Low-Coordinated Organophosphorus Compounds

Low-coordinate organophosphorus compounds can be prepared by steric protection. They are diphosphenes, phosphaethenes, phosphaallenes, phosphabutatrienes, phosphaalkynes, and so on, of coordination number 2 and 1 .     

New Carbamoyl Organophosphorus Compounds

Abstract

The syntheses of various organophosphorus compounds, which contain a function with potentially agropharmaceutical properties (acylureas [1], acylsemicarbazides [2] or imidazolidinetriones [3]) are described.     

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.     

Organophosphorus Compounds in Organic Electronics

This Minireview describes recent advances of organophosphorus compounds as opto‐electronic materials in the field of organic electronics. The progress of (hetero‐) phospholes, unsaturated phosphanes, and trivalent and pentavalent phosphanes since 2010 is covered. The described applications of organophosphorus materials range from single molecule sensors, field effect transistors, organic light emitting diodes, to polymeric materials for organic photovoltaic applications.     

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.     

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.     

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     

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.     

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.     

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.     

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.     

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。     

Substituent Effects And Structure-Reactivity Relationship of Organophosphorus Compounds

To evaluate the substituent effect in organophosphorus compounds, a series of model compounds, namely 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane-1-oxides, alkyl hydrogen p-substituted phenyl-phosphonates, dialkyl p-substituted phenylphosphonates, as well as alkyl hydrogen alkylphosphonates, were synthesized and studied. Since in these compounds the substituents are located far away from reaction centre and the contribution of the steric effect of substituents can thus be eliminated, the substituent polar effect was evaluated based on ³¹P NMR, pKa and charge density of phosphoryl oxygen of these compounds calculated by the quantum mechanies MNDO method. The results showed that the polar effects of substituent in carboxylic and organophosphorus esters are similar, and the variation in polar effect among the alkyl groups is not significant. In the meantime, some steric parameters E_s^p of substituents were suggested for organophosphorus compounds, which are different from the Taft's E_s and Charton's υ parameters^[1,2].     

一配位有机磷化合物的研究进展

综述了近10年来一配位有机磷化合物的加成反应,Ene反应、聚合反应和络合反应的研究进展。并就其在有机合成中的应用作简要概述。参考文献21篇。     

有机磷化合物硫逐-硫赶重排反应的理论研究

有机磷化合物硫逐┐硫赶重排反应的理论研究彭万华（湖北三峡学院化学系宜昌４４３０００）刘述斌（Ｄｅｐｔ．ｏｆｃｈｅｍ．，Ｕｎｉｖ．ｏｆＮｏｒｔｈｃａｒｏｌｉｎａ，ｃｈａｐｅｌＨｉｌ，２７５９９－３２９０，ＵＳＡ）杨小平（湘潭师范学院化学系湘潭４１１１０...     

Subtituent Parameters of Organophosphorus Compounds in Metal Extraction

Abstract

The polar and steric effect of long chain alkyl and alkoxyl groups attached directly to the phosphorus atom were evaluated by experimental method and the method of molecular mechanics calculation.     

Fast Atom Bombardment Mass Spectrometry of Organophosphorus Compounds

Abstract

Fast atom bombardment mass spectrometry has been applied to a range of ionic, zwitterionic, and thermally labile organophosphorus compounds and has been shown to be a potentially valuable aid to identification and characterisation. Results are presented for the positive ion spectra of quasiphosphonium salts, aminophosphonic, aminophosphonous, and aminophosphinic acids, phosphonopeptides, and a number of heat sensitive derivatives. The quasiphosphonium intermediates derived from alkyl esters of phosphorus (III) acids and halogeno compounds generally show base peaks corresponding to the phosphonium ion which fragments to give the protonated form of the Arbuzov product. Strong characteristic peaks are also obtained from various phosphonic and phosphinic derivatives. α- and ω-aminoalkanephosphonic acids and their guanidino analogues give base peaks corresponding to [M+H]⁺ ions and show simple fragmentations arising mainly from the loss of HPO₃ and H₃PO₃ Phosphonous derivatives give peaks corresponding to [M+H]⁺ and [2M+H]⁺ with the base peak apparently resulting from the elimination of HPO₃ from the dimeric structure. Elimination of H₃PO₂ is also indicated. Examples of phosphonopeptides are also shown to give base peaks at [M+H]⁺ and to exhibit characteristic fragmentations that are of potential value as aids to identification. Fast atom bombardment mass spectra have also been recorded for a number of pesticidal phosphorodithioates, their principal metabolites, and some related esters. Although [M+H]⁺ peaks are clearly present in all cases, the intensity is variable and fragmentations are generally more complex than those obtained for the compounds referred to above. O,O-Diethyl phosphorodithioates, for example, frequently give rise to (EtO)₂PS⁺, which fragments further by stepwise elimination of ethylene as is also observed in electron impact mass spectrometry. We are grateful to SERC for support of this work and for FAB mass spectrometry facilities at the Physico-Chemical Measurements Unit, Harwell.     

Mechanism on Iodine Induced Cyclization Reaction of Organophosphorus Compounds

Abstract

The iodine induced cyclization reaction of δ,?- or δ,γ- unsaturated phosphate, phosphonate or phosphoamidate were investigated by P-31 and C-13 NMR spectra. In each case, the diiodo-derivatives were observed and identified. For the δ,?-unsaturated phosphate and phosphonate the cyclized products formed predominately.