Polyhalogenalkoxy(aryloxy)chloro‐ and bromophosphoranes

Abstract

The data on the synthesis, stereochemistry, and molecular dynamics of alkoxy(ary1oxy)halogenphosphoranes of acyclic structure, as well as of halogenphosphoranes containing the pentacoordinate phosphorus atom in the 1,4,2-dioxophospholane cycle and the node of bicyclo[2.2.2]octane system, are systematized. The influence of spatial properties of polyhalogenalkyl substituents on thermal stability and structure of adducts from tris(po1yhalogenalkyI) phosphites with chlorine and bromine is ascertained. The eflect of the phosphorus atom inclusion into the cycle and node of the bicyclooctane system on its pentacoordinate state stability is investigated.

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

“…Thus the alcohol CF3OH decomposes at 20 °C. 49 The contribution of the mesomeric form 49 to the CF3OH structure is very large owing to the extremely effective no-Oco conjugation. 211 The introduction of a P(III) atom would have led to an even greater destabilisation of the CF3-O-P system owing to the additional shift of electron density from the phosphorus atom via the np-a* co conjugation mechanism; on the other hand, under these conditions the formation of products with a P-F bond is thermodynamically favourable because this bond is one of the strongest.…”

“…The phosphonate obtained from ethyl pyruvate (R = Me) partly undergoes the phosphonate-phosphate rearrangement during distillation, while the analogous phosphonate synthesised from the phenylglyoxylic acid ester (R = Ph) is fully converted into the rearrangement product 170. 99 acetoacetic 356> 359 and pyruvic 360 acids, 1,1-dichloroacetophenone, 266 pentafluorophenylbromoacetophenone, 361 dimethyl trichloroacetylphosphonate, 90 fluorinated aldehydes, 49 ' 208 and chloral and bromal. 362 -363 Hexafluoroacetone reacts with fluorinated P(III) derivatives to form phospholanes of three types: a 5 -l,3,2-and a-1,4,2dioxaphospholanes 174 85 The fluoroalkyl groups at the phosphorus atom in the 1-hydroxyalkyl phosphonate obtained from bis(tetrafluoropropyl) phosphite and 2-acetoxyethyl methyl ketone promote a more ready occurrence of the phosphonate-phosphate rearrangement compared with the fluoroalkyl groups in the 1-hydroxyalkylphosphonate obtained from diethyl phosphite.…”

Recent Reviews

“…Dynamics, intramolecular, 4 Eburnamine-vincamine alkaloids, 126 «•-Electron energy, of benzenoid hydrocarbons, 103 Electron transfer, 70, 110, [112][113][114]116 distance and angle effects, 111 photoinduced, 109,116 Electron-exchange luminescence, 112 Electronic behavior, of TCNQ salts, 56 Enantioselective rhodium catalysts, 24 Enediynes, 2 Energy transfer, 74 Enones, 72 Enumeration, of benzenoid systems, 104, 105 Enzyme processes, 67,68 Enzyme reactions, 50 electron transfer in, 115 Enzyme-catalyzed acyl transfer, 94 Enzymes, in synthesis, 65 Esters, cyclic vinylogous, ozonolysis, 107 Excited states, 70 Expansion, supersonic jet, 74 -Facial diastereoselection, 106 Flexible molecules, 22 Fluorine-containing compounds, 79,136 Four-membered heterocycles, 90 Four-membered ring compounds, 38 Free radical reactions, 73 Fullerene ions, 33 Functionalization, selective, 3 Fungicide intermediates, synthesis, 65 Furan, Dewar, 124 2,3,4-Furantriones, 12 Germanium compounds, 53 Glutatarates, ^-substituted, 67 C-Glycosides, synthesis, 100 Halophosphoranes, 49 Helicating ligands, 101 Heterocycles, 83,84 four-membered, synthesis, 90 fused, book, 142 literature of, 15 synthesis, 13,14,16 Heterocyclic systems, germanium in, 53 Heterodienophiles, 14 Hole transfer, 113 Homogeneous catalysis, book, 148 Hydrocarbons, pyrolysis of, 75 saturated,3 strained, 118 Hydrolysis of amides, 1 Hypochlorites, oxidation with, 63 Intermediates, reactive, book, 147 synthesis, 36 Interstellar chemistry, 33 Intramolecular addition reactions, 71 In...…”