Studies on aryl H-phosphonates. 3. Mechanistic investigations related to the disproportionation of diphenyl H-phosphonate under anhydrous basic conditions

Kers, Annika; Kers, Inger; Stawiński, Jacek; Sobkowski, Michał; Kraszewski, Adam

doi:10.1016/0040-4020(96)00525-x

Cited by 43 publications

(25 citation statements)

References 23 publications

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“…31 P NMR for 5b at δ1.30 ppm is similar with the literature value ranging between 1.08‐1.4 ppm. [ 17,59–61 ] The proton‐decoupled 31 P peaks for 3a , 3b , 3c , and 3d appeared at 130, 129, 128.7, and 128 ppm, respectively, agreed well with (±)0.04 – (±)1.0 ppm values that were previously reported. 53 Peaks at 2.60, 1.94, and 1.36 ppm were assigned to aryl hydrogen phosphonates 5a , 5c , and 5d , respectively.…”

Section: Methodssupporting

confidence: 88%

A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle

Ghosh

Greer

2020

J of Physical Organic Chem

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With interests in alkoxy radical formation on natural and artificial surfaces, a physical‐organic study was carried out with a Hammett series of triaryl phosphites (p‐MeO, H, p‐F, and p‐Cl) to trap adsorbed alkoxy radicals on silica nanoparticles. A mechanism which involves PhC (Me)2O• and EtO• trapping in a cumylethyl peroxide sensitized homolysis reaction is consistent with the results. The p‐F phosphite was able to indirectly monitor the alkoxy radical formation, and 31P NMR readily enabled this exploration, but other phosphites of the series such as the p‐MeO phosphite were limited by hydrolysis reactions catalyzed by surface silanol groups. Fluorinated silica nanoparticles helped to suppress the hydrolysis reaction although adventitious water also plays a role in hindering efficient capture of the alkoxy radicals by the phosphite traps.

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Section: Methodssupporting

confidence: 88%

A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle

Ghosh

Greer

2020

J of Physical Organic Chem

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“…10 This impurity was effectively removed to the level below 1% by vacuum distillation. Starting from a not purified 3 polycondensation results in polymers of M h n below 10 3 .…”

Section: Resultsmentioning

confidence: 99%

Preparation of Poly(alkylene H-phosphonate)s and Their Derivatives by Polycondensation of Diphenyl H-Phosphonate with Diols and Subsequent Transformations

et al. 1997

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A new method of preparation of poly(alkylene H-phosphonate)s (1) by polycondensation of diphenyl H-phosphonate with diols such as 1,10-decanediol or tetra(oxyethylene) glycol is described. These polymers can be converted into poly(alkylene phosphate)ssmimicking backbones of nucleic acids and other biomacromolecules. The described method is the only one allowing simple preparation of this important class of polymers. This method eliminates the major side reaction taking place when dialkyl H-phosphonates are used and is related to the C-alkylation and formation of the unreactive ether end groups. Reaction of diphenyl H-phosphonate with alcohols is practically irreversible and can be performed without removing phenol, formed as a byproduct of condensation. It can be carried out in solvent or in bulk at temperature 80-200°C. Removing phenol enhances, however, formation of polymers with higher M h n. Polymers with M h n ∼ 30 × 10 3 were obtained and characterized as such or in the form of their derivatives. Chlorination of 1 with gaseous Cl2 leads to corresponding poly(alkylene chlorophosphate)s transformed readily into further derivatives, for instance, poly(alkyl alkylene phosphate)s, poly(alkylene phosphate) salts, or/and acids, using the poly(alkylene phosphorimidazolide) as the reactive intermediate.

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“…We found that, similarly to other alcohols, the transesterification of 1 with tritanol 2 in acetonitrile in the presence of triethylamine or DBU was rather inefficient due to competing disproportionation of diphenyl H-phosphonate [15]. However, when diphenyl H-phosphonate 1 was treated with 2 (2 equiv.)…”

Section: Reaction Of Tritanol With Diphenyl Hphosphonate In Pyridinementioning

confidence: 70%

Studies on the reaction of trityl derivatives withH-phosphonate diesters: Their relevance to the synthesis of 4-pyridylphosphonates

et al. 1999

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Studies on aryl H-phosphonates. 3. Mechanistic investigations related to the disproportionation of diphenyl H-phosphonate under anhydrous basic conditions

Cited by 43 publications

References 23 publications

A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle

A fluorinated phosphite traps alkoxy radicals photogenerated at the air/solid interface of a nanoparticle

Preparation of Poly(alkylene H-phosphonate)s and Their Derivatives by Polycondensation of Diphenyl H-Phosphonate with Diols and Subsequent Transformations

Studies on the reaction of trityl derivatives withH-phosphonate diesters: Their relevance to the synthesis of 4-pyridylphosphonates

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