- A “masked” source for the phosphaalkene MesP=CH2: Trapping, rearrangement, and oligomerization
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We report the attempted synthesis of a “masked” phosphaalkene by treating MgA·3THF (A?=?anthracenide) with MesPCl(CH2Cl). Although the desired “masked” phosphaalkene could not be isolated, indirect evidence for its formation was obtained. The product of trapping MesP=CH2 with 1,3-cyclohexadiene was detected. In addition, the oxide MesPO(Me)A was isolated and crystallographically characterized from the MgA·3THF and MesPCl(CH2Cl) experiment described above. Finally, the attempted isolation of “masked” phoshaalkene afforded P-containing oligomers with a trimodal molecular weight distribution [Mn?=?640, 1.7?×?103 and 7.4?×?103?Da].
- Chen, Leixing,Wang, Shuai,Werz, Patrick,Han, Zeyu,Gates, Derek P.
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- Mild synthesis of organophosphorus compounds: Reaction of phosphorus-containing carbenoids with organoboranes
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Organoboranes react with phosphorus-containing carbenoids to produce a variety of functionalized organophosphorus compounds under mild conditions. In some cases, selective migration of one group atached to boron can be observed. Phosphonite-borane complexes are introduced as novel synthons for the synthesis of phosphinic esters.
- Antczak, Monika I.,Montchamp, Jean-Luc
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supporting information; experimental part
p. 977 - 980
(2009/04/10)
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- 1,4,2-Diazaphospholothiazoles and -pyridines by a Hantzsch-Type Condensation Using Chloromethyldichlorophosphane
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The cyclocondensation of 2-amino-1,3-thiazoline, 2-aminopyridines, 2- and 4-aminopyrimidines, 2-aminopyrazine, and 2-aminoquinoline with chloromethyldichlorophosphane in the presence of triethylamine yields regiospecifically 5,6-dihydrothiazolodiazaphosphole (3), 1,4,2-diazaphospholopyridines (12), 1,4,2-diazaphospholopyrimidines (15), 1,4,2-diazaphospholopyrimidine (17), 1,4,2-diazaphospholopyrazine (19), and diazaphospholoquinoline (22), respectively.Using 2-amino-1,3-thiazole (4) and 2-aminobenzothiazoles 8, we obtained mixtures of the 1,5- and 4,5-anellated 1,4,2-diazaphospholes 5/6, 9a/10a and 9b/10b, while in the case of the methyl derivative 8c only the diazaphospholobenzothiazole 10c was formed.In the reaction of 2-aminothiazole and 2-aminopyrazine with chloromethyldichlorophosphane the bis(diazaphospholo)-substituted chloromethylphosphanes 7 and 20 could be detected.The new anellated 1,4,2-diazaphospholes are colorless to pale yellow crystalline moisture-sensitive solids. - Key Words: Anellated azaphospholes/ Hantzsch-type cyclocondensation/ Chloromethyldichlorophosphane/ Regioselectivity/ 31P-, 1H-, 13-C-NMR spectra
- Karaghiosoff, Konstantin,Mahnot, Ruchi,Cleve, Cornelia,Gandhi, Neelam,Bansal, Raj K.,Schmidpeter, Alfred
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p. 581 - 588
(2007/10/02)
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- Spectra and structure of phosphorus-boron compounds - XXVII. Low-resolution microwave, IR and Raman spectra, conformational stability, ab initio calculations, vibrational assignment and normal coordinate calculations for (chloromethyl)difluorophosphine borane.
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The low resolution microwave spectrum of (chloromethyl)difluorophosphine borane, ClCH2PF2*BH3, has been investigated from 26.5 to 39 GHz.Based on the calculated dipole moments and the fact that the microwave spectrum is an α-type spectrum along with the spacing of the central transitions for the near-prolate top, it is concluded that the predominant spectrum is that for the conformer with the CCl bond trans to the PB bonds.The IR (4000-40/cm) and Raman (3500-20/cm) spectra of the gas and solid of five isotopic species has been recorded.Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization value have been obtained.Both the trans and gauche conformers have been identified in the vibrational spectra of the fluid phases.From a temperature study of the Raman spectrum of the liquid, the enthalpy difference between the trans and gauche conformers was determined to be 162 +/- 9 cm-1 (463 +/- 26 cal/mol) with the gauche conformer being the more stable rotamer.Depending on experimental circumstances upon crystallization, either a solid containing only the gauche conformer or a solid containing both the gauche and trans conformers can be obtained.All of the normal modes have been assigned based on IR band contours, depolarization values an group frequencies.Additionally, ab initio calculations have been carried out utilizing both 3-21G* and 6-31G* basis sets to obtain the stabilities, barriers to internal rotation, and optimized structural parameters.A normal coordinate analysis has also been performed with a force field determined from the 3-21G* basis set for both conformers.These results are compared with the corresponding quantities of some similar compounds.
- Veken, B. J. van der,Sanders, R. S.,Harlan, R. J.,Durig, J. R.
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p. 1833 - 1872
(2007/10/02)
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- HALOGENOTROPY IN PHOSPHORUS-CARBON DIAD
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Phosphorus-carbon diad halogenotropic transformations of P-halogenoylids 1,2 and α-halogenoalkylphosphines 3,4 are described.Kinetic studies reveal the monomolecular mechanism of 1a - 3a chlorotopic rearrangement.
- Kolodiazhnyi, Oleg I.,Golokhov, Dmitryi B.,Boldeskul, Igor E.
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p. 2445 - 2448
(2007/10/02)
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