15023-66-2

Upstream product

• 4755-50-4 4-(dimethylamino)benzoyl chloride 
• 100-02-7 4-nitro-phenol 
• 619-84-1 p-N,N-dimethylaminobenzoic acid 

Downstream Products

• 100-02-7 4-nitro-phenol 
• 619-84-1 p-N,N-dimethylaminobenzoic acid 
• 40591-10-4 p-N,N-dimethylaminobenzoyl nitrile 
• 14609-74-6 p-nitrophenolate 
• 10287-53-3 ethyl p-dimethyaminolbenzoate 
• 42824-44-2 piperidinium 4-nitrophenolate 

Relevant academic research and scientific papers

Kinetic study on nucleophilic substitution reactions of 4-Nitrophenyl X-Substituted-Benzoates with potassium ethoxide: Reaction mechanism and role of K+ Ion

A kinetic study on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-benzoates (7a-i) with EtOK in anhydrous ethanol at 25.0 ± 0.1 °C is reported. The plots of pseudo-first-order rate constants (kobsd) vs. [EtOK] curve upward. Dissection of kobsd into the second-order rate constants for the reactions with the dissociated EtOV and ion-paired EtOK (i.e., kEtO-and kEtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated EtOV. Hammett plots for the reactions of 7a-i with the dissociated EtOV and ion-paired EtOK exhibit excellent linear correlations with aX = 3.00 and 2.47, respectively. The reactions have been suggested to proceed through a stepwise mechanism in which departure of the leaving-group occurs after the RDS. The correlation of the kEtOK/kEtO{ ratio with the aX constants exhibits excellent linearity with a slope of V0.53. It is concluded that the ion-paired EtOK catalyzes the reaction by increasing the electrophilicity of the reaction center rather than by enhancing the nucleofugality of the leaving group.

Aminolysis of Y-substituted-phenyl 2-methoxybenzoates in acetonitrile: Effect of the o-methoxy group on reactivity and reaction mechanism

Second-order rate constants (kN) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 °C. The Bronsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ρ = 0.54 and r = 1.54. The ρ value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H2O (i.e., ρ = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T± in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T ± through an intramolecular H-bonding interaction.

Investigation of a general base mechanism for ester hydrolysis in C-C hydrolase enzymes of the α/β-hydrolase superfamily: A novel mechanism for the serine catalytic triad

Previous mechanistic and crystallographic studies on two C-C hydrolase enzymes, Escherichia coli MhpC and Burkholderia xenovorans BphD, support a general base mechanism for C-C hydrolytic cleavage, rather than the nucleophilic mechanism expected for a ser

Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles

A kinetic study is reported for the reactions of 4-nitrophenyl X-substituted benzoates (1a-l) and Y-substituted phenyl benzoates (2a-l) with two anionic nucleophiles (OH- and CN-) and three amines (piperidine, hydrazine, and glycylglycine) in 80 mol% H2O-20 mol% dimethyl sulfoxide (DMSO) at 25.0 ± 0.1 °C. Each Hammett plot exhibits two intersecting straight lines for the reactions of 1a-l with the anionic nucleophiles and piperidine, while the Yukawa-Tsuno plots for the same reactions are linear. The Hammett plots for the reactions of 2a-l with hydrazine and glycylglycine demonstrate much better linear correlations with σ- constants than with σ° or σ constants, indicating that the leaving group departure occurs at the rate determining step (RDS). On the contrary, σ- constants result in poorer Hammett correlation than σ° constants for the corresponding reactions with OH- and CN-, indicating that the leaving group departure occurs after the RDS for the reactions with the anionic nucleophiles. The large ρX value (1.7 ± 0.1) obtained for the reactions of 1a-l with the anionic nucleophiles supports the proposal that the reactions proceed through an addition intermediate with its formation being the RDS. The Royal Society of Chemistry 2006.

Evidence of substituent-induced electronic interplay. Effect of the remote aromatic ring substituent of phenyl benzoates on the sensitivity of the carbonyl unit to electronic effects of phenyl or benzoyl ring substituents

Carbonyl carbon 13C NMR chemical shifts δC(C=O) measured in this work for a wide set of substituted phenyl benzoates p-Y-C 6H4CO2C6H4-p-X (X = NO2, CN, Cl, Br, H, Me, or MeO; Y = NO2, Cl, H, Me, MeO, or NMe2) have been used as a tool to study substituent effects on the carbonyl unit. The goal of the work was to study the cross-interaction between X and Y in that respect. Both the phenyl substituents X and the benzoyl substituents Y have a reverse effect on δC(C=O). Electron-withdrawing substituents cause shielding while electron-donating ones have an opposite influence, with both inductive and resonance effects being significant. The presence of cross-interaction between X and Y could be clearly verified. Electronic effects of the remote aromatic ring substituents systematically modify the sensitivity of the C=O group to the electronic effects of the phenyl or benzoyl ring substituents. Electron-withdrawing substituents in one ring decrease the sensitivity of δC(C=O) to the substitution of another ring, while electron-donating substituents inversely affect the sensitivity. It is suggested that the results can be explained by substituent-sensitive balance of the contributions of different resonance structures (electron delocalization, Scheme 1).

Intramolecular charge transfer dual fluorescence of substituted-phenyl p-dimethylaminobenzoates with comparable electron acceptors

A series of substituted-phenyl p-dimethylaminobenzoates with para- or meta-substitution at the ester phenyl ring (p-OH, p-CH3, H, p-Br, m-Cl, and p-NO2) were synthesized and their fluorescence spectra were recorded. Intramolecular ch

MECHANISM OF ESTER AMINOLYSIS IN APROTIC MEDIA AND SPECIFIC SOLVENT EFFECTS

The n-butylaminolysis of nitro-substituted 4'-nitrophenyl benzoates and cinnamates as well as of phenylacetates in aprotic solvents is governed by a kinetic law implying higher order terms in nucleophile.It is shown that the attacking nucleophile forms a n-? type molecular complex with the substrate before reaching the transition state in the subsequent kinetic step.This molecular complex is a true reaction intermediate as evidenced by the observed negative activation enthalpy.Other nucleophile molecules intervene as general base catalysts.Tertiary amines also catalyse the reaction.Their catalytic activity is linearly related to their hydrogen bond forming ability and it is not a direct function of their proton basicity.By varying the nucleophile structure, an excellent Broensted relationship could be obtained for the first time in aprotic media, the β of which confirms that the catalytic collapse of tetrahedral intermediate is the rate determining step.The reaction of cinnamates turns out to be less sensitive to structural changes of the substrate than is the reaction of benzoates as shown by the corresponding Hammet ? values.The electronic effects of 2-nitro groups are strongly solvent dependent.Once more, it is established that whenever specific solvent effects (?-donor or n-donor ability) are present, they dominate the overall effect.A general reaction mechanism is proposed which not only explains the various roles played by the nucleophile but also accounts successfully for the great variety of kinetic schemes observed in aprotic media.