Radical telomerization of vinyltrimethylsilane with diethyl phosphite

Telomerization of vinyltrimethylsilane with diethyl phosphite was carried out in the presence of tert-butyl peroxide (TBP), affording a series of regular telomers (EtO)₂P(O)(CH₂CHSiMe₃)_nH (n=1–3)(T_n) and the compounds Me₃Si· (CH₂)₂CH(CH₃)OP(O)(OEt)(CH₂)₂SiMe₃(T₂). Arguments are presented which support a rearrangement with 1,5-H migration in the first propagating radical along a chain including P and O atoms. The partial chain-transfer constant C₁ (6.2) was evaluated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1883–1887, August, 1990.     

Action of diethyl phosphite on p-benzoquinone and 1,4-naphthoquinone

Summary The addition of diphenyl phosphite to p-benzoquinone and to 1,4-naphthoquinone in presence of sodium alkoxide led to the formation of diethyl p-hydroxyphenyl phosphate and diethyl 4-hydroxy-1-naphthyl phosphate, respectively.     

3-Chloroalkylfurans in the reaction with sodium diethyl phosphite

Reduction of 3-acylfurans with lithium alumohydride in ether yields stable secondary alcohols. By treatment with thionyl chloride in the presence of pyridine, they are converted to the corresponding chlorides. 3-(1-Chloroethyl)furan and 5-methyl-3-(1-chloroethyl)furan react with sodium diethyl phosphite to give two products: 3-(1-diethoxyphosphorylethyl)furans and 3-ethyl-2-(diethoxyphosphoryloxy)furans. The methyl group in position 5 of the furan ring increases the relative phosphate content of the mixture by a factor of approximately 2.5. Blocking of position 2 or both positions 2 and 5 of the ring with methyl groups leads to phosphoate formation only. The reaction of 2,5-dimethyl-3-(1-chloro-2-methylpropyl)furan also occurs according to the Michaelis-Becker scheme. The products of the side chain dehydrohalogenation with sodium diethyl phosphite were not found.     

Relative kinetics of the telomerization of 1-hexene by diethyl phosphite

Conclusions According to relative kinetic data on the telomerization of 1-hexene by diethyl phosphite, a system based on Mn₂(CO)₁₀ effectively activates the transfer of hydrogen at the chain transfer stage.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2389–2392, October, 1988.     

Telomerization of 1-hexene by diethyl phosphite in the presence of decacarbonyldimanganese and peroxides

Conclusions An induction period, post effect and shift in the telomer homolog distribution toward T₁ were observed upon the use of Mn₂(CO)₁₀ as the initiator of the telomerization of 1-hexene with diethyl phosphite.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 218–221, January, 1987.     

17O NMR investigation of phosphite hydrolysis mechanisms

The use of solution 17O NMR spectroscopy in verifying the mechanism of trialkyl phosphite hydrolysis is presented. Trimethyl phosphite was reacted with 17O-labeled H2O at different temperatures and two reactant concentrations, with the reaction being monitored by 17O NMR. Kinetic details elucidated from the NMR spectra are also discussed.     

Chiral ytterbium silylamide catalyzed enantioselective phospha-Michael addition of diethyl phosphite to chalcones

An efficient and enantioselective phospha-Michael addition of diethyl phosphite to chalcones has been established. In the presence of a catalytic amount of chiral lanthanide silylamide generated from [(Me₃Si)₂N]₃Yb(μ-Cl)Li(THF)₃ and salen, the reaction produced the target γ-oxophosphonates with high yields and enantioselectivity.     

Transformations of diethyl phosphite in the presence of Mn2(CO)10

Upon heating with Mn₂(CO)₁₀-BrR systems, diethyl phosphite is partially converted to (EtO)₃P(O). Evidence is given for a radical complex mechanism for these transformations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1903–1905, August, 1989.     

Synthesis ofO,O-diethylSe-alkyl selenophosphates by the reactions of diethyl phosphite with alkaneselenenyl halides

The reactions of diethyl phosphite with alkaneselenenyl halides in chloroform at 20°C afforded the correspondingO,O-diethylSe-alkyl selenophosphates. Dedicated to the memory of Academician M. I. Kabachnik on his 90th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2099–2101, October, 1998.     

NMR studies of the bishydroxy bisphosphonate synthesis from o‐phthalic aldehyde and diethyl phosphite

The reaction of the o‐phthalic aldehyde with diethyl phosphite leading to the bishydroxy bisphosphonate has been studied. It was found that the reaction is complex and a cyclic acetal formed from the monohydroxyphosphonate is the first relatively stable product. It slowly transforms to the bishydroxy bisphosphonate. The latter compound undergoes intramolecular nucleophilic substitution of the phosphorus atom by the hydroxy group which results in a cyclic structure, a phosphonate‐hydroxyphosphate compound. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:157–164, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10014     

2-(1-Chloroalkyl)furans in the reaction with sodium diethyl phosphite

2-(1-Chloroethyl) and 2-(1-chloro-2-methylpropyl)furans react with sodium diethyl phosphite to give two products, 2-(1-diethoxyphosphorylmethyl)furan and 2-alkyl-5-(diethoxyphosphoryloxy)furan. The fraction of the latter product increases with increasing size of the alkyl radical. 2-Methyl substitution in the substrate completely suppresses phosphate formation. 2-(1-Chloroethyl)-5-(2-methylpropyl)furan under the action of sodium diethyl phosphite eliminates hydrogen chloride to give the corresponding alkene.     

An efficient Negishi cross-coupling reaction catalyzed by nickel(II) and diethyl phosphite

A combination of diethyl phosphite-DMAP and Ni(II) salts forms a very effective catalytic system for the cross-coupling reactions of arylzinc halides with aryl, heteroaryl, and alkenyl bromides, chlorides, triflates, and nonaflates. The choice of solvent is quite important and the mixture of THF-N-ethylpyrrolidinone (NEP) (8:1) was found to be optimal. The reaction usually requires only 0.05 mol % of NiCl₂ or Ni(acac)₂ as catalyst and proceeds at room temperature within 1-48 h.