1983-26-2Relevant articles and documents
A “masked” source for the phosphaalkene MesP=CH2: Trapping, rearrangement, and oligomerization
Chen, Leixing,Wang, Shuai,Werz, Patrick,Han, Zeyu,Gates, Derek P.
, (2018)
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].
A study of the reaction of phosphorus trichloride with paraformaldehyde in the presence of carboxylic acids
Troev,Todorov,Naydenova,Mitova,Vassilev
, p. 1147 - 1155 (2013)
We investigated the mechanism of the reaction of paraformaldehyde with phosphorus trichloride in the presence of carboxylic acids (acetic, propanoic, and formic). Our results revealed that bisphosphonic acids were obtained without the use of water. The structures of the reaction products were studied by 1D and 2D homonuclear and heteronuclear 1H-, 13C-, 31P- NMR spectroscopy. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional tables.]
Mild synthesis of organophosphorus compounds: Reaction of phosphorus-containing carbenoids with organoboranes
Antczak, Monika I.,Montchamp, Jean-Luc
supporting information; experimental part, p. 977 - 980 (2009/04/10)
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.
[(Diphenoxyphosphinyl)methylidene]triphenylphosphorane - The double P +-stabilised carbanion: A crystallographic, computational and solution NMR comparative study on the ylidic bonding
Ch?cińska, Lilianna,Kudzin, Zbigniew H.,Ma?ecka, Magdalena,Nazarski, Ryszard B.,Okruszek, Andrzej
, p. 7681 - 7693 (2007/10/03)
The crystal and molecular structure of the title compound (1) was established by an X-ray diffraction analysis. Some geometrical parameters including a slightly pyramidal shape around its ylidic Cβ-atom were determined (trans-bent type conformation), providing evidence for a strong electron delocalisation in the PαCβP γOδ backbone. The charge density redistribution within this molecular unit and its other fully optimised geometries was evaluated in ab initio MO calculations using both the HF and DFT (B3LYP) formalism, which supported such a concept. As a result, the double zwitterionic form (structure C) was suggested as the best description of 1. The absence of an experimentally NMR observable 2JPα-Cβ -Hβ coupling was tentatively rationalised in terms of fast pyramidalisation of the Cβ-anionic site. Crystallographic and solution NMR data for ylide 1 were compared with those reported for the other mesomerically stabilised Wittig-type reagents and structurally related anionic species. It was concluded that all aforementioned systems have almost identical P-ylidic bonding most likely governed mainly by very strong electrostatic interactions, with a small contribution of negative hyperconjugation.
Optimal conditions for preparing chloromethylphosphonic dichloride
Nazarov,Muslinkin
, p. 1043 - 1047 (2007/10/03)
A procedure was developed for preparing chloromethylphosphonic dichloride, involving available raw materials and common process equipment. The optimal operation conditions were determined. This procedure can be used for production of chloromethylphosphonic dichloride both in laboratory and under industrial conditions.
Free radical reaction of α-haloalkylphosphonates with alkenes and alkynes: A new approach to modified phosphonates
Balczewski,Mikolajczyk
, p. 392 - 396 (2007/10/02)
A new approach to the synthesis of phosphonates 3 functionalized in the α- and γ-phosphonate positions by alkyl, ethoxy, butoxy, acetoxy, acetyl and cyanide groups and allylphosphonate 6 is described. It is based on the radical reaction of α-halosubstituted phosphonates 1 (X = Cl, Br, I) with the terminally unsubstituted alkenes 2 (1-heptene, ethoxyethene, butoxyethene, acetoxyethene, acrylonitrile, methyl vinyl ketone) and alkyne 5 (hept-1-yne). The reaction involving the tin hydride method (Bu3SnH/AIBN) was more effective with alkenes than with alkynes (40-72% versus 20-30%). With electron-rich alkenes, chloro- and bromomethylphosphonates 1 (X = Cl, Br) gave higher yields than iodomethylphosphonate 1 (X = I). Diethyl methylphosphonate 4, as a reduction product of 1, accompanied 3 and 6 in the above reactions. The yield of 4 could be reduced by optimizing the reaction conditions.
Optimization of Synthesis of Bis(chloromethyl)phosphinic Chloride
Nazarov, Yu. V.,Muslinkin, A. A.,Kutuev, A. A.
, p. 141 - 143 (2007/10/03)
Synthesis of bis(chloromethyl)phosphinic chloride on a pilot plant equipped with industrial reaction vessels has been optimized.
Process for preparing halogenomethane-phosphonic acid dihalides
-
, (2008/06/13)
Process for preparing halogenomethane-phosphonic acid dihalides of the formula EQU1 wherein X is halogen, preferably chlorine or bromine, by reacting hydroxymethane-phosphonic acids of the formula Their salts or functional derivatives or thio-analogs, with acid halides of the formula EQU2 where n is 1 or 2, in the presence of certain tri- or pentavalent nitrogen or phosphorus-containing compounds. The products are valuable intermediates for the preparation of pesticides and flame retardants.
