10259-20-8

Usage

InChI:InChI=1/C18H14NO4P/c20-19(21)15-11-13-16(14-12-15)23-24(22,17-7-3-1-4-8-17)18-9-5-2-6-10-18/h1-14H

Upstream product

• 100-02-7 4-nitro-phenol 
• 1499-21-4 Diphenylphosphinic chloride 
• 719-80-2 Ethyl diphenylphosphinite 
• 1079-66-9 chloro-diphenylphosphine 
• 4559-70-0 Diphenylphosphine oxide 
• 1707-03-5 diphenyl-phosphinic acid 

Downstream Products

• 137171-51-8 2,4,6-tris(4-methoxyphenyl)-2,4,6-trisulfanylene-1,3,5,2,4,6-trioxatriphosphinane 
• 68017-99-2 p-nitrophenyl diphenylphosphinothionate 
• 55025-89-3 morpholinodiphenylphosphine oxide 
• 100-02-7 4-nitro-phenol 
• 10364-94-0 1-benzoylimidazole 
• 1707-03-5 diphenyl-phosphinic acid 
• 14609-74-6 p-nitrophenolate 
• 98579-83-0 (Methyl-butyl-amino)-diphenyl-phosphinoxid 
• 21713-54-2 O-4-bromophenyl phenyl phenyl(phenyl)phosphinate 
• 1706-96-3 phenyl diphenylphosphinate 
• 21713-53-1 4-methyl-o-phenyl phenyl(phenyl)phosphinate 
• 21713-55-3 O-4-chlorophenyl diphenylphosphinate 
• 21713-56-4 4-acetylphenyl diphenylphosphinate 
• 102817-54-9 4-cyanophenyl diphenylphosphinate 

Relevant academic research and scientific papers

Reactions of N-aroxycarbonyltrichloroacetimidates with nucleophilic phosphorus derivatives

Aryl N-aroxycarbonyltrichloroacetimidates (Ar = Ph, 4-FC6H 4) react with diphenylphosphinite according to the scheme of the aza-Perkow reaction to give the corresponding aryl N-(1-aroxy-2,2-dichloro- vinyl)-N-diphenylphosphinoylcarba

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.

Highly Efficient and Convenient Access to Phosphinates via CHCl3-Assisted Direct Phosphorylation between R2P(O)H and ROH by Phosphonium Salt Catalysis

A mild, efficient, convenient and scalable method to synthesize phosphinates via direct phosphorylation between R2P(O)H and ROH was developed. All aromatic substrates completed this transformation with excellent yields (up to 98 %), and preliminary mechanistic studies suggest that a carbene-involving process from CHCl3 to CH2Cl2 facilitates the phosphorylation.

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

Kinetics and mechanism of the anilinolyses of aryl dimethyl, methyl phenyl and diphenyl phosphinates

The reactions of Z-aryl dimethyl (1), methyl phenyl (2), and diphenyl (3) phosphinates with X-anilines in dimethyl sulfoxide at 60.0 °C are studied kinetically. Kinetic results yield the primary normal deuterium kinetic isotope effects (DKIEs) involving deuterated aniline (XC6H4ND 2) nucleophiles, kH/kD = 1.03-1.17, 1.15-1.29, and 1.24-1.51, and the cross-interaction constants (CICs), ρXZ = 0.37, 0.34, and 0.65 for 1, 2, and 3, respectively. The steric effects of the ligands (R1 and R2) on reaction rates play a role, but are relatively much smaller compared to other phosphinate systems. A stepwise mechanism with a rate-limiting leaving group expulsion from the intermediate is proposed on the basis of the CICs positive signs. The dominant frontside nucleophilic attack through a hydrogen-bonded, four-center-type transition state is proposed on the basis of primary normal DKIEs and large magnitudes of the CICs for 2 and 3, while both frontside and backside attack are proposed on the basis of relatively small primary normal DKIEs for 1.

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.

Origin of the bell-shaped α-effect-solvent composition plots. pKa-solvent dependence of the α-effect at a phosphorus center

The rates of reaction of the "α" nucleophile, 2,3-butanedione monoximate (Ox-), and the "normal" nucleophile, 4-chlorophenoxide (4-ClPhO-), with the phosphorus ester, p-nitrophenyl diphenylphosphinate (PNPDPP), were measured in DMSO-H2O mixtures at 25.0 °C. Addition of small quantities of DMSO (up to ca. 10 mol %) to the aqueous solvent led to a decrease in the second-order rate constants of reaction for both nucleophiles. Additional increases in the DMSO content above 20 mol % resulted in smooth and regular increases in the rate for 4-ClPhO-, but for Ox- the corresponding increase in reaction rate upon increase of DMSO content is not linear, being best described as either curved or composed of two intersecting linear portions in the log k vs mole percent DMSO plot. The magnitude of the α-effect, KOx-/K4-ClPhO-, shows a bell-shaped dependence on solvent composition, with a maximum value of ca. 40 at ca. 50 mol % DMSO. The data is analyzed in terms of the recently developed novel procedure for Br?nsted-type plots, in which changes in basicity and reactivity of the nucleophile are brought about through changes in solvent composition rather than changes of remote substituent. This analysis suggests that the bell-shaped dependence of the α-effect magnitude upon solvent composition may stem from the effect of advanced desolvation of the Ox- nucleophile at the transition state relative to bond formation, i.e., imbalance or nonperfect synchronization effects.