Reaction Of Trimethyl Phosphite Research Articles

ChemInform Abstract: GAS‐PHASE CHEMISTRY OF TRIMETHYL PHOSPHITE

AbstractDie Reaktionen von Trimethylphosphit mit den Nucleophilen HzN′, MeHN", MC2N‐, H0′, MeO′, H", F′, HzP′ und CR2=CR‐CH (R: H, Me) werden untersucht, Produkte, Verzweigungsverhältnisse und Geschwindigkeitskonstanten ermittelt.

Gas-phase chemistry of trimethyl phosphite

Abstract : The reactions of trimethyl phosphite were investigated with a series of nucleophiles. Products, branching ratios, and reaction rate constants are reported. Reactions generally proceed through an ion-dipole complex (Z-. (CH3O) 3P), to a phosphoranide anion intermediate, (CH3O)3PZ-), to displacement of methoxide to form a new ion-dipole complex (CH3O-(CH3O)2PZ). If an additional acidic hydrogen is available on the nucleophile, the major products result from proton abstraction by methoxide: (CH3O-.(CH30)2PYH) yield (CH30)2PY-+CH3OH. While the displacement of methoxide from phosphorus is sufficiently endothermic, a competing attack at carbon by the original nucleophile occurs: (HY-.(CH3O)3P) yields CH3YH+ (CH3O)2Po-. Nucleophiles without an additional acidic hydrogen react similarly, but the final reaction products result from 1) SN2 reaction of methoxide, 2) SN2 reaction of the original nucleophile, and 3) stabilization of the phosphoranide intermediate, and 4) expulsion of methoxide from the ion- dipole complex. Reaction mechanisms are discussed in terms of the nature of the nucleophiles, the observed products, and the thermodynamics of the displacement reaction. Originator-supplied keywords include: Flowing afterglow; Trimethyl phosphite; Reaction mechanisms; Phosphorous; and Nucleophilic displacement.

Cyclic enediol phosphoranes obtained from the reaction of trimethyl phosphite with biacetyl and hexafluorobiacetyl give strikingly different acylation products

Cyclic enediol phosphoranes (2,2,2-trimethoxy-2,2-dihydro-l,3, 2-dioxaphospholenes), prepared from α-diketones, RCOCOR, and trimethyl phosphite (TMP), give strikingly different acylation products depending on the electronic properties of the groups, R, that occupy the 4,5-positions in the dioxaphospholene ring with pentacovalent phosphorus. Reaction of acetyl chloride or bromide with the hexafluorobiacetyl-TMP phosphorane gives exclusively the product of endo cyclic O-acylation, dimethyl(2-acetoxy- cis -1,2, - bis trifluoromethylvinyl) phosphate. Acylation of the biacetyl-TMP phosphorane gives mixtures of the product of exo cyclic O-acylation (a cyclic enediol phosphate) and the product of C-acylation (an α-hydroxy-β-diketone phosphate), the proportions depending on the structure of the acyl halide and the solvent. The parent 1,3,2-dioxaphospholene, i.e., the glyoxal-TMP phosphorane where R = H, gives exclusively the product of endo cyclic O-acylation with both acyl halides in all solvents.

ChemInform Abstract: REACTION OF PHOSPHORUS ACID ESTERS WITH α‐FLUOROCARBONYL COMPOUNDS

Abstract(VII) im Verhältnis von 5:4:2.

Reaction of phosphorous acid esters with ?-fluorocarbonyl compounds

1. The reaction of trimethyl phosphite with fluoral proceeds with the formation of a mixture of 2,2,2-trimethoxy-3,5-bis(trifluoromethyl)-1,4,2-dioxaphospholane, trimethyl phosphate, and dimethyl methylphosphonate. 2. The reaction of diethyl trimethylsilyl phosphite with fluoral gives diethylα-trimethylsiloxy-β,β,β-trifluoroethylphosphonate, which at an elevated temperature decomposes to diethylβ,β-difluorovinyl phosphate.

Reaction of phosphites with unsaturated acid chlorides: synthesis and reactions of dimethyl but-2-enoylphosphonate

Dimethyl trans-but-2-enoylphosphonate has been prepared in moderate yield from the reaction of trimethyl phosphite with excess of trans-but-2-enoyl chloride. When the reaction is carried out using equimolar quantities of reactants the major products is the trans-but-2-enoyl ester (5). This ester is formed by the facile reaction of the trans-but-2-enoyl phosphonate with trimethyl phosphite to give the pentacovalent oxaphospholen (6) which is then attacked by trans-but-2-enoyl chloride. The reactions of trialkyl phosphites with 2-methylpropenoyl and propenoyl chlorides follow similar pathways but at different relative rates.

Properties and reactions of trimethyl phosphite, trimethyl phosphate, triethyl phosphate, and trimethyl phosphorothionate by ion cyclotron resonance spectroscopy

Properties and reactions of trimethyl phosphite, trimethyl phosphate, triethyl phosphate, and trimethyl phosphorothionate by ion cyclotron resonance spectroscopy

Attack of trimethylphosphite upon a η 6 -benzene ligand to give 2–6-η-1- exo-dimethoxyphosphorylcyclo- hexadienyl(η 5-ethyltetramethylcyclopentadienyl)-rhodium(III) hexafluorophosphate

The title compound has been prepared by reaction of trimethylphosphite with η 6 -benzene(σ 5 -ethyltetramethylcyclopentadienyl)rhodium(III) hexafluorophosphate. IR and 1H, 13C and 31P NMR spectra of the product are reported.

Reaction of trimethyl phosphite with benzalacetophenone and benzal-α-tetralone

Benzalacetophenone and benzal-α-tetralone when heated (50–60o) for a long time with trimethyl phosphite form 1,2-oxa-4-phospholenes, which represent heat unstable compounds of pentacoordinated phosphorus.

Reaction of trimethyl phosphite and tri(dimethylamino)phosphine with C,N-diphenylnitrone and 2,5-diphenyl-3,4-diazacyclopentadien-l-one-3,4-dioxide

Reaction of trimethyl phosphite and tri(dimethylamino)phosphine with C,N-diphenylnitrone and 2,5-diphenyl-3,4-diazacyclopentadien-l-one-3,4-dioxide

Δ2,2′-Bis-(4,5-dicyano-1,3-dithiolidene)

Δ2,2′-Bis-(4,5-dicyano-1,3-dithiolidene) is prepared quantitatively by the reaction of trimethyl phosphite with 4,5-dicyano-1,3-dithiol-2-one.

ChemInform Abstract: AUTOXIDATION OF TRIMETHYL PHOSPHITE INITIATED BY ONE‐ELECTRON TRANSFER FROM PHOSPHITE TO QUINONES

AbstractUnter Luftzutritt reagiert Acenaphthenchinon (I) mit Trimethylphosphit (II) (ohne Lösungsmittel oder in Dioxan oder CHCl3) quantitativ zu dem Addukt (III) und Trimethylphosphat (IV), während bei der Reaktion unter N2 quantitativ (III) als einziges Reaktionsprodukt entsteht.

Reaction of trimethyl phosphite with benzylidenebenzoylacetic ester

1. Trimethyl phosphite reacts with benzylidenebenzoylacetic ester to give 2,2,2-trimethoxy-3,5-di-phenyl-4-carbethoxy-1-oxa-2-phospha-4-cyclopentene (I). 2. When (I) is reacted with water and acetic anhydride the opening of the phosphorane ring occurs at the P-O bond. Phosphorane (I) is stable toward alcohol. 3. The structure of all of the obtained products was confirmed by the IR spectra.

The reaction of dimethylamino phosphines and arsines and trimethylphosphite with bis(trifluoromethyl)nitroxide and trifluoromethylsulphenyl chloride

Tris(dimethylamino)phosphine and arsine react with bis(trifluoromethyl)nitroxide, (CF 3) 2-NO·, to form (Me 2N) 2 MON(CF 3) 2 ( M = P, As) and Me 2NON(CF 3) 2. The chlorophosphines and arsines (Me 2N) 2 MCl ( M = P, Cl) react with Hg[ON(CF 3) 2] 2 to form [Me 2N] 2 M[ON(CF 3) 2] ( M = P, As). The dichlorophosphine Me 2NPCl 2 gives Me 2NP[ON(CF 3) 2] 2. The reaction of trimethylphosphite with CF 3SCl gives an equimolar mixture of CF 3SP(O)(OMe) 2, (MeO) 2P(O)Cl, MeCl and CF 3SMe.

Tertiary phosphite–alkyl halide reactions in acetonitrile

Olefin elimination does not occur during the interaction of ca. 0.2 M triisopropyl phosphite and isopropyl iodide (and of other simple tertiary phosphite–alkyl halide mixtures) in acetonitrile, contrary to a previous report. At and below 50°, the Arbuzov reaction does occur very slowly in these systems. The reaction of trimethyl phosphite and n-butyl iodide in acetonitrile gives a larger yield of dimethyl methylphosphonate than of dimethyl n-butylphosphonate.

Reaction of trimethyl phosphite and dimethylphosphorous acid with 1-phenyl-3-methyl-4-benzylidene-5-pyrazolone

1. Trimethyl phosphite adds to l-phenyl-3-methyl-4-benzylidene-5-pyrazolone in two ways: To the\( - CH = C - C = N and - CH = C - \begin{array}{*{20}c} C \\ {||} \\ o \\ \end{array} -\) conjugated systems to form dimethyl (l-phenyl-2,3-dimethyl-5-pyrazolon-4-yl)benzylphosphinate and dimethyl (1-phenyl-3-methyl-5-methoxy-4-pyrazolyl)benzylphosphinate. 2. The structures of the products are confirmed by chemical and spectroscopic data.

Reaction of trimethyl phosphite with ethyl benzylideneacetoacetate

1. Trimethyl phosphite reacts with ethyl benzylideneacetoacetate forming 2,2,2-trimethoxy-3-phenyl-4-carbethoxy-5-methyl-l-oxa-2-phosphacyclopentene-4. 2. Reactions of the above phosphorane with water, methanol, and acetic anhydride were investigated. 3. The structure of all the products obtained was verified by special methods.

Phosphonic Acids and Esters. X. Oxygen to Carbon Methyl Migration in the Reaction of Trimethyl Phosphite with Dimethyl Acetylenedicarboxylate1,2

Phosphonic Acids and Esters. X. Oxygen to Carbon Methyl Migration in the Reaction of Trimethyl Phosphite with Dimethyl Acetylenedicarboxylate^1,2

A Crystalline Tetraalkoxyalkylphosphorane from the Reaction of Trimethyl Phosphite with an α,β-Unsaturated Ketone. 3-Benzylidene-2,4-pentanedione. P31 and H1 Nuclear Magnetic Resonance Spectra1,2

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA Crystalline Tetraalkoxyalkylphosphorane from the Reaction of Trimethyl Phosphite with an α,β-Unsaturated Ketone. 3-Benzylidene-2,4-pentanedione. P31 and H1 Nuclear Magnetic Resonance Spectra1,2Fausto Ramirez, O. P. Madan, and S. R. HellerCite this: J. Am. Chem. Soc. 1965, 87, 4, 731–734Publication Date (Print):February 1, 1965Publication History Published online1 May 2002Published inissue 1 February 1965https://doi.org/10.1021/ja01082a009RIGHTS & PERMISSIONSArticle Views177Altmetric-Citations88LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (419 KB) Get e-Alerts Get e-Alerts