121-45-9Relevant articles and documents
Phosphorus halides complexes with 4-dimethylaminopyridine and N-methylimidazole
Bezgubenko,Pipko,Sinitsa
, p. 911 - 918 (2009)
Formation of complexes between phosphorus halides and 4- dimethylaminopyridine or N-methylimidazole was studied. The following phosphorus halides: trichloride, oxychloride, and sulfochloride, were found to form equilibrium mixtures of the complexes containing different numbers of the ligand molecules. Among the studied phosphorus halides only pentachloride and tribromide form stable complexes with a constant composition.
Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
, p. 14983 - 15003 (2021/11/12)
A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
Synthesis of tervalent phosphorus esters in biphasic system using potassium phosphate as unique solid base
Ilia, Gheorghe,Iliescu, Smaranda,Macarie, Lavinia,Popa, Adriana
, p. 360 - 364 (2008/09/20)
The synthesis of tervalent phosphorus esters continues to be a significant area of interest, much of it again directed toward the synthesis of phosphite ligands for metal-catalyzed reactions. Typically, they were obtained through esterification of the corresponding phosphorus chlorides with the appropriate alcohols in the presence of an amine. In this paper, we present a new method for the synthesis of tervalent phosphorus esters, not yet mentioned in the literature, when potassium phosphate, as a unique base, is used in liquid-solid system. Symmetrical and unsymmetrical phosphites were obtained with good yields (65%-80%) using this method. The compounds were characterized by 31P NMR spectroscopy.
11,12-cyclic phosphite or phosphate derivatives of erythromycin and related macrolides
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, (2008/06/13)
Disclosed are the antibacterial compounds having the formulas: STR1 or pharmaceutically acceptable salts and esters thereof. Also disclosed are the processes for preparing compounds of formulas (I), and II) of the invention, pharmaceutical compositions comprising a therapeutically effective amount of a compound of the invention in combination with a pharmaceutically acceptable carrier, as well as a method for treating bacterial infections by administering to a mammal a pharmaceutical composition containing a therapeutically-effective amount of a compound of the invention.
2,4-diphosphoranediyl-l,3-diphosphetanes
Schroedel, Hans-Peter,Schmidpeter, Alfred
, p. 1519 - 1527 (2007/10/03)
The 1,3-dichloro- and 1,3-dibromo-substituted title compounds 5b, c result from the condensation of triphenylphosphonium-bis(trimethylsilyl)methylide 1 with PC13 and PBr3. The chloro derivative 5b undergoes a variety of single and double substitution reactions, of which some have merely been tested and others have been made preparative use of. The substitution of one chloride by an ylidyl, amino, phosphino, or metal carbonyl group is accompanied by the spontaneous dissociation of the other P-C1 bond to yield the 1,3-diphosphetenium chlorides 14/15, 19, 31 and 36, respectively. In other cases (9, 27, 32) dissociation can be achieved by means of a Lewis acid. Protonation of 5b occurs at the carbon ring members; methylation and formation of transition metal complexes occurs at a phosphorus ring member. PC13 degrades the four-membered ring of 5b or enlarges the ring to yield 3,5-diphosphoranediyl-l,2,4-triphospholane derivatives 39, 40, 42. Keywords: Phosphorus / Heterocycles / Phosphorus ylides / Phosphoranediyl and phosphonio substituants / P-C1 bond dissociation WILEY-VCH Verlag GmbH.
The kinetics and mechanism of the reaction of trimethyl phosphite with benzylideneacetophenones
Petnehazy, Imre,Clementis, Gyoergy,Jaszay, Zsuzsa M.,Toeke, Laszlo,Hall, C. Dennis
, p. 2279 - 2284 (2007/10/03)
The kinetics and mechanism of the equilibrium reaction of benzylideneacetophenones 4 with trimethyl phosphite (TMP) to yield, 2,2,2-trimethoxy-2,3-dihydro-1,2λ5-oxaphospholes 5 are reported. The second-order rate constants for the formation of 5 were determined using a polarographic method and the rate constants for the decomposition reaction were calculated from the equilibrium constants. The linear Hammett plots in some cases and the curved ones in others indicate that the rate-determining step depends on the character of the ring substituants in 4 and 5. A thermodynamic study of the forward reaction showed a relatively small enthalpy and a large negative entropy of activation in agreement with the existence of a strongly polarised and/or crowded structure in the transition state. The proposed mechanism, in cases where electron-donating substituents (Y) or hydrogen are on the aromatic ring next to the carbonyl carbon or where electron-donating substituents (X) are on the aromatic ring next to the double bond, involves nucleophilic attack of phosphite on the carbonyl carbon atom in the rate-limiting step to form intermediate I2 followed by a ring closure to an oxaphosphirane I2 and ring enlargement to the oxaphospholene 5. The use of electron-withdrawing substituents (both for X and Y) results in a change in the reaction pathway in which phosphite attacks the carbon atom β to the carbonyl group in the rate-limiting step followed by a fast ring closure of I3 to oxaphospholene 5.
Phosphitylation via the Mitsunobu reaction
Grice, I. Darren,Harvey, Peta J.,Jenkins, Ian D.,Gallagher, Michael J.,Ranasinghe, Millagahamada G.
, p. 1087 - 1090 (2007/10/03)
Treatment of a dialkyl phosphite with triphenylphosphine and diisopropyl azodicarboxylate in toluene, followed by addition of an alcohol, results in the formation of the corresponding trialkyl phosphite. Similarly, dialkyl phosphonites can be synthesised from monoalkyl phosphites (alkyl phosphinates).
Route to glycals in the allal and gulal series
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, (2008/06/13)
Axial anomeric sulfoxides generated via thiophenol Ferrier rearrangement of glucal and galactal derivatives are used to synthesize glycals of the gulal and allal series. An application of the method led to the synthesis of the esperamicin thiosugar.
