Phosphinic Acid Derivatives Research Articles

Synthesis of dimeric 1,3,2λ5‐benzoxazaphospholes from phosphinic acid derivatives by silylation/desiloxylation

AbstractThe reaction of N,N,O‐tris(trimethylsilyl)‐o‐aminophenol with two equivalents of phosphinic chloride yielded dimeric 2,2‐disubstituted 1,3,2λ5‐benzoxazaphospholes and trimethylsilyl phosphinate. The chlorides having the bulk substituents (o‐chlorophenyl or tert‐butyl) at phosphorus or containing PN and PO bonds (instead of a PC bond) either didn't react at all or reacted to retain the phosphoryl group. Being stable in solution at 20°C, the individual diastereoisomers of dimeric 1,3,2‐benzoxazaphospholes were converted upon warming to an equilibrium mixture of isomers. When reacted with another dimer each gave a mixed dimeric compound having two different phosphorus atoms in the molecule.

ChemInform Abstract: Organophosphorus Compounds. Part 120. Experiments for the Detection of “Phosphenes” Generated from Suitable Phosphinic Acid Derivatives by Elimination.

AbstractReaction of benzylphenylphosphinic acid fluoride (I) with benzaldehyde (II) in the presence of strong bases yields stilbene (III).

Glycosyl imidates, 37. Direct O‐glycosylation of compounds containing a PO(OH) moiety

AbstractThe O‐benzylated α and β‐glucosyl trichoroacetimidates 1a–α and 1a–β afforded with the phosphinic acid derivative 2 and the phosphonic acid derivative 3 directly the corresponding O‐glucosylated products 4 and 5, resp., with inversion at the anomeric center. The corresponding O‐acetylated trichloroacetimidates 1b–α and 1b–β provided both the β‐products due to neighboring group participation. With the amidophosphoric acid derivative 6 and the trichloroacetimidate 1b–α the O‐glucosylated compound 8–β was obtained. The O‐acetylated 6‐deoxy‐L‐talopyranosyl donor 12 behaved similarly. With compound 2 the α‐phosphinate 13 was formed. Dibenzyl phosphate gave the α‐phosphate 14; subsequent debenzylation led to the 6‐deoxy‐α‐L‐talopyranosyl phosphate 15.

ChemInform Abstract: Organic Phosphorus Compounds. Part 82. Preparation, Properties, and Herbicidal Activity of 2‐Substituted 5‐Phenoxy‐ and 5‐Pyridyloxyphenylphosphonic and ‐phosphinic Acid Derivatives.

AbstractReaction of the dinitrobenzenes (III) with the trialkyl phosphites (II) produces the substituted nitrophenylphosphonates (I).

N‐Aryl‐O‐(diphenylphosphinoyl)hydroxylamines: Electrophilic Amination of Amines to Hydrazines; a Model Reaction for the Carcinogenicity of Aromatic Amines

The phosphinic acid derivatives 1 are stable hydroxylamine esters that react with amines HNR2R3 to give hydrazines 2. They are model compounds for metabolites of carcinogenic aromatic amines in living organisms, which include compounds also formed by electrophilic amination of N-arylhydroxylamine derivatives.

Evaluation of phosphinic acid derivatives as reagents for amine protection in peptide synthesis

The results of a kinetic study of the acid-catalysed methanolysis of a series of N-(2-phenyl-ethyl)phosphinamides incorporating selected substituents on phosphorus have been evaluated in order to define the optimum reagent and conditions for amine protection of α-amino acids during peptide synthesis.

Studies on the biosynthesis of bialaphos (SF-1293) Part 3. Production of phosphinic acid derivatives, MP-103, MP-104 and MP-105, by a blocked mutant of [formula omitted] SF-1293 and their roles in the biosynthesis of bialaphos

During biosynthetic studies on bialaphos to reveal the formation mechanisms of carbon-phosphorous bonds in detail, three new metabolites containing a HPC bond structure were isolated from the fermentation broth of a mutant of Streptomyces hygroscopicus SF-1293. Based on the spectroscopic analysis, the structures of these compounds have been determined as shown in Fig. 1. Transformation experiments of these metabolites to bialaphos suggested that the reduction of the phosphorous atom in phosphate will take place at an early biosynthetic stage.

Advances in Organophosphorus Chemistry Based on Dichloro(methyl)phosphane

AbstractBesides phosphorus trichloride and phosphane, dichloro(methyl)phosphane is gaining importance as a starting material for the synthesis of organophosphorus compounds. It provides ready access to phosphonic, phosphinic and phosphonous acid derivatives, as well as their secondary products. The synthetic and application potential of organophosphorus compounds—based on industrially produced dichloro(methyl)phosphane—is illustrated by means of numerous examples.

Alkylation of Phenyl Phosphinic Acid

Abstract Phosphinic acids have been used as intermediates in the preparation of unsymmetrical tertiary phosphine oxides,1 including optically active oxides. These phosphinic acid derivatives are prepared by the Arbuzov rearrangement of a phosphonite,2 which, in turn, usually comes from the corresponding phosphine dichloride. This route to phosphinic acid works well but involves exceptionally malodorus, air sensitive, hydrolytically unstable intermediates. We wish to report a simple method to prepare phenylphosphinic acids which utilizes odorless, stable solid species.

Structure of the product obtained from the reaction of an αα′-dibromophosphane oxide with 1,5-diazabicyclo[4.3.0]non-5-ene and other bases

The compound previously assigned a triphenylphosphiren oxide structure, as well as other base-induced rearrangement products of bis-(α-bromobenzyl)phenylphosphane oxide, are shown to be (E)-1,2-diphenylvinyl(phenyl)phosphinic acid derivatives.

ChemInform Abstract: STUDIES ON DIALKYLMETAL PHOSPHORIC AND PHOSPHINIC ACID DERIVATIVES OF ALUMINUM, GALLIUM, INDIUM, AND THALLIUM. IV. DIMETHYLGALLIUM‐N‐METHYLDIFLUOROPHOSPHORAMIDE

Chemischer InformationsdienstVolume 8, Issue 40 Organoelement Compounds ChemInform Abstract: STUDIES ON DIALKYLMETAL PHOSPHORIC AND PHOSPHINIC ACID DERIVATIVES OF ALUMINUM, GALLIUM, INDIUM, AND THALLIUM. IV. DIMETHYLGALLIUM-N-METHYLDIFLUOROPHOSPHORAMIDE H. SCHREM, H. SCHREMSearch for more papers by this authorJ. WEIDLEIN, J. WEIDLEINSearch for more papers by this author H. SCHREM, H. SCHREMSearch for more papers by this authorJ. WEIDLEIN, J. WEIDLEINSearch for more papers by this author First published: October 4, 1977 https://doi.org/10.1002/chin.197740305Read 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. Volume8, Issue40October 4, 1977 RelatedInformation

Synthesis and anti-herpes simplex activity of analogues of phosphonoacetic acid.

The synthesis of monoesters (P and C) of phosphonoacetic acid (PA) is given. The carboxyl esters were prepared by two methods: the reaction of chloroacetates with tris(trimethylsilyl) phosphite, followed by hydrolysis; and by the acid-catalyzed esterification of PA with the appropriate alcohol. P-Monoesters of PA were prepared either by the reaction of alkyl[bis(trimethylsilyl)] phosphite with benzyl chloroacetate followed by deprotection or by the reaction of dimethylphenyl phosphite with benzyl bromoacetate followed by hydrogenolysis. Three aryl- (alkyl-)phosphinic acid derivatives are reported. The above compounds were evaluated for anti-herpes activity against HSV-induced DNA polymerase and in animals infected with herpes dermatitis.

Organometallic complexes in synthesis. Nucleophilic reactions on tricarbonylcyclohexadienyliron cations: Some cyclohexadienyl phosphinic, phosphonic and sulphonic acid derivatives

Organometallic complexes in synthesis. Nucleophilic reactions on tricarbonylcyclohexadienyliron cations: Some cyclohexadienyl phosphinic, phosphonic and sulphonic acid derivatives

Polymers and copolymers of divinyl phosphinate

The radical-chain bulk polymerization of divinyl phosphinic acid derivatives gives three-dimensional, hard to rubber-like products. The thermomechanical properties of these polymers are governed by the nature of the monomers used and by the polymerization conditions. Polymerization of ethylvinyl phosphinate in benzene or ethanol disclosed the part played by the solvent affinity for the polyphosphinate chains, and also cyclolinear growth on polymer production. The use of benzene yielded only a steric product, while a soluble, cyclolinear oligomer formed in ethanol. It is concluded that the crosslinks consist of cyclo-linear units together with vinyl phosphinate ones in the steric polymerization of divinyl phosphinates, as for other 1,4-dienes. The ethyldivinyl phosphinate was found to be less reactive in copolymerizations with styrene or methyl methacrylate, than the monomers; steric and soluble copolymers with phosphate as ligand were produced.

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis‐(ß‐chloräthyl)‐phosphinsäure‐Derivaten [1

AbstractReaction of ClCH2CH2PCl2 with ethylene oxide gives the phosphonous acid ester ClCH2CH2P (OCH2CH2Cl)2 which on heating to 120° rearranges to the phosphinic acid ester (ClCH2CH2)2P(O)OCH2CH2Cl (3). Chlorination of 3 with PCl5 in CCl4‐solution yields the phosphinic chloride (ClCH2CH2)P(O)Cl (4), which on treatment with P2S5 at 170° produces the thioderivative, (ClCH2CH2)2P(S)Cl, (5). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH2CH2) P (X)Y, (X = O, S; Y = OR, SR, NR2) (6). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH2 = CH)2P (X) Y (X = O, S; Y = OR, SR, NR2) (7).Bis‐(ß‐chloroethyl)‐phosphinates, e. g. (ClCH2CH2)2P (O) OEt, undergo a Michaelis‐Arbuzov reaction when heated with phosphites to 160–170° to give bis‐(phosphonylethyl)‐phosphinates, e.g. (EtO) (O)P[CH2CH2CH2P(O)(OEt)2]2 (8), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO2P(CH2CH2PO3H2)2.

Phospholin-derivate aus phosphor-trihalogeniden und dienen

1,1,1-Trihalophospholines can be prepared from dienes and phosphorus trihalides. Phosphinic and thiophosphinic acid derivatives, respectively, have been obtained by solvolysis of these compounds, whereas 1-oxo-1-chlorophospholines resulted from acetanhydride or sulfur dioxide treatment. The latter products have been converted to phosphine oxides by Grignard-compounds. The reaction described is simpler and more versatile than the addition of aryl- and alkyldichlorophosphines to dienes. It was found that the CC-double bond in the reaction products from trihalophospholines with the reagents described had shifted to the 2,3-position.

Investigations in phosphinic and phosphinous acid derivatives—XIV. Polymerization of some unsaturated esters of ethylphosphinic acid : I. A. Krivosheeva, A. I. Razumov and H. S. Kolesnikov, Vysokomol. soedin. 3: No. 8, 1247–1250, 1961

Investigations in phosphinic and phosphinous acid derivatives—XIV. Polymerization of some unsaturated esters of ethylphosphinic acid : I. A. Krivosheeva, A. I. Razumov and H. S. Kolesnikov, Vysokomol. soedin. 3: No. 8, 1247–1250, 1961