Trivalent Phosphorus Compounds Research Articles

1, 1‐dichloroalkylphosphonates: Convenient starting materials for low‐coordinated trivalent phosphorus compounds

AbstractDiisopropyl 1,1‐dichloroalkylphosphonates bearing various groups (alkyl, aryl, allyl, benzyl, phenylthiolate, trimethylsilyl) in the α‐position were reduced to the corresponding primary 1,1‐dichlorophosphines by the LiAlH4‐AlCl3 system in diethyl ether. Subsequent dehydrochlorination with tertiary amines in the presence of trapping dipolar compounds (ethyl diazoacetate or n‐hexylazide) led to the expected 1,2,4‐diazaphospholes or 3H‐1,2,3,4‐triazaphospholes.

Oxidative fluorination of low-valent phosphorus compounds

In phosphorus chemistry, carbon tetrachloride has been well established as a mild oxidant of high selectivity. In combination with various nucleophiles it enables the oxidative derivatisation of low-valent phosphorus compounds. With fluorides as nucleophiles different types of PF compounds can be obtained in this manner. Trivalent phosphorus compounds possessing a sufficiently high nucleophilicity react with the reagent combination CCl 4/Et 3NHF via fluorophosphonium salts, formed as intermediates, to fluorophosphoranes or hexacoordinated fluorophosphates, (eqn. 1): ▪ Phosphanes with alkoxy groups (X  OR′) form preferentially phosphoryl or phosphinyl fluorides, R 2P(O)F (eqn. 1). Less nucleophilic phosphorus compounds are not oxidized. They undergo fluoridolysis reactions. In the presence of Et 3N, tetracoordinated compounds with PH functions are converted into the corresponding PF compounds (eqn. 2): R 2P(Y)H+CCl 4+F −→R 2P(Y)F+CHCl 3+Cl − (ROR′, NR′ 2, Ar, Alk; YO, S; R′Alk); yields > 80% Even spirocyclic PH compounds undergo this reaction. In this way ( OC 2H 4NH) 2P F, ( OC 6H 4NH) 2P F, N(CH 2CMe 2O)P (OMe)F and OC 2H 4OP F 4 − can be prepared in good yields.

Dediazoniation of arenediazonium salt with trivalent phosphorus compounds by one-electron transfer mechanism

Trivalent phosphorus compounds, triphenylphosphine and triethyl phosphite, gave rise to dediazoniation of an arenediazonium salt in alcoholic solvent at ambient temperature in the dark. The reaction was well interpreted in terms of radical-chain mechanism initiated by an electron transfer from the trivalent phosphorus to a diazonium salt, which postulates a cation radical from the trivalent phosphorus as an intermediate.

The chemical repair reaction of thymine and thymidine diol derivatives, models of oxidatively damaged nucleic acids, by trivalent phosphorus compounds.

When treated with trivalent phosphorus compounds, thymine and thymidine diol derivatives, models of oxidatively damaged nucleic acids, were reductively repaired to regenerate the original thymine and thymidine derivatives. A possible mechanism is proposed.

ChemInform Abstract: Reactions of Cyclic Halo Ketones with Trivalent Phosphorus Compounds.

Abstract7,7‐Dichlorobicyclo(3.2.0)hept‐2‐en‐6‐one (I) reacts with the dialkyl phosphites (II) to give the phosphonates (III), which are O‐acylated with acetic anhydride (IV), producing the acetates (V).

Synthesis of Substituted Phosphonates and Their Reactions with Carbonyl Compounds

Abstract The reaction of the derivatives of 3-phenyl-3-chloro-2-oxopropionic acid with the trivalent phosphorus compounds has been studied. The esterification or amidation of this acid have been shown to influence the course of reaction with Ph3P. In the reaction with esters enolphosphonium salts are produced, ketophosphonium salts are obtained when amides are involved. Properties of these compounds have also been studied in the Wittig reaction. 3-(α-chlorobenzyl)-2-oxoquinoxaline which reacted with trialkyl phosphates (Arbuzov reaction) has been synthesized. These phosphonates are obtained in nearly quantitative yields, in alkaline conditions (Horner-Emmons reaction) they react smoothly with aromatic aldehydes to give the substituted vinylyuinoxalines.

Advances in Chalcogene Glycerophosphate Chemistry

Abstract Achievements in the chemistry of trivalent phosphorus and phosphocyclic compounds find wide application in the synthesis of natural compounds. This paper provides fresh data on the possible use of these substances for the production of glycerophospholipids as well as their thio- and seleno-analogues. Thiol- and selenoanalogues of phosphatidylhomo-choline were obtained by a convenient thion-thiol/selenone-selenole isomerization of triester glycerophosphates in the presence of phosphonium salts as catalysts.

The synthesis of 1‐aminoalkylphosphonic acids. A revised mechanism of the reaction of phosphorus trichloride, amides and aldehydes or ketones in acetic acid (Oleksyszyn reaction)

AbstractThe mechanism of the amidoalkylation of trivalent phosphorus compounds in acetic acid has been reinvestigated. Evidence is presented that 1‐(acylamino)alkyl acetates 5 and not N,N′‐alkylidenebisamides 2 are the intermediates in this reaction. Supporting literature analogies are discussed. This paper also describes a convenient procedure for the preparation of crude (acylamino)alkyl alkanoates 5, which are excellent amidoalkylating agents. The usefulness of these reagents is demonstrated by a simple two‐step “one pot” synthesis of 1‐aminoalkylphosphonic acids 1.

Electron capture by trivalent phosphorus compounds: A single crystal ESR study of the chlorodithiaphospholane anion

The 2-chloro-1,3,2-dithiaphospholane anion has been trapped in an X-irradiated single crystal of 1. The anion has been identified by comparing its 31P and 35Cl hyperfine tensors with the corresponding couplings obtained from ab initio calculations on H 2PCl −. and PCl 3 −.. The structure of R 2PCl − is discussed. Increasing the temperature causes the dissociation reaction to occur, and the phosphinyl radical has been observed after annealing at 220 K.

ChemInform Abstract: Reaction of Trivalent Phosphorus Compounds with Dialkyl Acetylenedicarboxylates in the Presence of Carbon Dioxide.

AbstractThe phosphinite (I) reacts with the components (II) and (III) to form the oxaphospholene (IV) which in the presence of an excess phosphinite decomposes to give the di‐ylide (V).

Charge-transfer complexes with trivalent phosphorus compounds

Abstract Charge-transfer complexes between triphenylphosphine and triethylphosphite as donors, and maleic, itaconic and citraconic anhydrides as acceptors are studied.

Advances in Chalcogene Glycerophosphate Chemistry

Abstract Achievements in the chemistry of trivalent phosphorus and phosphocyclic compounds find wide application in the synthesis of natural compounds. This paper provides fresh data on the possible use of these substances for the production of glycerophospholipids as well as their thio- and seleno-analogues. Thiol- and selenoanalogues of phosphatidylhomo-choline were obtained by a convenient thion-thiol/selenone-selenole isomerization of triester glycerophosphates in the presence of phosphonium salts as catalysts.

ChemInform Abstract: Addition Reactions of the P‐H Functions of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 3.

ChemInform Abstract: Addition Reactions of the P‐H Functions of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 3.

Studies of the reaction of trivalent phosphorus compounds with dialkyl acetylenedicarboxylates in the presence of carbon dioxide

Alkyl diphenylphosphinites react with dialkyl acetylenedicarboxylates in the presence of carbon dioxide to form 1,2-oxaphosphol-3-enes (5) which in the presence of excess phosphinite decompose to give di-ylides (6). The 1,2-oxaphosphol-3-enes (5) from dialkyl phenylphosphonites and trialkyl phosphites react with a further phosphorus component to give the ylides (9) which can readily be converted into dialkyl 1,2,2-tris(alkoxycarbonyl)ethylphosphonates (11). Studies using 13C- and 2H-labelled precursor provide evidence for rearrangement occurring via ketene intermediates.

ChemInform Abstract: Addition Reactions of the P‐H Function of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 3.

ChemInformVolume 19, Issue 51 Reviews ChemInform Abstract: Addition Reactions of the P-H Function of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 3. W. WOLFSBERGER, W. WOLFSBERGER Inst. Anorg. Chem., Univ., D-8700 WuerzburgSearch for more papers by this author W. WOLFSBERGER, W. WOLFSBERGER Inst. Anorg. Chem., Univ., D-8700 WuerzburgSearch for more papers by this author First published: December 20, 1988 https://doi.org/10.1002/chin.198851353Read 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. Volume19, Issue51December 20, 1988 RelatedInformation

ChemInform Abstract: Addition Reactions of the P‐H‐Function of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 2.

ChemInformVolume 19, Issue 28 Reviews ChemInform Abstract: Addition Reactions of the P-H-Function of Trivalent Phosphorus Compounds to Unsaturated Systems. Part 2. W. WOLFSBERGER, W. WOLFSBERGER Inst. Anorg. Chem., Univ., D-8700 WuerzburgSearch for more papers by this author W. WOLFSBERGER, W. WOLFSBERGER Inst. Anorg. Chem., Univ., D-8700 WuerzburgSearch for more papers by this author First published: July 12, 1988 https://doi.org/10.1002/chin.198828348Read 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. Volume19, Issue28July 12, 1988 RelatedInformation

ChemInform Abstract: Nucleophilic Phosphorylation of N‐(α‐Chlorobenzyl)benzimidoyl Chloride with Trivalent Phosphorus Compounds.

AbstractIn the phosphorylation reaction of the benzimidoyl chloride (II) with the phosphine (Ia), the phosphinite (Ib), or the phosphite (Id), the chlorine atom at the sp3 carbon atoms is substituted, yielding the phosphonium salt (III), the phosphine oxide (IVb), or the phosphonate (IVc).

ChemInform Abstract: Synthesis of Novel Carbo‐ and Heteropolycycles. Part 6. Reactions of Some Bridgehead‐ and Bridge‐Azides Related to Adamantane with Some Selected Trivalent Phosphorus Compounds.

AbstractThe reactivity of the phosphines (IIa) and (IIb) or triethyl phosphite (IIc) towards the bicyclic azides (I) is tested.

ChemInform Abstract: Pesticides and Phosphorus

More than 20 % of about 300 active ingredients of pesticides registered in Japan are phosphorus compounds. Although they are mainly insecticides including acaricides, organophosphorus fungicides and herbicides have recently been developed. Moreover, nematicides, rodenticides, plant growth regulators, insect chemosterilants, and insecticide synergists are also known. Majority of organophosphorus pesticides are P (V) oxyacid derivatives, carrying a phosphoryl or thiophosphoryl group. Phosphonium salts and trivalent phosphorus compounds are rather rare as pesticides. The role of phosphorus moiety in pesticides is 1) the principal in phosphorylation, 2) a leaving group in alkylation, 3) a carrier for other active moiety, and 4) an analogous group for the carboxyl group. In order to display a certain pesticidal activity, the compound should have a structure suitable for selectivity or affinity to the target organism and biomacromolecule.

ChemInform Abstract: Silyl Peroxides as Selective Oxygenation Reagents in Phosphorus Chemistry.

AbstractUsing stoichiometric amounts of bis(trimethylsilyl) peroxide (II), the trivalent phosphorus compounds (I) are transformed into the P=O derivatives (III).