2325-27-1Relevant articles and documents
Reactivity of N phenyl iminophosphoranes towards ozone: Evidence of trioxo azaphospholane intermediates
El Khatib, Fayez,Bellan, Jacques,Koenig, Max
, p. 391 - 398 (1998)
The ozonation of N-phenyl-iminophosphoranes R3P=NPh 1a-b leads, after the P-N bond breakage, to the corresponding phosphorus oxides 2a-b with the formation of complex adducts 3a-b which precipitate at room temperature. The stoichiometry and the reaction mechanism depend on the nature of substituents R linked to the phosphorus atom. For R=Ph we detected the phosphonium intermediate 5a, whereas for R=OEt the trioxoazaphospholanes 7b-9b were characterized by 31P NMR.
A new synthetic utility of iminophosphoranes. Synthesis of trifluoromethylated enamino and imino esters
Shen, Yanchang,Gao, Shu
, p. 37 - 39 (1996)
A new synthetic utility of iminophosphoranes, including the reaction of iminophosphoranes with trifluoroacetic anhydride and organozinc compounds, to afford trifluoromethylated amino and imino esters is described.
Preparation of 1,2,5-Trisubstituted 1H-Imidazoles from Ketenimines and Propargylic Amines by Silver-Catalyzed or Iodine-Promoted Electrophilic Cyclization Reaction of Alkynes
Zhou, Xiaorong,Jiang, Zheng,Xue, Lexing,Lu, Ping,Wang, Yanguang
supporting information, p. 5789 - 5797 (2015/09/15)
From readily available propargylic amines, 1,2,5-trisubstituted imidazoles are efficiently obtained through a cascade reaction catalyzed by AgOTf or promoted by molecular iodine. The AgOTf-catalyzed reaction involves nucleophilic addition of propargylic amine to ketenimine, a silver-catalyzed electrophilic cyclization reaction of alkyne, and a tautomerism/isomerism/metal-H exchange cascade. The iodine-mediated counterpart yields 5-formyl-1,2-disubtituted imidazoles, which presumably includes a cascade hydrolysis/oxidation reaction. Furthermore, the presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazole can be converted into fused indeno[1,2-d]imidazole. 1,2,5-Trisubstituted imidazoles are efficiently prepared from readily available propargylic amines through a AgOTf-catalyzed or molecular iodine-promoted cascade reaction. The presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazoles can be converted into fused indeno[1,2-d]imidazoles.
Kinetics and mechanism of the nitrosobenzene deoxygenation by trivalent phosphorous compounds
Khursan,Shamukaev,Chainikova,Khursan,Safiullin
, p. 2477 - 2486 (2014/11/08)
The reaction of aryl nitroso compounds with organic phosphines and phosphites in aerated media is a convenient non-photolytic procedure to generate aromatic nitroso oxides. The reaction rate constants and activation parameters of the key (for the proposed method of nitroso oxide generation) reaction of nitrosobenzene with tripenyl phosphite or para-substituted phosphines (4-RC 6H4)3P (R = MeO, Me, H, F), as well as that of para-methoxynitrosobenzene with triphenylphosphine in acetonitrile were determined by kinetic spectrophotometry and chemiluminescence. A significant transfer of the electron density to the nitroso compound occurs in the transition state of the reaction as was revealed using the Hammett correlation analysis and DFT calculations in the M06L/6-311+G(d,p) approximation. The introduction of the electron-donor substituent MeO into the para-position of PhNO decreases the reactivity of the nitroso compound by two orders of magnitude. The reactivity of triphenyl phosphite in the oxygen atom transfer reaction is lower by two orders of magnitude compared to that of triphenylphosphine. In the case of the reactions of PhNO with phosphines, the apparent rate constant depends on the oxygen content in the reaction medium.