Kinetics of the hydrolysis of tri- and diethyl phosphite

Conclusions We have studied the kinetics of the hydrolysis of triethyl phosphite in water and dilute KOH, and of the hydrolysis of diethyl phosphite in water and dilute HCl. The temperature dependences of the velocity constants have been determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2551–2552, November, 1967.     

Reaction of triethyl phosphite with polyfluoroaromatic compounds that contain activated fluorine atoms

Conclusions Polyfluoroaromatic compounds that contain activated fluorine atoms enter into the Arbuzov reaction with triethyl phosphite to give the corresponding diethyl esters of arylphosphonic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2839–2840, December, 1977.     

Tetraalkyl Hydroxymethylene-bisphosphonate and Dialkyl 1-Diphenylphosphinoyl-1-hydroxy-ethylphosphonate Derivatives by the Pudovik Reaction and Their Rearranged Products

The reaction of diethyl α-oxoethylphosphonate and diethyl oxobenzylphosphonate with diethyl phosphite, dimethyl phosphite, and diphenylphosphine oxide affords, depending on the substrates and conditions (nature and quantity of the amine catalyst, temperature, and solvent), the Pudovik adduct and/or the corresponding >P(O)–CH–O–P(O)< product formed by rearrangement. The nature of the substituent on the central carbon atom (a methyl or phenyl group) influences the inclination for the rearrangement. The asymmetric products (either adducts or rearranged species) with different P(O)Y functions (Y = RO or Ph) exhibit interesting NMR features.     

Penta- and tetracoordinated phosphorous in reactions of biacetyl with diethylacetylphosphite and diethyl chlorophosphite

Conclusions Diethylacetyl phosphite and diethyl chlorophosphite react with biacetyl, intermediately forming, as do other derivatives of phosphorous acid, 1,3,2-dioxaphospholenes with a pentacoordinated phosphorous atom; the latter are rapidly transformed to noncyclic or cyclic derivatives of tetracoordinated phosphorous.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2609–2611, November, 1968.Deceased.     

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.     

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.     

Properties of Onium Salts of Phosphorus and Nitrogen

Ammonium and phosphonium halides when heated with excess dimethyl or diethyl phosphite can undergo anion exchange as a result of alkylation of halide ions with dialkyl phosphites. Experimental data were obtained, that cast some doubt in the commonly accepted opinion that reactions of tertiary amines and phosphines with dihalides in apolar media result in exclusive formation of monosalts.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1137–1139.Original Russian Text Copyright © 2005 by Ovakimyan, Barsegyan, Kikoyan, Indzhikyan.     

In(OTf)3 catalysed simple one-pot synthesis of α-amino phosphonates

A new efficient one-pot synthesis of α-amino phosphonates derived from nitro substituted anilines, aldehydes and diethyl phosphite has been carried out by employing 5 mol% of In(OTf)₃. The method is equally effective for the generation of α-amino phosphonates from various carbonyl compounds and other amines.     

The Kabachnik–Fields and Pudovik Reactions on the Basis of E,Z‐Citral and Its Imines and (R,S)‐Citronellal

The Kabachnik–Fields reaction of E,Z‐citral with diethyl phosphite in the presence of isobutylamine has been found to form α‐aminophosphonates. The Pudovik reactions of diethyl phosphite with prenyl imines prepared on the basis of E,Z‐citral with isobutylamine also allowed us to obtain the same α‐aminophosphonates. We have managed to synthesize α‐aminophosphonates by the reaction of O,O‐dialkyl trimethylsilyl phosphites with prenyl imines in the presence of water or diethylamine. α‐Aminophosphonates were also synthesized by the reaction of diethyl phosphite with (R,S)‐citronellal in the presence of alkylamines. α‐Aminophosphonates obtained showed bacteriostatic activity against Staphylococcus aureus and Bacillus cereus. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 24:36–42, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21060     

Enantioselective reductive multicomponent coupling reactions between isatins and aldehydes

A metal-free stereoselective reductive coupling reaction between isatins and aldehydes is reported. The reaction relies on commercial diethyl phosphite (∼€70 kg^–1) as the stoichiometric reductant. Base-catalyzed Pudovik addition and phosphonate/phosphate rearrangement achieved polarity inversion on the isatin, and the derived carbanions were trapped by aldehydes with subsequent dialkoxyphosphinyl migration. Chiral iminophosphoranes were used as basic catalysts to achieve high diastereo- and enantioselectivities with excellent yields.     

Reactions of esters of cyclopropylfurancarboxylic acids in the system paraform-hydrogen chloride-zinc chloride and phosphorylation of reaction products

Ethyl 2- and 5-cyclopropylfuran-3-carboxylates react with the system comprising Paraform, hydrogen chloride, and zinc chloride to form chloromethyl derivatives. This process is accompanied by selective cleavage of the cyclopropane ring, leading to appearance of a -chloropropyl fragment. Phosphorylation of the resulting halides with sodium diethyl phosphite in benzene involves exclusively the chloromethyl group.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1279–1281.Original Russian Text Copyright © 2004 by Pevzner.This revised version was published online in April 2005 with a corrected cover date.     

Reactions of some nitrosoperfluoroalkanes with trimethylsilyl phosphites

Nitrosotrifluoromethane or nitrosopentafluoroethane reacted with trimethylsilyl diethyl or tris(trimethylsilyl) phosphite to give phosphato-fluorocarbimino- or phosphato-trifluoroacetimino-phosphonates and fluorotrimethylsilane. Some intermediate compounds could be detected by NMR spectroscopy, namely, diethyl (N-trimethylsiloxy-N-trifluoromethyl)- or diethyl (N-trimethylsiloxy-N-pentafluoroethyl)amidophosphate and difluorocarbimino diethyl phosphate. © 1996 John Wiley & Sons, Inc.     

Isolation and investigation of the thermal stability of the ozonide of [L(−)-menthyl][O-phenylene] phosphite

Conclusions The optically active ozonide of [L(–)-menthyl] [o-phenylene] phosphite was obtained; its thermal stability was studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1381–1383, June, 1988.     

Specific Features of Reactions of Halomethyl Derivatives of 2-Isobutylfuran with Nucleophiles

3,4- and 3,5-bis(chloromethyl)-2-isobutylfurans react with sodium diethyl phosphite by the Michaelis-Becker reaction scheme to form phosphonates whose yield significantly depends on the location of the halomethyl group in the furan ring. 3,4-Bis(chloromethyl)-2-isobutyl-5-methylfuran under analogous conditions gives a diphosphonate, while in 3,5-bis(chloromethyl)-2-isobutylfuran phosphorylation of the α-chloromethyl group competes with dehydrochlorination leading to a chloromethylated alkene, the second process being preferred. Further phosphorylation involves only one chloromethyl group of the alkene. Ethyl 5-(bromomethyl)-2-isobutylfuran-3-carboxylate reacts with sodium acetate to give a substitution product, while its isomer with the reverse location of the substituents eliminates hydrogen bromide exclusively. In the latter case, the acetate is formed only as a minor product.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 991–998.Original Russian Text Copyright © 2005 by Pevzner.     

Direct and stereoselective synthesis of β-d-mannosides using 4,6-O-benzylidene-protected mannosyl diethyl phosphite as a donor

A direct and practical method for the construction of β-mannosidic linkages is described. While β-selectivities in the TMSOTf-promoted glycosidation of 2,3,4,6-tetra-O-benzyl-d-mannosyl diethyl phosphite are found to be highly dependent on the reactivity of acceptor alcohols, 2,3-di-O-benzyl-4,6-O-benzylidene-d-mannosyl diethyl phosphite reacts with a wide range of acceptor alcohols in the presence of TMSOTf in CH₂Cl₂ at −45 °C to give β-mannosides in high yields with good to high β-selectivities.     

Electroanalytical study of diethyl and dibutyl phthalate in micellar and oil-in-water emulsified media

A polarographic study was carried out of the reduction processes of diethyl and dibutyl phthalate in micellar solutions with the cationic surfactant Hyamine 1622, and in an emulsified medium from aliquots of the phthalates dissolved in a diethyl ether: ethyl acetate (1:9) mixture and Hyamine 1622 as emulsifying agent. The characteristics of the reduction processes in both media were established. The number of electrons involved was higher for the base form of the electroactive species. Using dpp at E=–50 mV, the detection limits obtained in the emulsified medium were 6.7×10^–8 and 7.4×10^–7 moll^–1 for diethyl phthalate and dibutyl phthalate, respectively. Interferences between the two phthalates were studied, and the possibility of carrying out the overall determination of both phthalates was demonstrated. Good results were obtained when applying the polarographic method developed in the emulsified medium to determine diethyl phthalate by dpp in spiked milk after extraction of the analyte with diethyl ether: ethyl acetate (1:9).     

Preparation of Complexes η<Superscript>4</Superscript>-4-(1,3-Diphenyl-2-propen-1-one)-η<Superscript>3</Superscript>-3-(1,3,5-triorganyl-1,3,5-triazacyclohexane)carbonyltungsten(0) and Their Reactions with Diethyl Phosphite

New tungsten complexes were prepared of a composition η³-[(1,3,5-triorganyl)-1,3,5-triazacyclohexane]-tricarbonyltungsten(0) where a tridentate coordination of the triazinane fragment to the metal center was found. The reaction of tricarbonyltriazinane tungsten complexes with 1,3-diphenyl-2-propen-1-one (chalcone) under thermochemical activation resulted in replacement of two carbon monoxide molecules in the coordination sphere of tungsten by a chalcone molecule linked to the transition metal atom through a system of π-bonds C=C and C=O. The phosphorylation of η⁴-(1,3-diphenyl-2-propen-1-one)-η³-[(1,3,5-triphenyl)-1,3,5-triazacyclohexane]-monocarbonyltungsten(0) with diethyl phosphite occurred at the carbonyl group of the coordinated heterodiene; the phosphonate thus formed underwent intracomplex phosphonate-phosphate rearrangement affording an organometallic phosphate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 793–797.Original Russian Text Copyright © 2005 by Kuramshin, Asafyeva, Cherkasov.     

31P NMR study of the hydrolytic activity of ethriol phosphite and triphenyl phosphite in a two-phase system

The hydrolytic activity of ethriol phosphite and triphenyl phosphite in the p-xylene/water two-phase system was studied by the³¹P NMR method. It was shown that the rate of hydrolysis can be controlled by varying the pH of the aqueous phase. Hydrolysis of triphenyl phosphite is much slower than that of ethriol phosphite in the tested pH range. Coordination of ethriol phosphite with a rhodium carbonyl complex completely suppresses its hydrolysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1026–1030, May, 1991.     

A STUDY ON THE TRANSESTERIFICATION REACTION OF DIMETHYL AND DIETHYL PHOSPHITE WITH 1,3-DICHLOROPROPANOL-2

Abstract

The transesterification process of dimethyl and diethyl phosphite with 1,3-dichloropropanol-2 is examined. It is found that the reaction proceeds in the absence of catalyst at a temperature of 155°, whereas in the presence of morpholine as a catalyst it takes place at 126°C. The transesterification of dimethyl phosphite and diethyl phosphite with 1,3-dichloropropanol-2 is accompanied by the evolution of dimethyl and diethyl ethers and alkyl halides (methyl chloride and ethyl chloride).