46206-23-9

Upstream product

• 329-71-5 2,5-dinitrophenol 
• 1523-08-6 2,5-dinitro-phenyl-acetate 
• 3229-70-7 phenolate 
• 14609-76-8 4-cyanophenolate 
• 18938-17-5 4-formylphenoxide ion 
• 108-99-6 3-Methylpyridine 
• 138554-68-4 2,5-dinitrophenyl diphenylphosphate ester 
• 261172-44-5 4-acetylphenoxide 

Relevant academic research and scientific papers

Structure and mechanism of PhnP, a phosphodiesterase of the carbon-phosphorus lyase pathway

PhnP is a phosphodiesterase that plays an important role within the bacterial carbon-phosphorus lyase (CP-lyase) pathway by recycling a "dead-end" intermediate, 5-phospho-α-d-ribosyl 1,2-cyclic phosphate, that is formed during organophosphonate catabolism

Reactions of phosphate and phosphorothiolate diesters with nucleophiles: Comparison of transition state structures

A series of methyl aryl phosphorothiolate esters (SP) were synthesized and their reactions with pyridine derivatives were compared to those for methyl aryl phosphate esters (OP). Results show that SP esters react with pyridine nucleophiles via a concerted SN2(P) mechanism. Bronsted analysis suggests that reactions of both SP and OP esters proceed via transition states with dissociative character. The overall similarity of the transition state structures supports the use of phosphorothiolates as substrate analogues to probe mechanisms of enzyme-catalyzed phosphoryl transfer reactions. This journal is The Royal Society of Chemistry.

Dependence of Transition-state Structure on Nucleophile in the Reaction of Aryl Oxide Anions with Aryl Diphenylphosphate Esters

Second-order rate constants have been measured for reaction of aryl oxide anions with substituted phenyl diphenylphosphate esters in aqueous media at 25 deg C.The rate constants obey good Broensted type correlations with the pKa of either the leaving group or nucleophile.Both βnuc and βlg values vary substantially with basicity of leaving group and nucleophile, respectively, providing evidence for coupling between bond fission and formation.Attack of phenolate ions on 2,4-dinitrophenyl diphenylphosphate has a βnuc value of 0.12 giving a Kreevoy's tightness parameter value, τ, of 0.18 which is consistent with an 'exploded' transition state for the identity reaction involving 2,4-dinitrophenolate ion as the nucleophile.Transfer of the diphenylphosphinoyl group between 2,4-dinitrophenolate ion nucleophiles has a τ value of 0.28, consistent with an 'exploded' transition state for this reaction also.The identity reaction involving transfer of the diphenylphosphoryl group between phenolates ions has a τ value of 1.20, indicating an almost synchronous process.The data for transfer of the diphenylphosphinoyl and diethylphosphoryl groups between phenolate ion nucleophiles indicates that the identity reaction for the parent phenol has an almost synchronous mechanism for the former phosphinoyl species (τ = 0.92) whereas the latter (τ = 1.45) is almost associative.

Concerted Acetyl Group Transfer between Substituted Phenolate Ion Nucleophiles: Variation of Transition-State Structure as a Function of Substituent

Second-order rate constants (kArO) have been measured for the concerted displacement of aryl oxide from aryl acetates in aqueous solution by substituted phenoxide ions.Values of kArO obey linear Bronsted correlations when either the leaving group or the attacking phenolate ion structures are varied.The Bronsted coefficients obey the equations βnuc = 0.20pK1g - 0.68 and β1g = 0.15pKnuc - 1.73 to a good degree of precision, and the variation indicates that the structure of the transition-state changes within the range of phenolate ions studied; this alsoprovides confirmation that a concerted mechanism operates.The equations for βnuc and β1g predict the equation (log kii = 0.17pKa2 - 2.41pKa + C) for kii, the rate constant for the reaction of aryl oxide ion with acetates bearing identical aryl oxide leaving groups.The identity rate constants may be interpolated from the observed rate constants (kArO) and exhibit excellent fit to the above equation with the single disposable parameter, C, set at 6.5.This is the first report of curvature in a Bronsted plot of identity rate constants.Effective charge development and loss on leaving and attacking oxyanions is fully balanced in the transition state when entering and leaving nucleophiles have a pKa of 7.1.Tetrahedral or acylium ion-like transition-state structures are predicted for hypothetical phenols with pKa's of 11.7 and 2.0, respectively.

HYDROGEN BONDING AND PROTON TRANSFER IN HYDRIDO-BIS-PHENOLATE COMPLEXES IN ACETONE

The homoconjugation, (ArO)2H-, and heteroconjugation, Ar'O- HOAr, (where Ar is aromatic) with proton transfer have been determined in acetone at 298 K.Tetra-alkylammonium phenolates were titrated with a variety of phenols to given ho

Change of Selectivity in Modified Cyclodextrin Catalyst

β-Cyclodextrin having a hydroxamate functional group was newly prepared and its catalytic activity for hydrolysis of a series of mono- or dinitrophenyl acetates was estimated.Relative enhacement of catalytic hydrolysis, kcat(CD-hydroxamate)/ks