Stereoselective Synthesis and Resolution of P-Chiral Phosphine Chalcogenides.

Abstract

New synthetic methods and resolution procedures securing ready access to the resolved P-chiral phosphinoylethenes, phosphinoylacetates and secondary phosphine oxides of diversified structures have been developed. The methods are based on processes employing stereoselective nucleophilic displacement at phosphorus, asymmetric deprotonation, immolative vinyl and chirality transfer from sulfur to phosphorus, chemical and enzymatic kinetic resolution, resolution via covalent diastereoisomers, as well as direct resolution of racemates by classical resolving agents and by chromatography on chiral stationary phases.     

手性有机磷化合物液相拆分的研究进展

 综述了近年来手性有机磷化合物液相拆分的研究进展。对间接拆分和直接拆分法,特别是各类手性固定相法在拆分有机磷化合物中的应用作了介绍,探讨了相应的拆分机理。85篇。     

Electrochemistry of Organophosphorus Compounds

Progress in electrochemistry of organophosphorus compounds is rewieved. Mechanisms of oxidation and reduction reactions under the conditions of homogenous electrocatalysis and possibility of use the primary compounds for the synthesis of various organic and organoelement compounds are considered.     

Direct Obtention of Pure Compounds from Crude Plant Extracts by Preparative Liquid Chromatography

It has been possible to submit the crude hexane extract of the barks of a medicinal plant directly to preparative liquid chromatography. A two step solvent elution gave 6 peaks, four of which readily afforded crystalline material. The entire process required 2–3 hours whereas conventional chromatography required ca. 2 weeks.     

The First Chromatographic Resolution and Electronic Effects of Multifunctional Carbon Compounds on Cellulose-Based Adsorbents

Abstract

Direct chrornatographic resolution of some tri- and tetrafunctional chiral carbon compounds 1-6 has been studied. Among the columns examined, CHIRALCEL OB exhibited fairly satisfactory resolution ability. The electronic effects associated with the presence of plural functional groups for chiral recognition by the OB adsorbent is discussed.     

Microwave-Assisted Synthesis of Organophosphorus Compounds

Abstract

Kabachnik-Fields reactions of a variety of amines, phospha-Michael additions to maleimide derivatives and alcoholysis of dialkyl phosphites were studied under microwave conditions.     

Sterically and Electronically Stabilized Organophosphorus Compounds

Abstract

The diatkylamino groups and the methoxy group were employed in a protective group and attempts were made to prepare dithioxo- and selenoxo-phosphoranes.     

Structure and Basicities of Aliphatic Organophosphorus Compounds

Abstract

As an extension of our previous works concerning the basicities of aliphatic phosphoric amides and phosphinoxides, the influence of structure is studied for some series of parent compounds, such as :

XP(tBu)₃ with X=lone pair; O; S; NH ˙ OP[N(CH₂)_X]₃ with x=2; 3; 4; 5.

The techniques used here are mainly:

determination of gas phase basicities by ion cyclotron resonance mass spectrometry

determination of Broensted basicities by titration in an non-aqueous solvent system

dipole moment measurements     

Synthesis and Reactivity of New Organophosphorus Compounds

Abstract

Synthesis of functionally substituted organophosphorus compounds on the basis of reactions of the tri-n-butylphosphine/carbon disulfide, tri-n-butylphosphine/phenylisothiocyanate, tris(dimethylamino)phosphine/phenylisothiocyanate adducts with a wide range of different dipolarophiles are reported. The development of application of S-Li tri-n-butylphosphonio-dithioformiate derivatives to the synthesis of new types of organophosphorus compounds are reported.     

Osmosedimentation Methods: Preparative and Analytical Applications

Mass transfer occurs in every uniform, many-component system. The net result of submitted to a gravitational or inertial field. this mass transfer is a lowering of the mass center of the system and the concurrent formation of concentration gradients. The Lower-density components move upwards, the higher density components move downwards, until every component reaches a uniform chemical potential, throughout the system.     

Molecular Mechanics Study of Organophosphorus Compounds

Abstract

Molecular Mechanics calculation (Allinger's force field and MM2 1985 program) was successfully applied for the structure-reactivity studies of organophosphorus compounds in our laboratory.     

Organocatalytic Asymmetric Synthesis of Organophosphorus Compounds

240 Years have passed since the discovery of elemental phosphorus. During that time organophosphorus chemistry has emerged as an interesting and exciting field of research. Recently organophosphorus chemistry has been raised to a new level. Organophosphorus compounds have found applications in asymmetric organocatalysis for the synthesis of optically active compounds of synthetic or biological importance. The aim of this review article is to present recent contributions to this developing field of chemistry and to point out synthetic advantages of methodologies developed so far.     

有机磷化合物的电子结构与成键

本文叙述了有机磷化合物的成键与性质,以及在理论上的新发展,分下面两个内容讨论:(1)磷原子的性质与成键。(2)各类有机磷化合物的电子结构与成键。     

手性仲丁胺的制备拆分和光学纯度的测定

为了获取仲丁胺的两种光学纯对映异构体，采用D-或L-酒石酸作为拆分试剂， 经过多次结晶，分别得到S-(+)-仲丁胺·乙-(+)-酒石酸盐和R-(-)-仲丁胺·D-(-) -酒石酸盐晶体，从而成功实现了其分离．产物的光学纯度通过用光活性(R)-联萘 酚磷酰氯衍生成(R)-联萘酚磷酰胺后，经^31P NMR测定，o_p_＞99％，拆分剂D-或 L-酒石酸经过强酸型阳离于交换树脂(001×7×7型)方便回收，回收率＞80％．     

New Method of Halogenation of Organophosphorus Compounds

Abstract

N-Chloroalkylamines react usually with tervalent phosphorus compounds to afford products, containing the phosphorus-nitrogen bond. We found that the sterical hindrances favour to the nucleophilic attack of the tervalent phosphorus atom on the “positive” halogen atom with the formation of phosphorus halogenated products. Sterical hindered N-halogenoalkylamines I (Hlg[dbnd]Cl,Br) possess active halogenating properties to react with tervalent phosphorus compounds similarly to methane tetrahalides. Reaction proceeds via the formation of halogenophosphonium intermediates 2, containing an anion R₂N, which reacts with alcohols to afford alkoxyphosphonium salts, transforms into halogenophosphonium salts or P-halogenoylids. Advantages of N-halogenoalkylamines 1 over methane tetrahalides are more high chemical selectivity. Moreover the inclusion of chiral substituents R into N-halogenoalkylamines gives enantioselective halogenating reagents.     

Production of Organophosphorus Compounds from Hydrogen Phosphide

Abstract

Technical processes for the production of PH₃ and for its radical induced addition to nonactivated olefins are detailed. The influence of the reaction conditions chosen on the selectivity of the PH₃/Olefin-reaction is discussed.     

联用色谱数据的局部分辨

提出了一种对二维数据严重重叠峰中待测组份进行分辨的新方法：子窗口分析法（ｓｕｂｗｉｎｄｏｗ ａｎａｌｙｓｉｓ，ＳＡ）。该方法充分利用重叠区信息，成功地解析出严重重叠峰中待测组份的光谱，进而利用正交投影求得待测组份色谱曲线．这种对二维数据进行局部分辨的方法，降低了对色谱分离条件的要求，可直接应用于未知组份的定性定量分析。     

Stereoselective Synthesis of 1,5-Diionic Organophosphorus Compounds

The reactive 1:1 intermediate produced in the reaction between triphenylphosphine and alkyl propiolates or ethynyl phenyl ketone was trapped by isopropylidene Meldrum's acid (5-isopropylidene-2,2-dimethyl-1,3-dioxane-4,6-dione) to produce alkyl 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanoates or 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanone in 75-86% yield. These 1,5-diionic phosphorus betaines exist as (Z) geometrical isomer in CDCl 3 solution.