Unsaturated Organophosphorus Research Articles

µSR studies for radical reactions of unsaturated organophosphorus compounds

In this paper, the µSR studies of some unsaturated organophosphorus compounds containing heavier congeners of cyclobutane-1,3-diyl and anthracene are reviewed by discussing the usefulness of µSR for main group chemistry. The regioselective addition of muonium (Mu = [µ+e–]) to one of the skeletal phosphorus atoms in an electron-donating air-stable crystalline 1,3-diphosphacyclobutane-2,4-diyl leading to the paramagnetic 4-membered P-heterocycle was characterized by the Δ1 (ΔM = ± 1) resonance signal observed by muon (avoided) level-crossing resonance (µLCR). Meanwhile, a crystalline 1,3-diphosphacyclobutane-2,4-diyl bearing an electron-deficient nitrogen heterocyclic unit was analyzed by transverse-field muon spin rotation (TF-µSR) to characterize predominant muoniation at the skeletal radical carbon centre. A 9-phosphaanthracene bearing the trifluoromethyl (CF3) stabilizing groups at the peri positions was also investigated from the views of radical reactivity, and the regioselective addition of muonium to the skeletal sp2-type phosphorus atom was characterized by the muon hyperfine coupling (hfc) constant observed by TF-µSR and the Δ0 (ΔM = 0) signal of µLCR. The light mass of muon (Mass = 0.1134 amu) causes the larger zero-point energy and promotes the high-energy molecular structure in which the fused aromatic rings are almost flat, although the CF3 groups would prefer the non-planar saddle-like 9-phosphaanthracene skeleton.

Frontispiece: Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

Frontispiece: Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds.

The positive muon (μ+ ) can be regarded as a light isotope of proton and has been an important tool to study radical reactions of organic compounds. Recently, muons have been applied to produce short-lived paramagnetic species from the heavier unsaturated organic molecules including the p-block elements. This article overviews recent muon spin rotation/resonance (μSR) studies on the phosphorus analogs of alkenes, anthracenes, and cyclobutane-1,3-diyls together with the fundamentals of μSR. The acyclic phosphaalkene of P=C and phosphasilenes of P=Si can accept muonium (Mu=[μ+ e- ]) at the heavier double bonds, and the corresponding radicals have been characterized. The phosphorus atom in 9-phosphaanthracene, whose P=C double bond is stabilized by the peri-substituted CF3 groups, predominantly captures muonium to provide the corresponding paramagnetic fused heterocyclic system. The peri-trifluoromethyl groups are functional to promote the unprecedented light isotope effect of muon providing the planar three-cyclic molecular structure to consume the increased zero-point energy. The formally open-shell singlet 1,3-diphosphacyclobutane-2,4-diyl unit can accept muonium at the (ylidic) phosphorus or the skeletal radicalic carbon, and the corresponding paramagnetic phosphorus heterocycles can be characterized by μSR. The findings on these muoniation processes to the unsaturated phosphorus-containing compounds will contribute not only to development of novel paramagnetic functional species but also to progress on muon science.

Epoxidation of 4,5-dialkyl-2,3-dihydro-1Н-phosphole 1-oxides

A method was developed for the synthesis of 1,5-dialkyl(cycloalkyl,phenyl)-2-phenyl-6-oxa-2-phosphabicyclo[3.1.0]hexane 2-oxides from alkynes, involving the epoxidation of unsaturated cyclic organophosphorus compounds with m-chloroperbenzoic acid. The organophosphorus compounds were obtained by a reaction sequence consisting of catalytic cycloalumination of symmetrical acetylenes with triethylaluminum in the presence of bis(cyclopentadienyl)zirconium(IV) dichloride catalyst leading to the formation of 2,3-disubstituted aluminacyclopent-2-enes and in situ reaction of the latter with dichlorophenylphosphine.

Tetracoordinate phosphorus cage compounds with endocyclic P–C bonds: Synthesis and reactivity

The survey summarizes modern methods of synthesis and reactivity of tetracoordinated phosphorus cage compounds containing one or more endocyclic P–C bonds (phosphine oxides, phosphinates and phosphonates, phosphatripticenes and others). Intramolecular cyclization reactions including electrophilic aromatic substitution with unsaturated organophosphorus compounds, reactions of P–H-derivatives with carbonyl compounds as well as cycloaddition reactions involving I–IV-coordinated phosphorus derivatives are considered.

Synthesis of new functionalized mono‐ and bisorganophosphorus acids and their derivatives with unsaturated and aromatic fragments

AbstractConvenient procedures for the synthesis of functionalized mono‐ and bisorganophosphorus acids and their derivatives with unsaturated and aromatic fragments, starting from the available derivatives of trivalent phosphorus acids, unsaturated and aromatic aldehydes, and carboxylic acid chlorides, are proposed, and some properties of the new unsaturated organophosphorus compounds are presented. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 23:32–40, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20749

Reaction of phosphorus pentachloride with N-vinylimidazole and N-vinylbenzimidazole

Earlier, we have found that N-vinylpyrazoles are phosphorylated with phosphorus pentachloride at the double bond to give rise to unsaturated organophosphorus compounds [1]. N-Vinylimidazoles contain-ing in the ring highly basic separated nitrogen atoms of the pyridine type react with phosphorus pentachloride in a different manner. In these reactions, the first and foremost are the donor–acceptor interactions. N-Vinylimidazole I reacts with phosphorus pentachloride (even in the excess of the latter) to give the donor– acceptor complex III with participation of the pyridinium nitrogen atom. As a result, the electron–acceptor properties of the ring increase and the nucleophilicity of the N-vinyl group decreases hampering its phosphorylation. The treatment of azole I with the solution of phosphorus pentachloride in benzene saturated with hydrogen chloride affords complex compound IV containing the protonated nitrogen atom in the 3 position.

Phosphorylation of C-alkenylsubstituted pyrazoles with phosphorus pentachloride

The reaction of phosphorus pentachloride with styrenes affords unsaturated organophosphorus compounds in which the phosphorus chloride substituent is attached to the carbon atom of the double bond [1]. NVinylsubstituted azoles are also phosphorylated at the double bond [2–3]. Phosphorylation of С-alkenylazoles with phosphorus pentachloride was not studied until now. The presence in the azole cycles the “pyridine” nitrogen atoms with enhanced nucleophilicity could direct the attack of phosphorus pentachloride to the heterocycle rather than to the double bond of Сvinylazoles to give donor–acceptor complexes. Indeed, the reaction of phosphorus pentachloride with 1-allyl3,5-dimethylpyrazole led to formation of the donor– acceptor complex I. DOI: 10.1134/S1070363209060358

Functionalization of the unsaturated organophosphorus compounds. Study of reaction of dialkylaminoethynephosphonates with malonic acid derivatives and benzenesulfonylacetonitrile

Reactions of some CH-acids with dimethyl dialkylaminoethynephosphonates were studied aiming to develop methods of syntheses of the functionalized organophosphorus compounds. Reactions with malonodinitrile, ethyl cyanoacetate, and benzenesulfonylacetonitrile were shown to proceed effectively in anhydrous acetonitrile in the presence of catalytic amounts of potassium carbonate to form products of CHacids addition at the triple bond followed by prototropic isomerization to give the corresponding β-dialkylamino-β-phosphonomethyl-α-substituted acrylonitriles. In reaction with malonic acid aminoethynephosphonates are hydrolyzed to form phosphonoacetic acid dialkylamides as main products.

Anionic ring-opening polymerization of a strained phosphirene: A route to polyvinylenephosphines

A strained 1-phenyl-2,3-dimethylphosphirene undergoes anionic ring-opening polymerization upon initiation with n-butyl lithium at ambient temperature to yield polyvinylenephosphine, an unsaturated organophosphorus polymer.

Synthesis of 2-(p-Toluenesulfonamido)-4-phenyl-4, 5-dihydro-1H-1, 3, 4-diazaphosphole 4-oxides

Some novel unsaturated five-membered organophosphorus heterocyclic compounds, 2-(p-toluenesulfonamido)-4-phenyl-4, 5-dihydro-1H-1, 3, 4-diazaphosphole 4-oxides 8 have been synthesized by Mannich-type reaction of p-toluenesulfonylguanidine with phenyldichlorophosphine and ketones.

ChemInform Abstract: Methylenephosphonium Ions: A New Class of Unsaturated Organophosphorus Compounds

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Methylenephosphonium-ions: A New Class of Unsaturated Organophosphorus Compounds

Abstract Methylenephosphonium ions, R2P=CR'2 + X−, could be prepared by either adding electrophiles to the carbene R2P[sbnd]C-R' (R = iPr2N, R' = SiMe3) or abstracting chloride from P-halogenated ylides R2PCl=CR'2 (R = tBu, R' = SiMe3 or Aryl). Their structures and reactivity is discussed.

ChemInform Abstract: New Unusual Reactions in the Chemistry of Unsaturated Organophosphorus Compounds

ChemInformVolume 21, Issue 46 Reviews ChemInform Abstract: New Unusual Reactions in the Chemistry of Unsaturated Organophosphorus Compounds B. I. IONIN, B. I. IONIN Leningrad Lensovet Inst. Technol., Leningrad 198013, USSRSearch for more papers by this authorA. A. PETROV, A. A. PETROV Leningrad Lensovet Inst. Technol., Leningrad 198013, USSRSearch for more papers by this author B. I. IONIN, B. I. IONIN Leningrad Lensovet Inst. Technol., Leningrad 198013, USSRSearch for more papers by this authorA. A. PETROV, A. A. PETROV Leningrad Lensovet Inst. Technol., Leningrad 198013, USSRSearch for more papers by this author First published: November 13, 1990 https://doi.org/10.1002/chin.199046366Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue46November 13, 1990 RelatedInformation

Coordination Chemistry of Unsaturated Organophosphorus Ligands

Abstract Similarities between phosphorus and carbon in un-saturated systems and their transition metal complexes are presented and discussed.

New Unusual Reactions in the Chemistry of Unsaturated Organophosphorus Compounds

Abstract Arbusov reaction of trialkyl phosphites with haloalkynes opened a new route to the synthesis of acetylenic phosphonates as well as attracted the investigators attention to the nucleoohilic substitution of halogene at sphybridized carbon atoms. The most important compounds of this type are chloro- and bromoethyne phosphonates formed by the action of dihaloethynes upon phosphites. These polyfunctional compounds may interact via triple bond opening and/or halogene substitution. The latter pathway results in the formation of different phosphonates and diphosphonates (1):

X-ray structural study of 2,3-diphenyl-4-morpholinomethyl-5-ethynyl-2-thio-2-phosphabicyclo[4.4.0]decan-5-ol

X-ray structural analysis was previously used [i] to study the individual stereoisomers of derivatives of thiophosphabicyclodecanone with two phenyl substituents. The present paper gives the results of an x-ray structural study of the stereoisomer of 2,3-diphenyl-4-morpholinomethyl-5-ethynyl-2-thio-2-phosphabicyclo[4.4.0]decan-5-ol (I) with mp = 238-239~ [2]. Acetylenic alcohols of the phosphorinane and phosphabicyclodecane series with four-coordinate phosphorus representatives of unsaturated organophosphorus compounds are of interest from the viewpoint of conformational analysis. Moreover, they can be used to study the reactivity of new polyfunctional organophosphorus compounds and syntheses based on them. The determination of the three-dimensional structure of these compounds by IR and NMR spectroscopy often encounters serious difficulties. The use of x-ray structural analysis (XSA) to study these compounds, in addition to establishing their structure, gives a picture of the novalence intramolecular interactions, determined by the size and orientation of the exocyclic substituents. Data on the angles and bond lengths make it possible to establish correlations between the NMR spectra characteristics and the three-dimensional structures of the molecules of the compounds being considered.

Structural effect on the iodolactonization of unsaturated organophosphorus compounds

The compound 1a , γ,δ-unsaturated phosphate was not able to perform the iodolactonization reaction. But a minor change of its structure makes the iodine induced cyclization reaction succeed.

Synthesis of potential drugs based on hydrophosphoryl compounds. IV. Synthesis and antifungal activity of unsaturated organophosphorus compounds

Synthesis of potential drugs based on hydrophosphoryl compounds. IV. Synthesis and antifungal activity of unsaturated organophosphorus compounds

ChemInform Abstract: UNSATURATED ORGANOPHOSPHORUS COMPOUNDS FROM 1‐VINYLBENZOTRIAZOLE

Chemischer InformationsdienstVolume 14, Issue 34 Organoelement Compounds ChemInform Abstract: UNSATURATED ORGANOPHOSPHORUS COMPOUNDS FROM 1-VINYLBENZOTRIAZOLE V. G. ROZINOV, V. G. ROZINOVSearch for more papers by this authorG. A. PENSIONEROVA, G. A. PENSIONEROVASearch for more papers by this authorV. I. DONSKIKH, V. I. DONSKIKHSearch for more papers by this authorA. V. KALABINA, A. V. KALABINASearch for more papers by this authorE. S. DOMNINA, E. S. DOMNINASearch for more papers by this authorG. G. SKVORTSOVA, G. G. SKVORTSOVASearch for more papers by this author V. G. ROZINOV, V. G. ROZINOVSearch for more papers by this authorG. A. PENSIONEROVA, G. A. PENSIONEROVASearch for more papers by this authorV. I. DONSKIKH, V. I. DONSKIKHSearch for more papers by this authorA. V. KALABINA, A. V. KALABINASearch for more papers by this authorE. S. DOMNINA, E. S. DOMNINASearch for more papers by this authorG. G. SKVORTSOVA, G. G. SKVORTSOVASearch for more papers by this author First published: August 23, 1983 https://doi.org/10.1002/chin.198334253Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume14, Issue34August 23, 1983 RelatedInformation