Organophosphorus compounds reaction with

Addition of di-teri-butylperoxide or benzoyl peroxide to a solution of white phosphorus in an olefin under nitrogen at elevated temperatures results in the formation of a viscous yellow mixture of unidentified organophosphorus compounds (33). With di-leri-butylperoxide, the reaction may be represented approximately by the equation. 

Organophosphorus compounds. Phosphorus-carbon bond fonnation takes place by the reaction of various phosphorus compounds containing a P—H bond with halides or tritlates. Alkylaryl- or alkenylalkylphosphinates are prepared from alkylphosphinate[638]. The optically active isopropyl alkenyl-methylphosphinate 778 is prepared from isopropyl methylphosphinate with retention[639]. The monoaryl and symmetrical and asymmetric diarylphosphi-nates 780, 781, and 782 are prepared by the reaction of the unstable methyl phosphinate 779 with different amounts of aryl iodides. Tnmethyl orthoformate is added to stabilize the methyl phosphinate[640]. 

The addition of isocyanides and azide to aldehyde-derived enamines has led to tetrazoles (533,536). On the other hand the vinylogous amide of acetoacetic ester and related compounds reacted with aldehydes, isocyanides and acids to give a-acylaminoamides (534). Iminopyrrolidones and imino-thiopyrrolidones were obtained from the addition of cyclohexylisocyanide and isocyanates or isothiocyanates to enamines (535). An interesting method for the formation of organophosphorus compounds is found in the reactions of imonium salts with dialkylphosphites (536). 

Indeed, these reactions proceed at 25 °C in ethanol-aqueous media in the absence of transition metal catalysts. The ease with which P-H bonds in primary phosphines can be converted to P-C bonds, as shown in Schemes 9 and 10, demonstrates the importance of primary phosphines in the design and development of novel organophosphorus compounds. In particular, functionalized hydroxymethyl phosphines have become ubiquitous in the development of water-soluble transition metal/organometallic compounds for potential applications in biphasic aqueous-organic catalysis and also in transition metal based pharmaceutical development [53-62]. Extensive investigations on the coordination chemistry of hydroxymethyl phosphines have demonstrated unique stereospe-cific and kinetic propensity of this class of water-soluble phosphines [53-62]. Representative examples outlined in Fig. 4, depict bidentate and multidentate coordination modes and the unique kinetic propensity to stabilize various oxidation states of metal centers, such as Re( V), Rh(III), Pt(II) and Au(I), in aqueous media [53 - 62]. Therefore, the importance of functionalized primary phosphines in the development of multidentate water-soluble phosphines cannot be overemphasized. 

In the course of the tempestuous development of organophosphorus chemistry, interest has only recently been focused on compounds of formally quinquevalent phosphorus having coordination number 3, such as 1, 2, or 3, although one of the other species of this kind has long been postulated as reactive intermediate of solvolysis of phosphorylation reactions. Definite evidence of even proof of the existence of such coordinatively unsaturated phosphorus compounds, however, has been obtained only recently in mechanistic studies, by trapping reactions with suitable cycloaddends, or actually by direct isolation. 

The fifth chapter l-(2,4,6-Trialkylphenyl)-lH-Phospholes with a Flattened P-Pyramid Synthesis and Reactivity presents the interesting chemistry of these compounds including electrophilic substitution and Diels-Alder reactions and sigmatropic rearrangements, making a variety of organophosphorus compounds accessible. 

In contrast to the reactions of the cycloamyloses with esters of carboxylic acids and organophosphorus compounds, the rate of an organic reaction may, in some cases, be modified simply by inclusion of the reactant within the cycloamylose cavity. Noncovalent catalysis may be attributed to either (1) a microsolvent effect derived from the relatively apolar properties of the microscopic cycloamylose cavity or (2) a conformational effect derived from the geometrical requirements of the inclusion process. Kinetically, noncovalent catalysis may be characterized in the same way as covalent catalysis that is, /c2 once again represents the rate of all productive processes that occur within the inclusion complex, and Kd represents the equilibrium constant for dissociation of the complex. 

As known, compounds of the (R3Sn)2X type enter readily into various exchange reactions.62 No intermediate silicon organophosphorus betaine 61 with the oxide anionic center was detected in the reactions of thiobetaines 20a, with (R3Sn)20 in ether at room temperature.84,96,100 In solutions they... 

Reaction 39 shows the condensation of acylstannanes with primary amines. The only isomer produced was tentatively ascribed the Z-configuration291. Acylstannanes undergo Wittig-type processes with organophosphorus compounds to yield vinyl stannanes, as illustrated in reactions 40 and 41. In the latter reaction products are preferably of Z-configuration292. 

Handbook of Organophosphorus Chemistry, Engel, R., Ed., Marcel Dekker, Inc., New York, 1992 — Contributed chapters are concerned with particular types of reactions of organophosphorus compounds, industrial applications of them, and their spectroscopic characteristics. 

In this chapter, we first review the nature of the several forms of elemental phosphorus and then proceed to consider their uses for specific types of syntheses of compounds containing the carbon-phosphorus bond. Prior reviews have also been concerned with these topics.1 2 Our purpose here is to update these presentations and provide fundamentals for the practicing chemist venturing into the use of elemental phosphorus. We limit this discussion to the more-or-less direct syntheses of organophosphorus compounds from elemental phosphorus. We will consider reactions that generate monophosphorus species without C-P bonds as critical intermediates, pro-... 

The existence of three equivalent bonds to each of the phosphorus atoms, which must be broken in the formation of mono-phosphorus organophosphorus compounds, might appear to be a problem at first all must be broken as new bonds are being generated to phosphorus. However, the fundamental approaches toward the use of white phosphorus accomplish this necessary action with relatively few extraneous reaction processes. 

In situ reaction of the resultant phosphine, converted to its conjugate base, with several types of electrophiles has been investigated for organophosphorus syntheses. While early reports of the use of white phosphorus in basic solution with haloalkanes did not in themselves provide procedures for the efficient preparation of organophosphorus compounds, they pointed the way for the development of more useful techniques. 

Inmost instances, a haloorganic subject to either SN2 displacement reaction or SN1 substitution is heated at reflux with the trivalent phosphorus ester with the concomitant formation of the valence-expanded organophosphorus compound and haloorganic by-product, as illustrated with an example in Equation 3.1. 

Tewari, R.S. and Shukla, R., Organophosphorus compounds. Addition reaction of 0,0-dialkyl hydrogen phosphites with substituted aromatic and long chain aliphatic aldehydes, Labdev, Part A, 9,112,1971. 

Sidky, M.M., Mahran, M.R., and Zayed, M.F., Organophosphorus compounds. XXIX. On the reaction of dialkyl phosphites with p-ben z.oqu i noned i benzene-sulfonamide, Phosph. Sulf, 9, 337, 1981. 

Sidky, M.M., Soliman, F.M., and Shabana, R., Organophosphorus compounds. XIV. Reaction of dialkyl phosphites and thiol acids with 4-benzylidene-l,2-diphenyl-3,5-pyrazolidinedione, Egypt. J. Chem., 15, 79, 1972. 

Selected entries from Methods in Enzymology [vol, page(s)] Types of organophosphorus inhibitors, 11,686-688 toxicity hazards, 11,688 purity and analysis, 11,688 solutions of organophosphorus compounds, 11,689 estimation of specific radioactivity of organophosphorus compounds, 11,689-690 method for estimating phosphorus content, 11,691 reactions with enzymes, 11,691 -701 [rate constants, 11,692 phosphorylation of chymotrypsin, 11, 694-696 identification of phosphoryl and phosphonyl peptides,... 

At about the same time, hydroxamic adds and oximes were found to react directly with organophosphorus compounds.85 2-PAM I was found to react In vitro with sarin with marked deviation from first-order kinetics that suggested that the reaction actually consists of (at least) two sequential reactions. Green showed that quatemlzed pyridine aldoximes react with an organophosphorus (OP) compound In three steps ... 

The reaction of phosphonic acid chloride (254) with (S)-proline ethyl ester afforded a mixture of diasteromeric amides (255) in high diastereoselectivity. The diastereomers (255) can easily be purified by chromatography. The chiral, practically optical pure organophosphorus compound (256) was obtained from purified (255) by acid alcoholysis. 

Some diastereoselectivity was also observed in the reaction of (S)-prolinol with the dichloride (257) leading to the chiral organophosphorus compounds (258). 

The majority of studies on the TiOz photocatalysis of organophosphorus compounds rely primarily on the disappearance of the initial substrate coupled with the monitoring of the mineralization products. Because of the complex mixtures formed in the TiOz photocatalysis of these compounds, there is limited information on the reaction pathways and mechanisms involved in the degradation processes. A recent report by Konstantinou et al. identified a number of intermediate products in the degradation of dichlofenthion and bromophos methyl by TiOz... 

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