102817-54-9

Upstream product

• 10259-20-8 4-nitrophenyl diphenylphosphinate 
• 135339-83-2 Lithium; 4-cyano-phenolate 
• 767-00-0 4-cyanophenol 
• 4559-70-0 Diphenylphosphine oxide 
• 14609-76-8 4-cyanophenolate 
• 21713-56-4 4-acetylphenyl diphenylphosphinate 
• 1079-66-9 chloro-diphenylphosphine 
• 1707-03-5 diphenyl-phosphinic acid 
• 1499-21-4 Diphenylphosphinic chloride 
• 3328-57-2 sodium 4-cyanophenolate 
• 5633-96-5 potassium p-cyanophenoxide 

Downstream Products

• 24625-67-0 N-n-butyl diphenylphosphinic acid amide 
• 767-00-0 4-cyanophenol 
• 6230-68-8 diphenyl(piperidin-1-yl)phosphine oxide 
• 1733-55-7 ethyl diphenylphosphinate 
• 5633-96-5 potassium p-cyanophenoxide 
• 14609-76-8 4-cyanophenolate 
• 1707-03-5 diphenyl-phosphinic acid 

Relevant academic research and scientific papers

Kinetic study on nucleophilic substitution reactions of aryl diphenylphosphinates with butane-2,3-dione monoximate and aryloxide anions: Reaction mechanism and origin of the α-effect

A kinetic study is reported for nucleophilic substitution reactions of X-substituted-phenyl diphenylphosphinates (3a-3f) with butane-2,3-dione monoximate (Ox-) and a series of Y-substituted-phenoxide (Y-PhO-) ions in 50 mol % H2O/50 mol % DMSO at 25.0 ± 0.1°C. The reactions of 3a-3f with Ox- and 4-chlorophenoxide (4-ClPhO-) result in linear Br?nsted-type plots with βlg = -0.70 and -0.64, respectively, a typical βlg value for reactions reported previously to proceed through a concerted mechanism. The Br?nsted-type plots for the reactions of 4-chloro-2-nitrophenyl diphenylphosphinate (3a), 4-nitrophenyl diphenylphosphinate (3b), and 4-acetylphenyl diphenylphosphinate (3d) with Y-PhO- are also linear with βnuc = 0.15-0.35. The current reactions have been concluded to proceed through a concerted mechanism in which the bond formation is much less advanced than the bond rupture in the TS on the basis of the βlg and βnuc values. The α-effect observed in this study is very small (i.e., the kOx-/kp-ClPhO- ratio=4.61-43.5) and is independent of the leaving-group basicity. It has been concluded that the α-effect shown by Ox- in the current reactions is mainly due to desolvation of Ox- in the reaction medium (ground-state contribution) rather than stabilization of the transition-state (TS contribution) on the basis of the kinetic results.

The Phenomenology of Differently Constructed Broensted-type Plots

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.

The effect of alkali metal ions on the reaction of 4-nitrophenyl diphenylphosphinate with aryloxides in ethanol

Rate constants have been measured for the reaction of p-nitrophenyl diphenylphosphinate with aryloxides in ethanol. The reactivity of the less basic phenoxide decreases in the order K+-18-crown ether-6 > K+ > Na+ > Li+, which leads a conclusion that alkali metal-bound aryloxides are less reactive than the dissociated ones in the present system.

Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.

Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds

Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.

Preparation method of compound containing P-O bond or P-S bond

The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method comprises the following steps: a compound containing hydroxyl or sulfydryl and a phosphorus reagent are taken as initial raw materials; then, the initial raw materials are put into an inert gas atmosphere; and under the action of trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO), the compound containing hydroxyl or sulfydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide in a molar ratio of (1-5): (1-2.5): (2-3): 2 react inan organic solvent at the reaction temperature of 25-100 DEG C for 6-20 hours to obtain the compound with the structural general formula (I). The reagents used in the method are low in toxicity and environmentally friendly, and use of precious metal catalysts high in price and toxicity is avoided. The reagents trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO) used in the method are low in toxicity and very low in cost, so that the method is green, environment-friendly, high in economy and suitable for large-scale production.

The α-effect in nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates with HOO- and OH -

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

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

(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.

A NOVEL SUBSTITUENT EFFECT ON 31P NMR CHEMICAL SHIFTS IN THE ARYL DIPHENYLPHOSPHINATE SERIES

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.