21713-56-4Relevant academic research and scientific papers
Electrochemical Enabled Cascade Phosphorylation of N?H/O?H/S?H Bonds with P?H Compounds: An Efficient Access to P(O)-X Bonds
Abdukader, Ablimit,Dong, Xiaojuan,Jin, Weiwei,Liu, Chenjiang,Wang, Bin,Wang, Ruige,Xia, Yu,Xue, Fei,Zhang, Yonghong
supporting information, p. 14931 - 14935 (2021/10/06)
An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2PH has been established. Electricity is used as the “traceless” oxidant and water and air are utilized as the “green” oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)-N/P(O)-O/P(O)-S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.
A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH
Li, Yujun,Yang, Qi,Yang, Liquan,Lei, Ning,Zheng, Ke
supporting information, p. 4981 - 4984 (2019/05/21)
A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.
The α-effect in nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates with HOO- and OH -
Hong, Hyo-Jeong,Bae, Ae Ri,Um, Ik-Hwan
, p. 2251 - 2255 (2013/09/24)
Second-order rate constants (kHOO-) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with HOO- in H2O have been measured spectrophotometrically. The a-nucleophile
Kinetics and reaction mechanism for alkaline hydrolysis of Y-substituted-phenyl diphenylphosphinates
Hong, Hyo-Jeong,Lee, Jieun,Bae, Ae Ri,Um, Ik-Hwan
, p. 2001 - 2005 (2013/09/02)
The second-order rate constants (kOH-) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with OH- in H 2O at 25.0 ± 0.1 °C have been measured spectrophotometrically. Comparison of kOH- with kEtO- (the second-order rate constants for the corresponding reactions with E tO- in ethanol) has revealed that EtO- is less reactive than OH- although the former is ca. 3.4 pKa units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Bronsted-type plot for the reactions of 4a-4i with OH- is linear with βlg = -0.36. The Hammett plot correlated with σ- constants results in a slightly better correlation than that correlated with σo constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with OH- have been concluded to proceed through a concerted mechanism. Copyright
Aminolysis of Y-substituted phenyl diphenylphosphinates and benzoates: Effect of modification of electrophilic center from C=O to P=O
Um, Ik-Hwan,Shin, Young-Hee,Han, Jeong-Yoon,Mishima, Masaaki
, p. 7715 - 7720 (2007/10/03)
(Chemical Equation Presented) The effect of modification of the electrophilic center from C=O to P=O on reactivity and reaction mechanism has been investigated for aminolysis of Y-substituted phenyl diphenylphosphinates (1a-j) and benzoates (2a-i). The phosphinates 1a-j are less reactive than the benzoates 2a-i. The reactions of 2,4-dinitrophenyl diphenylphosphinate (1a) with alicyclic secondary amines resulted in a linear Bronsted-type plot with a βnuc value of 0.38, while the corresponding reactions of 2,4-dinitrophenyl benzoate (2a) yielded a curved Bronsted-type plot. Similarly, a linear Bronsted-type plot with a β1g value of -0.66 was obtained for the reactions of 1a-j with piperidine, while the corresponding reactions of 2a-i gave a curved Bronsted-type plot. The linear Bronsted-type plots for the reactions of 1a-j have been taken as evidence for a concerted mechanism, while the curved Bronsted-type plots for the reactions of 2a-i have been suggested to indicate a change in the rate-determining step of a stepwise mechanism. The Hammett plot for the reactions of 1b-j exhibited a poor correlation with σ- constants (R2 = 0.962) but slightly better correlation with σo (R2 = 0.986). However, the Yukawa-Tsuno plot for the same reactions resulted in an excellent correlation (R2 = 0.9993) with an r value of 0.30. The aminolysis of 1a-j has been suggested to proceed through a concerted mechanism with an early transition state on the basis of the small βnuc and small r values.
The Phenomenology of Differently Constructed Broensted-type Plots
Buncel, E.,Tarkka, R.,Hoz, S.
, p. 109 - 110 (2007/10/02)
Two different methodologies for the construction of Broensted-type plots are compared; curved plots using the traditional approach and linear plots by a novel approach are obtained for the reaction of phenoxides with p-nitrophenyl diphenylphosphinate in dimethyl sulfoxide-water media at 25 deg C.
A NOVEL SUBSTITUENT EFFECT ON 31P NMR CHEMICAL SHIFTS IN THE ARYL DIPHENYLPHOSPHINATE SERIES
Hoz, S.,Dunn, E. J.,Buncel, E.,Bannard, R. A. B.,Purdon, J. G.
, p. 321 - 326 (2007/10/02)
The 31P NMR chemical shifts of a series of meta- and para-substituted phenyl diphenylphosphinates, Ph2P(O)OC6H4-X, have been determined.The δ 31P values exhibit an increasing downfield trend as the electron-withdrawing properties of the substituent X become greater and a reasonable correlation between δ 31P and Hammett-Taft substituent constants is obtained.This trend is opposite to that exhibited in several families of compounds of the type ArP(O)Y2, where δ 31P values show an increasing upfield trend as the electron-withdrawing ability of the substituent in Ar is increased.The results are explained by proposing varying degrees of d-orbital occupancy in the phosphorous-oxygen bonds (P-OAr and P=O) in the series of compounds as a factor influencing 31P chemical shifts.
