18938-11-9

Upstream product

• 16331-64-9 ethanolate 
• 139-28-6 3-acetylphenyl benzoate 
• 110-89-4 piperidine 
• 62568-45-0 3-acetylphenyl 4-nitrobenzoate 
• 1048998-17-9 C₇H₇O₃S^(1-)*C₁₅H₁₄NO₃⁽¹⁺⁾ 
• 912946-27-1 3-acetylphenyl diphenylphosphinate 
• 1268380-12-6 C₁₅H₁₂O₄ 
• 1325726-17-7 C₁₅H₁₂O₃S 
• 121-71-1 3-Hydroxyacetophenone 
• 1005-56-7 phenylcarbonochloridothioate 
• 124-40-3 dimethyl amine 
• 14941-17-4 Butane-2,3-dione monooximate anion 
• 24573-38-4 4-chlorophenolate 
• 1092513-16-0 3-acetylphenyl methanesulfonate 

Relevant academic research and scientific papers

Kinetic study on aminolysis of aryl X-substituted-cinnamates in acetonitrile: Differential medium effect determines reactivity and reaction mechanism

A kinetic study on nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted-cinnamates (1a-1f) and Y-substituted-phenyl cinnamates (2a-2g) with a series of alicyclic secondary amines in MeCN at 25.0 ± 0.1 °C is reported. The Br?nsted-type pl

Kinetic Study on Nucleophilic Substitution Reactions of O-Phenyl O-Y-substituted-Phenyl Thionocarbonates with 1,8-Diazabicyclo[5.4.0]undec-7-ene in Acetonitrile

Second-order rate constants (kN) for nucleophilic substitution reactions of O-phenyl O-Y-substituted-phenyl thionocarbonates (4a–4k) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN at 25.0 ± 0.1°C are reported. The reactivity of 4a–4k decreases as basicity of the leaving group increases except O-2,4-dinitrophenyl O-phenyl thionocarbonate (4a), which is less reactive than O-3,4-dinitrophenyl O-phenyl thionocarbonate (4b) although the former possesses 2 pKa units less basic nucleofuge than the latter. The Br?nsted-type plot for the reactions of 4b–4k is linear with βlg = ?0.50, a typical βlg value for reactions reported to proceed through a concerted mechanism. The Hammett plot correlated with σY? constants for the reactions of 4b–4k results in a better linear correlation than that correlated with σYo constants. Besides, the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρY = 2.12, r = 0.68 and R2 = 0.990, indicating that a negative charge develops partially on the O atom of the leaving group in the rate-determining step (RDS). Thus, the reactions have been concluded to proceed through a forced concerted mechanism. Effects of steric hindrance on reactivity and reaction mechanism are also discussed in detail.

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.

Alkaline hydrolysis of Y-substituted phenyl phenyl thionocarbonates: Effect of changing electrophilic center from C=O to C=S on reactivity and mechanism

Second-order rate constants (kOH-) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with OH- in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The ksu

Pitfalls in assessing the α-effect: Reactions of substituted phenyl methanesulfonates with HOO-, OH-, and substituted phenoxides in H2O

Toward resolving the current controversy regarding the validity of the α-effect, we have examined the reactions of Y-substituted phenyl methanesulfonates 1a-1l with HOO-, OH-, and Z-substituted phenoxides in the gas phase versus solu

Analysis of linear free-energy relationships combined with activation parameters assigns a concerted mechanism to alkaline hydrolysis of X-substituted phenyl diphenylphosphinates

A kinetic study is reported for alkaline hydrolysis of X-substituted phenyl diphenylphosphinates (1a-i). The Bronsted-type plot for the reactions of 1a-i is linear over 4.5 pKa units with βlg= -0.49, a typical βlg value for reactions which proceed through a concerted mechanism. The Hammett plots correlated with σo and σ- constants are linear but exhibit many scattered points, while the corresponding Yukawa-Tsuno plot results in excellent linear correlation with ρ= 1.42 and r=0.35. The r value of 0.35 implies that leaving-group departure is partially advanced at the rate-determining step (RDS). A stepwise mechanism, in which departure of the leaving group from an addition intermediate occurs in the RDS, is excluded since the incoming HO - ion is much more basic and a poorer nucleofuge than the leaving aryloxide. A dissociative (DN + AN) mechanism is also ruled out on the basis of the small βlg value. As the substituent X in the leaving group changes from H to 4-NO2 and 3,4-(NO2)2, ΔH≠ decreases from 11.3 kcal mol-1 to 9.7 and 8.7 kcal mol-1, respectively, while ΔS≠ varies from -22.6 cal mol-1 K-1 to -21.4 and -20.2 cal mol-1 K-1, respectively. Analysis of LFERs combined with the activation parameters assigns a concerted mechanism to the current alkaline hydrolysis of 1a-i.

A study on a primitive artificial esterase model: Reactivity of a calix[4]resorcinarene bearing carboxyl groups

The host molecule octacarboxymethyl calix[4]resorcinarene 1 catalyses the hydrolysis of substituted phenyl N-methylpyridinium-4-carboxylate esters 3a-f by complexation followed by intracomplex reaction via an anhydride intermediate. The reactivity in the

Aminolyses of aryl diphenylphosphinates and diphenylphosphinothioates: Effect of modification of electrophilic center from P=O to P=S

(Chemical Equation Presented) A kinetic study is reported for aminolysis of aryl diphenylphosphinothioates (2a-i). The phosphinothioates 2a-i are less reactive than aryl diphenylphosphinates (1a-i), the oxygen analogues of 2a-i, regardless of the basicity

Aminolysis of Y-substituted phenyl X-substituted benzoates with piperidine: Effect of nonleaving group substituent

The title reaction has been suggested to proceed through a zwitterionic tetrahedral intermediate with a change in the rate determining step on the basis of the curved Bronsted-type plots obtained. The curvature center of the curved Bronsted-type plots is at pKa = 6.4 regardless of the electronic nature of the substituent X in the benzoyl moiety.

Curved Hammett Plot in Alkaline Hydrolysis of O-Aryl Thionobenzoates: Change in Rate-Determining Step versus Ground-State Stabilization

Second-order rate constants have been measured for alkaline hydrolysis of O-aryl thionobenzoates (X-C6H4-CS-OC6H 4-Y) in 80 mol % H2O-20 mol % DMSO at 25.0 ± 0.1 °C. The Hammett plot for the reaction of O-4-nitrophenyl X-substituted thionobenzoates (X-C6H4-CS-OC6H 4-NO2, 1a-e) exhibits a downward curvature. However, a possible traditional explanation in terms of a change in the rate-determining step (RDS) has been considered but rejected. The proposed explanation involves stabilization of the ground-state (GS) through-resonance interaction between the electron-donating substituent X and the thionocarbonyl functionality on the basis of the linear Yukawa-Tsuno plot obtained for the same reaction. The Bronsted-type plot for the reaction of O-aryl thionobenzoates (C 6H5-CS-OC6H4-Y, 2a-i) is linear but exhibits many scattered points with a small βlg, (-0.35). The Hammett plot for the same reaction shows rather poor correlation with σ- constants but much better correlation with σ° constants. The alkaline hydrolysis of O-aryl thionobenzoates (1a-e and 2a-i) has been proposed to proceed through an addition intermediate in which bond formation is the RDS.