Acylphosphonates. 6. Reaction mechanism of Zn/Me3SiCl mediated conversion of 2,2,2-trichloroethoxycarbonylphosphonates to silyl phosphites

It was elucidated by ³¹P nmr spectroscopy that the conversion of 2,2,2-trichloroethoxycarbonylphosphonates to dialkyl trimethylsilyl phosphites by treatment with Me₃SiCl-Zn-acetylacetone proceed with retention configuration at phosphorus. In this study, optical active dinucleoside 2,2,2-trichloroethoxycarbonylphosphonates were synthesized and employed as the reaction substrates.     

Reaction of salicyl phosphites with hexafluoroacetone imine

Benzo-1,3,2,dioxaphosphorin-4-ones react with hexafluoroacetone imine to form 2-R-2,5-dioxo-3,3-bis(trifluoromethyl)-6,7-benzo,1,4,2-oxozaphosphepanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No, 12, pp. 3008–3010, December, 1996.     

Reaction of trialkyl phosphites with 1,1,1-trifluoroacetone

Conclusions Trialkyl phosphites react with 1,1,1-trifluoroacetone to give 2,2,2-trialkoxy-3,5-dimethyl-3,5-bis(trifluoromethyl)-1,4,2-dioxaphospholanes, which slowly isomerize to trialkoxy--trifluoromethyl--(1-methyl-2,2-difluorovinyloxy)ethoxyfluorophosphoranes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 910–914, April, 1980.     

Reaction of thiobenzophenone with trialkyl and triaryl phosphites

Thiobenzophenone reacts with trimethyl and triethyl phosphites at 100° to give trialkyl thiophosphate, tetraphenylethylene, O,O-dialkyl S-benzhydryl thiophosphate, and dialkyl benzhydrylphosphonate, while triaryl phosphites do not react with thiobenzophenone even at elevated temperature. Probable courses of these reactions are discussed on the basis of the products and effect of additives.     

Reaction of dialkyl phosphites with 1,1-dichloronitrosoalkanes

Conclusions Dialkyl phosphites react with 1,1-dichloronitrosoalkanes at 20C over 5–6 days to give the corresponding alkylchloroformimlnodialkyl phosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 226–228, January, 1987.     

Organophosphorus chemistry,XII. Reaction of furil with alkyl phosphites and ylide-phosphoranes

Summary The reaction of furil (1) with trialkyl phosphites2 yielded caged phosphorane derivatives of types3a-c. Dry hydrogen chloride gas converted3a-c into the respectivea-hydroxyvinyl-phosphates8a-c which are equally produced by reacting furil with the appropriate dialkyl phosphite7. The reaction of furil with ylide-phosphoranes10 proceeded according to the Wittig reaction mechanism to give the respective ethylenes11a-c. The new compounds have been characterized by their spectroscopic data (IR, PMR,³¹P-NMR, MS) and elementary analyses.Dedicated to Prof. M. Sidky on the occasion of his 60th birthday     

Reaction of neutral phosphites with N-phenylamides of acrylic acid

Conclusions The reaction of neutral phosphites with acrylic acid N-arylamides took place with participation of the carbamide group and led to the formation of dialkyl esters of N,N-alkylarylcarbamoylethyl phosphonic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2584–2586, November, 1969.     

Spectral properties of mono-and dihydroxychromones

The uv, ir, and nmr spectra of a number of hydroxy-and methoxychromones, substituted only in the benzene ring, were studied. The results are particularly useful in determining the position of the hydroxyl groups. Chromatographic data on paper are also given.     

Reaction of silyl enol ethers with cyanogen chloride

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1447–1448, June, 1988.     

Synthesis and properties of polyfluoro(silyl)acetylene nanoparticles by reaction of fluoro(silyl)acetylenes with triethylamine

Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side.

Synthesis of novel mono-and bisaminophosphoryl compounds and their membrane transport properties for acidic substrates

Some novel aminophosphoryl compounds were synthesized by the Kabachnik-Fields reaction. Their membrane transport properties for mono-and polyfunctional carboxylic acids with different number of functional groups were studied to establish that the transport rate of acidic substrates through liquid impregnated membranes increases in going from mono-to diphosphoryl carriers. Additional hydrophilic groups in the substrate molecule, too, affect transport efficiency.     

Synthesis and some physicochemical properties of the carbazine acid silyl esters

Structure of the dimethylcarbazine acid trimethylsilyl ether and pyrolysis of its derivative, the trimethylsilyl ester of N,N-dimethyl-N′-trimethylsilylcarbazine acid, were studied by the metods of X-ray diffraction and gas chromatography/mass spectrometry. The presence of the bifurcated hydrogen bonds between the trimethylsilyl dimethylcarbazinate molecules was detected. It was revealed why impossible to obtain dimethylaminoisocyanate even by the low-temperature pyrolysis.