Decomposition of triphenyl phosphite ozonide catalyzed by pyridine

Pyridine accelerates the decomposition of triphenyl phosphite ozonide in CH₂Cl₂. The addition of alcohol to the system (PhO)₃PO₃–C₅H₅N–CH₂Cl₂ increases the rate of this process. The kinetics of (PhO)₃PO₃ decomposition in pyridine, in ethanol-pyridine, 2-propanol-pyridine mixtures and in CH₂Cl₂ were investigated.     

Reaction of triphenyl phosphite witho-aminophenol

Conclusions The reaction ofo-aminophenol with triphenyl phosphite gave spirophosphorane (III).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, p. 1426, June, 1973.     

Oxidation of diazo compounds by triphenyl phosphite ozonide. Quenching of singlet oxygen by diazo compounds

The reaction of triphenyl phosphite ozonide with various types of diazo compounds results in their oxidation, which is accomplished by singlet oxygen (¹O₂) evolved during thermal decomposition of the ozonide. A decrease in the ionization potential of the substrate results in an increase in the overall rate constant of quenching of¹O₂. In the case of 9-diazofluorene, the main channel of¹O₂ quenching is physical quenching.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1567–1571, September, 1994.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-5231).     

Reactions of triphenyl phosphite with di- and tribromoacetaldehydes

Conclusions The reaction of triphenyl phosphite and di- and tribromoacetaldehydes proceeds through initial halophilic attack with subsequent formation of triphenyl phosphate and tetraphenylphosphonium bromide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1668–1670, July, 1988.     

Oxidation of 2-trimethylsilyloxy-1,3-dienes with triphenyl phosphite ozonide. A regioselective α′-hydroxylation of α,β-unsaturated ketones

The present work deals with a novel method for the introduction of hydroxyl group to the α′-carbon of α,β-unsaturated ketones using triphenyl phosphite ozonide.     

Regioselective oxygenations of s-trans dienes, silyl dienol ethers (SDEs), by triphenyl phosphite ozonide (TPPO) and its mechanistic study

The direct oxygenation of s-trans dienes, silyl dienol ethers (SDEs) 2, by triphenyl phosphite ozonide (TPPO) has been examined in detail. The regioselective oxygenation was found to give hydroperoxide 3, alcohol 4, ketone 5, dimer 6, and peroxy phosphate 7 with concomitant formation of triphenyl phosphate 8 and diphenyl trimethylsilyl phosphate 10. The formation of peroxy phosphate 7 was found for the first time in TPPO oxygenation reactions. The low temperature (31)P and (1)H NMR spectroscopic analyses proved the direct reaction of SDEs with TPPO without generation of singlet oxygen. The formation of the oxygenated products 3-7 is reasonably explained by the intervention of the zwitterion ZI, which can be formed by the nucleophilic attack of SDE to the central oxygen of the ozonide. The regioselective attack of SDE to the central oxygen of the ozonide was supported by the quantum chemical calculation (B3LYP/6-31G).     

Orientational correlations in the glacial state of triphenyl phosphite

Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structure of the glacial and supercooled liquid states in triphenyl phosphite. The observed diffraction patterns have been interpreted using a Reverse Monte Carlo modeling technique. The results show that the glacial state forms unusually weak intermolecular hydrogen bonds between an oxygen atom connected to a phenyl ring and an adjacent phenyl ring aligned in an approximately antiparallel configuration. The structure is very different from the hexagonal crystal which is characterized by two weaker hydrogen bonds between linear arrays of molecules which are offset from each other and packed in a hexamer arrangement.     

Reaction of triphenyl borate with 1,3,5-trioxane

Triphenyl borate was prepared by reaction of boric acid with phenol in xylene. Its reaction with 1,3,5-trioxane involved replacement of protons in the para positions of the benzene rings by methylene group.     

Reaction of gem-nitronitroso-compounds with triethyl phosphite

2-Nitro-2-nitrosopropane reacts with triethyl phosphite by deoxygenation of the nitroso- group to give 2-nitriminopropane; 1-nitro-1-nitrosocyclohexane reacts similarly. The reaction proceedsvia an intermediate detectable byNMR; possible structures for this intermediate and for the course of the reaction are discussed. Some reactions of nitrimines are also reported.