanism of the present reaction was proposed.     

氧化铝和氧化锆催化剂上2-取代苯并咪唑和1,5-二取代苯并二氮的合成(英文)

In this study, alumina, zirconia, manganese oxide/alumina, and manganese oxide/zirconia have been investigated for their catalytic activity in the condensation reaction between o-phenylenediamine and an aldehyde or a ketone to synthesise 2-substituted benzimidazoles and 1,5-disubstituted benzodiazepines respectively. Surface area, surface acidity, and morphology of the catalysts have been analysed and correlated with their catalytic activity. The isolated yields of 2-substituted benzimidazoles and 1,5-disubstituted benzodiazepines are in the range of 30% to 95%. A good correlation between the amount of surface acid sites as well as the surface morphology of the catalysts and the catalytic activity has been observed. This method has been found to be simple and economical. The solid supports could be regenerated and reused without much loss in their activity. Further, the solid supports have been also found to be effective as general catalysts in the condensation of o-phenylenediamine with other substituted aldehydes and ketones.     

Mannich反应合成3,6(8)-二取代-2,4-二氢-1,3-苯并噁嗪及其杀菌活性

以取代苯酚、多聚甲醛和取代苯胺为原料,在无催化剂的条件下,通过Mannich缩合反应合成了一系列新型3,6(8)-二取代-2,4-二氢-1,3-苯并噁嗪类化合物。 结果表明,取代苯酚和取代苯胺的取代基为供电子基时,合成产物的产率高于吸电子取代基的。 产物的结构用1H NMR、13C NMR、IR和MS等进行了表征。 初步测试了目标化合物的杀菌活性,部分化合物具有较好的杀菌活性。 当浓度为25 mg/L时,化合物4j和4d对菌核病菌的抑制率分别为86.1％和81.5％,化合物4i对灰霉病菌的抑制率为81.6％。     

酸性离子液体催化合成1,5-苯并二氮衍生物

以邻苯二胺和酮为原料,酸性离子液体[hmim]HSO4和乙醇为催化体系,合成了一系列1,5-苯并二氮衍生物,其结构经1^H NMR,IR和元素分析表征。催化体系可循环使用3次。     

2,3,4,5-四氢-1,5-甲桥-1H-3-苯并氮杂的合成

以1,4-二氢-1,4-甲桥萘为起始原料,经臭氧化、还原性胺化及还原反应合成了新型戒烟药伐仑克林的重要中间体2,3,4,5-四氢-1,5-甲桥-1H-3-苯并氮杂,其结构经1HNMR和MS确证。     

4,7-非对称二取代苯并噻二唑的合成

以邻甲苯胺为起始原料,经3步反应制得4-甲基-2,1,3-苯并噻二唑(1);1经溴代、水解和IBX选择性氧化制得系列4,7-非对称二取代苯并噻二唑砌块;通过砌块4-甲酰基-7-溴-2,1,3-苯并噻二唑与给电子基团的缩合或偶联反应,合成了具有4,7-非对称苯并噻二唑D-π-A型分子结构的新化合物4-甲酰基-7-N,N-二甲氨基-2,1,3-苯并噻二唑和4-甲酰基-7-[4-(N,N-二甲氨基)]苯基-2,1,3-苯并噻二唑,其结构经NMR和HR-MS表征.     

合成1,5-苯并二氮杂卓衍生物的催化剂研究进展

根据催化剂种类的不同,综述了近十年在1,5-苯并二氮杂(草)衍生物的合成过程中使用的催化剂的研究进展,包括路易斯酸、布朗斯特酸、有机酸、负载催化剂、离子液体催化剂、哌啶类催化剂、介孔材料等,分析了各方法的优缺点,期望能够为探索出更好的催化剂提供启发.     

二氢和四氢-2-甲基-4-芳基(1,5)苯并硫氮杂的构象分析(Ⅰ)

本文研究了2-甲基-4-芳基(1,5)苯并硫氮杂的光谱和构象分析,确立了二氢化物具有类船式构象。形成二氢化物的成环反应是高度立体选择性的,分子内杂环并联的苯环和取代的芳环的平面夹角约为50度,但4位的芳环仍能和杂环并联的苯环发生明显的共轭效应,氮原子在这里起着关键作用。二氢化物用硼氢化钠还原,得到的四氢化物的构象是扭船式的,也是稳定的,这显然是由这个体系的结构所决定的。还原反应是立体专一性的。     

Reactions of 1,5-diphenyl-2,4-dimethyl-1,5-pentanedione with hydrogen sulfide

1,5-Diphenyl-2,4-dimethyl-1,5-pentanedione reacts with hydrogen sulfide in the presence of boron trifluoride etherate or 70% perchloric acid to give the corresponding thiapyrylium salts and 2,6-diphenyl-3,5-dimethyldihydrothiopyran; complete disproportionation to give 2,6-diphenyl-3,5-dimethylthiacyclohexane and 2,6-diphenyl-3,5-dimethylthiapyrylium bromide occurs in the presence of hydrogen bromide. The possibility of catalytic hydrogenation in the presence of 10% Pd/C of compounds with a thiopyran ring was established.     

Tetrahydro-1,2,3,4 pyrimidines et octahydro-1,2,3,4,5,6,7,8 quinazolines dithiones-2,4 et diones-2,4 synthese et etude du mecanisme

A synthesis of tetrahydropyrimidine-dithiones and octahydroquinazoline-dithiones has been realized by direct action, in basic media, of alkyl or aryl isothiocyanates on ketones possessing at least an hydrogen atom in an α-position. The clarification of the complex mechanism of this reaction has been attempted. It is possible to reach corresponding diones by desulphurization of the dithiones.     

Synthesis of cis-1,5-Dimethyl-2,4-dinitro-2,4-diazabicyclo[3.1.0]hexan-3-one and cis-1,5-dimethyl-2,4-dinitro-2,4-diazabicyclo[3.2.0]heptan-3-one

cis-1,5-Dimethyl-2,4-dinitro-2,4-diazabicyclo[3.2.0]heptan-3-one and cis-1,5-dimethyl-2,4-dinitro-2,4-diazabicyclo[3.1.0]hexan-3-one were both synthesized in three steps each from a common precursor, 1,3-diacetyl-4,5-dimelhyl-4-imidazolin-2-one.     

1,5-Dimethyl-2,3,3,4-Tetrachloro-1,5-Diaza-2,4-Diphosphorinan-6-One and some derivatives

A synthesis of C-chlorinated analogues of 1,5-diaza-2,4-diphosphorinan-6-ones is described. The P-chlorophosphine 3 , a key compound for all reported substitution reactions, reacts in an unusual way with N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea to give the unsymmetrical product 5 , the formation of which is accounted for by a silatropy of the intermediate compound 4 . Compound 5 is stable in solution but rearranges quantitatively into isomer 6 without solvent at room temperature. Compound 3 , its fluoro derivative 9 , and the alkoxy derivatives 10a–d exist as cis-and trans-isomers. Some stereochemical aspects, as well as the possibility of 1,2-chlorotropy, are discussed.     

Cyclization of 2,4-dichloro-1,5-pentanediones with nucleophilic reagents

The mechanism of reaction of 2,4-dichloro-1,5-pentanediones with ammonia has been studied. Intramolecular cyclization of the intermediate resulting from nucleophilic attack at the carbonyl group can occur in two ways, depending on the reaction conditions, either at the -chloromethylene fragment or at the second carbonyl group, leading to the formation of 2-aroylpyrroles or 3-chloropyridines, respectively. In reactions with thio- and phenylthiourea both chlorophenacyl fragments are involved, resulting in the formation of di(2-amino-4-arylthiazolyl-5)methanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1095–1099, August, 1991.     

Studies on Enethiol-Thione Equilibrium of Some 1,5-Disubstituted 2,4-Dithiobiurets

Eaethiol contents of 1, 5-diphenyl 2, 4-dithiobiuret (DP); 1, 5-di-p-tolyl 2, 4-dithiobiuret (DPT); 1-phenyl 5-p-tolyl 2, 4-dithiobiuret (PPT); 1-phenyl 5-o-tolyl 2, 4-dithiobivret (POT); and 1-methyl 5-p-tolyl 2, 4-dithiobiuret (MPT) have been studied by alkali titration method in methanol and by spectrophotometric method in different solvents of varying polarities, ranging from pyridine (Z, 64.0) to methanol (Z, 83.6). Free energy of tautomerisation has been calculated. The effect of substituents on the phenyl group on enethiol contents have been studied. It has been observed that temperature has no effect on enethiol-thione equilibrium.