Phosphonium Compounds. II. Decomposition of Phosphonium Alkoxides to Hydrocarbon, Ether and Phosphine Oxide

Grayson, Martin; Keough, Patricia Tarpey

doi:10.1021/ja01500a033

Cited by 100 publications

(47 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…It has been previously reported that tetraalkylphosphonium cations can undergo decomposition to tertiary phosphine oxides and alkanes in the presence of base (equation 1). 13,14 [R3P-CH2-R'] + + OH -R3P=O + CH3-R' (1)…”

mentioning

confidence: 99%

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂

Bothwell

Marr

2017

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

We describe the autocatalytic synthesis of SiO 2 and TiO 2 ionic liquid gels using a basic ionic liquid as the solvent, template, and catalyst for the sol−gel reaction. Basic gels were synthesized using a two-component mixture of the basic ionic liquid [P 66614 ][OH] and either tetraethylorthosilicate or titanium isopropoxide (Ti(OiPr) 4 ). The gels formed were clear glassy materials. The unstable basic ionic liquid was stabilized by the matrix and showed both increased thermal stability (by thermogravimetric analysis) and chemical stability (by solid-state NMR) after over 1 year of storage.

show abstract

mentioning

confidence: 99%

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂

Bothwell

Marr

2017

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…Commercial NaBH 4 , selenium powder, and 2,4-dinitrophenylhydrazine were used as received. Ph 3 (CH 2 Ph)PBr [12], n-BuLi [13] [5] were prepared according to literature procedures. All reactions were monitored by thin layer chromatography (TLC) at intervals.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, spectroscopic characterization and reactivities of linear and butterfly chromium/selenium complexes containing substituted cyclopentadienyl ligands: crystal structures of [{η5-MeC5H4Cr(CO)2}2Se] and [{η5-EtO2CC5H4Cr(CO)2}2Se2]

Song

Cheng

2004

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…Instead, the tert-butoxide ion effects a nucleophilic attack on phosphorus, and cleaves the PN skeleton (Scheme 2). The subsequent elimination of isobutene or (less probably) an ether (9,10) then produces the novel linear oxophosphazene (NHMe)(PMe,N),PMe,O (9) in high yield (92%). The reaction of the tetrameric salt (NPMe,),.MeI with KO-t-Bu shows a marked contrast to the one just described.…”

Section: Reactions Of Quaternary Methylphosphazeniummentioning

confidence: 99%

The deprotonation and rearrangement of N-methyl methylphosphazenium quaternary salts: a novel synthetic route to cyclic azaphosphorins

Oakley¹,

Paddock²

1977

Can. J. Chem.

View full text Add to dashboard Cite

RICHARD T. OAKLEY and NORMAN L. PADDOCK. Can. J. Chem. 55, 3651 (1977). The N-methyl methylphosphazenium salts (NPMe,),,,.MeI and N3P3Ph4Me2.MeI can be deprotonated by a variety of bases to yield the novel azaphosphorins Me2,-,(NHMe)P,N,-,-CH (n = 3, 4) and Me(NHMe)Ph4P3N2CH, formed by a rearrangement in which the methylated nitrogen atom is displaced from the PN ring by the initially produced exocyclic methylene group. The 'H nmr spectra of the azaphosphorins indicate a rapid proton exchange between the endocyclic carbon and the exocyclic nitrogen, which can be slowed by the addition of an auxiliary base. When KO-t-Bu reacts with the quaternary salts, nucleophilic attack competes with proton removal, and the linear oxides (NHMe)(PMe2N).PMe20 (n = 2-4) have been isolated from these reactions. The azaphosphorins Me2,-l(NHMe)P,N,-lCH (n = 3, 4) are hydrolysed in aqueous ethanol to give the cyclic oxides Me2,-,(O)P,N,_ ,CH2, and react with methyl iodide by a proton transfer reaction to givelthe hydroiodides Me2.-,(NHMe)P.N,-,-CH.HI. Their reaction with benzoyl chloride leads to the derivatives Me7(NHMe)P4N3CCOPh and Me7(NMeCOPh)P3N2CCOPh, the initial substitution on carbon indicating that it is the primary basic centre. Model calculations of x-electron energies suggest that both the azaphosphorin rearrangement and the proton exchange reactions depend on the relative orbital electronegativity of the ring and exocyclic atoms, the less electronegative atom being more stable in the endocyclic position. Lorsque le KO-t-Bu rtagit avec les sels quaternaires, une attaque nucleophile concurrence l'abstraction du proton et il resulte de ces reactions des oxydes lintaires (NHMe)(PMe2N),PMe,0 (n = 2-4). Les azaphosphorines Me2.-,(NHMe)P.N,.. ,CH (n = 3, 4) sont hydrolyskes dans l'ethanol aqueux pour conduire aux oxydes cycliques Me2,-1-(O)P,N,-,CH2, et elles reagissent avec I'iodure de mCthyle par une reaction de transfert de protons pour conduire aux hydroiodures Me2,-,(NHMe)P,N, -lCH. HI. Elles rtagissent avec le chlorure de benzoyle pour conduire aux derives Me7(NHMe)P4N3CCOPh et Me7(NMeCOPh)P3N2CCOPh; la substitution initiale sur le carbone indique que celui-ci est le premier centre basique. Des calculs modeles des energies pour les electrons-n suggerent que tant le rearrangement des azaphosphorines que les reactions d'echange de protons dependent de l'electron6gativite relative des orbitales du cycle et des atomes exocycliques, I'atome le moins Clectrontgatif ttant plus stable en position endocyclique.[Traduit par le journal]

show abstract

Phosphonium Compounds. II. Decomposition of Phosphonium Alkoxides to Hydrocarbon, Ether and Phosphine Oxide

Cited by 100 publications

References 0 publications

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂

Synthesis, spectroscopic characterization and reactivities of linear and butterfly chromium/selenium complexes containing substituted cyclopentadienyl ligands: crystal structures of [{η5-MeC5H4Cr(CO)2}2Se] and [{η5-EtO2CC5H4Cr(CO)2}2Se2]

The deprotonation and rearrangement of N-methyl methylphosphazenium quaternary salts: a novel synthetic route to cyclic azaphosphorins

Contact Info

Product

Resources

About

Phosphonium Compounds. II. Decomposition of Phosphonium Alkoxides to Hydrocarbon, Ether and Phosphine Oxide

Cited by 100 publications

References 0 publications

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO2 and TiO2

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO2 and TiO2

Synthesis, spectroscopic characterization and reactivities of linear and butterfly chromium/selenium complexes containing substituted cyclopentadienyl ligands: crystal structures of [{η5-MeC5H4Cr(CO)2}2Se] and [{η5-EtO2CC5H4Cr(CO)2}2Se2]

The deprotonation and rearrangement of N-methyl methylphosphazenium quaternary salts: a novel synthetic route to cyclic azaphosphorins

Contact Info

Product

Resources

About

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂

Taming the Base Catalyzed Sol–Gel Reaction: Basic Ionic Liquid Gels of SiO₂ and TiO₂