- Reactivity of Ph3PNLi towards PIII and PV electrophiles
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A study of the reactivity of Ph3P{double bond, long}NLi towards phosphorus electrophiles allowed us to develop a general method to isolate, or cleanly generate in situ, a broad family of polyphosphinimines displaying P{double bond, long}N-P bon
- Rahier, Nicolas J.,Volle, Jean-No?l,Lacour, Marie Agnès,Taillefer, Marc
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p. 6645 - 6650
(2008/12/20)
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- Fluorescent compounds
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Novel compounds obtainable by reacting together an imido-reagent such as diphenylphosphonimido-triphenylphosphorane), or a phosphine oxide such as p-tolyldiphenylphosphine oxide, with a chelate of a transition or lanthanide or actinide metal, such as tris(dibenzoylmethide)europium III, have the property of fluorescing in UV radiation. The invention includes solid polymer bodies containing such compounds, or chelates of transition or lanthanide or actinide metals generally, the bodies having the property of emitting light or infra-red radiation when subjected to a flux of ultra-violet or ionising radiation by virtue of internally generated, e.g. by tritium ionising radiation. The body is preferably of polystyrene formed by polymerising the monomer in the presence of the compound or metal chelate.
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- NEW SYNTHETIC APPLICATIONS OF METALLATED YLIDS
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The reaction of diylids 1 toward carbonates, carbamates, thiocarbamates, isocyanates, carbodiimides and sulfinates allow the quantitative preparation of functional Wittig reagents, which can be used in situ in the E-stereoselective synthesis of the corresponding α,β-unsaturated derivatives of carboxylic (or sulfinic) acids. The diylids 2 or yldiid 3 can be used as synthetic equivalents of RNH2- or NH2- anions and allow normal or functional alkylation of the nitrogen atom.
- Cristau, Henri-Jean,Perraud, Anne,Manginot, Eric,Torreilles, Eliane
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- PHOSPHONIUM AZA-YLDIID AS REAGENT FOR ONE-POT SYNTHESIS OF PHOSPHINIMINES WITH FUNCTIONAL N-SUBSTITUENTS.
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A new procedure for the one-pot synthesis of phosphinimines with functional N-substituents using the alkylation of phosphonium aza-yldiid 1 with α-bromo esters or the direct introduction of phosphorus and sulfur groups.
- Cristeau, Henri-Jean,Manginot, Eric,Torreilles, Eliane
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p. 347 - 350
(2007/10/02)
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- Synthesis of N-Acyl-, N-Sulfonyl-, and N-Phosphinylphospha-λ5-azenes by a Redox-Condensation Reaction Using Amides, Triphenylphosphine, and Diethyl Azodicarboxylate
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The reaction of phosphines and amides with diethyl azodicarboxylate (DAD) produced phospha-λ5-azenes.Thus aromatic amides and those aliphathic amides with electron-withdrawing substituents gave N-acyl-P,P,P-triphenylphospha-λ5-azenes (5) when triphenylphosphine (TPP) was employed.Both aryl- and alkylsulfonamides reacted with TPP and DAD to produce the N-sulfonylphospha-λ5-azenes (9).Diphenylphosphinamide (10) and ethyl carbamate (12) also produced the respective phosphazenes (11 and 13) with TPP and DAD.Secondary carboxamides and sulfonamides did not react with TPP and DAD.The reaction of triethyl phosphite with sulfonamides in the presence of DAD produced the phosphorimidates (20) in an analogous reaction, along with the corresponding N,N-diethylsulfonamides and the deethylated adduct of triethyl phosphite and DAD (23).Triethyl phosphite-DAD failed, however, to give a phosphorimidate with carboxamides but gave, instead, the rearranged adduct of DAD and triethyl phosphite (19).Tris(dimethylamino)phosphine reacted with sulfonamides and DAD but the products were the corresponding ethyl N-sulfonylcarbamates (26) rather than the phosphazenes.Tris(dimethylamino)phosphine reacted with azodicarbonamide (a molecule which contains both the azo and carboxamide groups) with the production of N,N-dimethylurea, again without formation of the phosphazene.Finally, the reaction of triphenylarsine with benzenesulfonamide and DAD produced N-(phenylsulfonyl)triphenylarsa-λ5-azene (30) but triphenylstibene with DAD and benzenesulfonamide only gave triphenylstibene oxide.Mechanistic possibilities for these reactions are also discussed.
- Bittner, Shmuel,Assaf, Yonit,Krief, Penina,Pomerantz, Martin,Ziemnicka, Barbara T.,Smith, Christina G.
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p. 1712 - 1718
(2007/10/02)
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