Synthesis and Spatial Structure of the Derivatives of 2,5-Dioxo-3,3-Bis(Trifluoromethyl)-6,7-Benzo-1,4,2-and 2,5-Dioxo-4,4-Bis(Trifluoromethyl)-6,7-Benzo-1,3,2-Oxazaphosphepines

Abstract

Hexafluoroacetone imine easily interacts with compounds (I, R = OMe, OCH₂CF₂CHF₂, NEt₂, Ph) in two directions unlike hexafluoroacttone and gives 1,4,2-oxazaphosphepines (II) (pathway I) or 1,3,2-oxszaphosphepines (III) (pathway 2). The compound (II) (R = NEt₂) lightly hydrolyzes to yield the salt (IV). The structure of heterocycles II-IV) has been confirmed by X-ray analysis (see fig. I, II, R = OMe; fig. 2, IV). The detail structural peculiarities of the compounds am discussed.     

Sereoselective Addition of Benzaldehyde N,N-Dimethyl-Hydrazone to 2-RfO-4-Oxo-5,6-Benzo-1,3,2-Dioxaphosphorinanes. The Spatial Structure of 2-Pentafluorophenoxy-4-Dimethylamino-2,5-Dioxo-3-Phenyl-6,7-Benzo-1,4,2-Oxazaphosphepine

Abstract

[3+2]-Cycloaddition of N,N-dimethylhydrazone benzaldehyde (I) to 2-R_FO-4-oxo-5,6-benzo-l,3,2-dioxaphosphorinanes (II) yields the new heterocycle - 2-R_FO-4-Me₂N-2,5-dioxo-3-phenyl-6,7-benzo- 1,4,2-dioxaphosphepine (III) [R_F = C₆F₅, CH(CF₃)₂) with high stereoselectivity (above 94%). The reaction is likely to involve the initial interaction of nitrogen as a nucleophile with wbonyl carbon as an electrophile. The hydrolysis of (III) leads to phosphonic acid (IV) (OR_F = OH).     

Multicomponent Synthesis of 2,5-Dioxo- and 4-Aryl-5-oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydroquinazolines

Ten 2,5-dioxo- and 4-aryl-5-oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydroquinazolines have been synthesized in three-component interactions of 1,3-cyclohexanedione or dimedone, urea or thiourea, and substituted benzaldehydes (3-bromo-, 4-bromo-, 4-fluoro-, 4-methoxy-, 3,4-methylenedioxy-, and 3-nitro-). 9-Aryl-4,5-dioxo-1,2,3,4,5,6,7,8-octahydro-9H-xanthenes were also formed in these reactions.     

Reactions of 2-Alkoxy-4-oxo-5,6-benzo- 1,3,2-dioxaphosphorinanes with Imines. Synthesis and Steric Structure of 6,7-Benzo-1,4,2-oxazaphosphepine Derivatives

2-Alkoxy-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinanes containing an electron-withdrawing fluorinated exocyclic substituent at the P atom react with aromatic aldimines to give 6,7-benzo-1,4,2-oxaza- phosphepines with a high regio- and stereoselectivity. The major diastereomers were isolated, and their configuration was determined by single crystal X-ray diffraction.     

Molecular and Solution Structure of 5,6-Benzo-1,3,2-dioxaphosphinin-4-one Derivatives

2-X-5,6-benzo-1,3,2-dioxaphosphinin-4-ones (X = N = C = O, Cl, NEt₂), regardless of their aggregative state, prefer one and the same conformation (flattened sofa); the exocyclic substituent occupies either an axial (N = C = O, NEt₂) or an equatorial (Cl) position.     

6,7-二氧代-4-芳胺香豆素的设计、合成及分子对接研究

茶酚-氧位-甲基转移(COMT)酶抑制剂在治疗帕金森病中起到重要作用.通过对现有COMT酶抑制剂托卡朋和恩托卡朋结构与活性关系分析,推断含有儿茶酚结构的香豆素类化合物可能具有潜在的COMT酶抑制活性,因此设计合成了一类新型的6,7-二氧代-4-芳胺香豆素,通过理论计算,研究了此类化合物对COMT酶抑制活性.结果表明,设计的10种6,7-二氧代-4-芳胺香豆素与COMT酶的对接效果均较好,其中具有甲氧基乙基保护的儿茶酚结构化合物6,7-二[2-(甲氧基)乙氧]-4-(苯胺)香豆素(6b4)和6,7-二[2-(甲氧基)乙氧]-4-[(3-乙炔基)苯胺]香豆素(6b5)与COMT酶的对接效果尤为显著.     

Benzaldehyde N,N-Dimethylhydrazone in the Reaction with 4-Oxo-2-pentafluorophenoxy-5,6-benzo- 1,3,2-dioxaphosphorinane. Preparation and Spatial Structure of 4-Dimethylamino-2,5-dioxo-2-pentafluorophenoxy-3-phenyldihydro-6,7-benzo-1,4,2-oxazaphosphepine

Benzaldehyde N,N-dimethylhydrazone with 4-oxo-2-pentafluorophenoxy-5,6-benzo-1,3,2-dioxaphosphorinane is capable to yield with high stereoselectivity a product of the phosphorus heterocycle expansion: unstable to hydrolysis 4-dimethylamino-2,5-dioxo-2-pentafluorophenoxy-3-phenyldihydro-6,7-benzo-1,4,2-oxazaphosphepine. The configuration of the prevailing isomer of the latter was determined by X-ray diffraction study.     

Synthesis and Structure of Some 1,3,2-Oxazaphospholenes

Abstract

The reaction of trialkyl phosphites and phosphines with o-quinones result in the formation of oxyphosphoranes [1]. In an effort to prepare o-quinone monoimine metal complexes with amine [2] and phosphine ligands it has been found that in the reaction either of o-quinones (1) with phosphines in the presence of ammonia or of o-quinone monoimines (2) with phosphines 1,3,2-oxazaphospholenes (3) are formed in good yields.     

Reaction of 5,6-Benzo-1,3,2-dioxathiepane 2-Oxide with Acetonitrile

Russian Journal of General Chemistry -     

1-芳基-3-苯甲酰基-2,5-二苯基吡咯的合成及其性质

文献报导[1],1-芳基-2,5-二甲基3-醛基吡咯和3-亚氩烃甲基吡咯,具有降血压效应。我们曾报导1-芳基-2-甲基-3-乙酰基-5-对氯苯基吡咯和1-芳基-2-甲基-3-乙酰基-5-间硝基吡咯化合物。1-取代-2,5-二苯基吡咯具有止痛作用。     

Synthesis of 1-Aryl-4-azolylbutanones

A convenient method was developed for the synthesis of substituted 4-azolyl-1-arylbutanones from the available γ-chlorobutyrophenones by successive stages of transformation into ketals, alkylation of sodium imidazolate or 1,2,4-triazolate by the ketals in DMF, and removal of the ketal protection. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1161–1167, August, 2005.     

Quantum-Chemical Investigation of Reaction Mechanism of 2-R-4-Oxo-5,6-Benzo-1,3,2-Dioxaphosphorinanes with Chloral and Fluoral

Abstract

Reaction of 2-R-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinanes I with chloral leading to formation of seven-membered heterocycles - 1,4,2-dioxaphosphepines is characterized by the high degree of stereoselectivity. We investigated the model reactions of 2-R-4-oxo-1,3,-dioxaphosphorin-5-enes with CX₃CHO by PM3 and ab initio methods in STO-3G, 3-21G, 6-31G*, MP2/6-31G* basis set and also DFT method (B3LYP).     

1-芳基-3，5-二甲基吡唑-4-羧酸有机锡酯的合成、结构及杀菌活性研究

由1-芳基-3,5-二甲基吡唑-4-羧酸与适当的有机锡反应,合成表征了一系列的1-芳基-3,5-二甲基吡唑-4-羧酸有机锡酯(1～14),并通过单晶衍射确定了1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯(7)的结构。该化合物与一分子水共同结晶,通过分子间O-H…O及O-H…N氢键形成二维网状结构。杀菌活性筛选表明新合成的化合物对于番茄早疫菌、花生褐斑菌、小麦赤霉菌、苹果轮纹菌及灰霉菌全部具有良好的生长抑制作用。1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯及1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯在50μg.mL-1浓度下的体外实验中表现出很高的生长抑制率。对于高活性的三取代锡羧酸酯进行了EC50值的测定,结果表明1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯对苹果轮纹菌的EC50值为0.06μg.mL-1,对小麦赤霉菌的EC50值为0.14μg.mL-1。     

Conformational Composition of 2,5-Disubstituted 1,3,2-Dioxaborinanes

We have used ¹H NMR spectra and also MM+ and AM1 calculation methods to show that the conformational equilibrium of 2,5-disubstituted 1,3,2-dioxaborinane molecules, including two sofa forms, is shifted toward the equatorial conformer. We have established the values of G ⁰ for a number of substituents on the C₍₅₎ ring atom.