7511-31-1

Upstream product

• 122-04-3 4-nitro-benzoyl chloride 
• 1193-00-6 sodium 4-chlorophenolate 
• 1037-31-6 4-nitrophenyl 4-nitrobenzoate 
• 24573-38-4 4-chlorophenolate 
• 106-48-9 4-chloro-phenol 
• 555-16-8 4-nitrobenzaldehdye 
• 62-23-7 4-nitro-benzoic acid 

Downstream Products

• 64026-23-9 N-dodecyl-p-nitrobenzamide 
• 106-48-9 4-chloro-phenol 
• 62-23-7 4-nitro-benzoic acid 
• 64001-52-1 4-chlorophenyl-4-aminobenzoate 
• 106841-09-2 4'-amino-5-chloro-2-methoxy-benzophenone 
• 76442-97-2 5-chloro-2-methoxy-4'-nitro-benzophenone 
• 84443-36-7 (5-chloro-2-hydroxyphenyl)(4-nitrophenyl)methanone 

Relevant academic research and scientific papers

Metal-free aerobic oxidative esterification of aromatic aldehydes promoted by potassium fluoride (KF)

We investigated the oxidative esterification of aldehydes with alcohols/phenols to produce a range of esters. In this approach, we conducted the reaction under metal-free conditions at room temperature. The reactions were promoted by potassium fluoride (KF) as the additive, resulting in the desired product in good to high yields. This procedure was found to be effective for the production of aryl esters, which are challenging in most of the available reports. It is vital for this procedure not to exclude air as the source of oxygen.

Crystal engineering of hand-twisted helical crystals

A strategy is outlined for the design of hand-twisted helical crystals. The starting point in the exercise is the one-dimensional (1D) plastic crystal, 1,4-dibromobenzene, which is then changed to a 1D elastic crystal, exemplified by 4-bromophenyl 4'-chlorobenzoate, by introduction of a molecular synthon -O-CO-in lieu of the supramolecular synthon Br···Br in the precursor. The 1D elastic crystals are next modified to two-dimensional (2D) elastic crystals, of the type 4-bromophenyl 4'-nitrobenzoate where the halogen bonding and C-H· · ·O hydrogen bonding are well-matched. Finally, varying the interaction strengths in these 2D elastic crystals gives plastic crystals with two pairs of bendable faces but without slip planes. Typical examples are 4-chlorophenyl and 4-bromophenyl 4'-nitrobenzoate. This type of 2D plasticity represents a new type of bendable crystals in which plastic behavior is seen with a fair degree of isotropic character in the crystal packing. The presence of two sets of bendable faces, generally orthogonal to each other, allows for the possibility of hand-twisting of the crystals to give grossly helical morphologies. Accordingly, we propose the name hand-twisted helical crystals for these substances.

Kinetics of the reaction of 4-nitrophenyl benzoates with 4-chlorophenol in the presence of potassium carbonate in dimethylformamide

The effect of the substituent in the benzoyl group on the relative rate and activation parameters of transesterification of substituted 4-nitrophenyl benzoates with 4-chlorophenol in dimethylformamide in the presence of potassium carbonate was studied by the competing reaction technique. The whole series of benzoates showed the enthalpy-entropy compensation effect. 4-Nitrophenyl benzoates having electronacceptor substituents give rise to isokinetic relationship with an isokinetic temperature β of 382 K. The mechanism of the transesterification process is discussed. Pleiades Publishing, Inc., 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).

The effect of acyl substituents on the α-effect: Contrasting α-effect profiles for reactions of 4-nitrophenyl substituted benzoates with neutral and anionic nucleophiles

The magnitude of the α-effect for reactions of 4-nitrophenyl substituted benzoates with a pair of anionic nucleophiles is independent of the electronic nature of the acyl substituent, while the one for the corresponding reactions with a pair of neutral nucleophiles increases as the acyl substituent changes from a strong electron withdrawing substituent to electron donating ones.

Evidence of a stepwise acyl-transfer reaction mechanism: Nonlinear hammett plots for reactions of p-nitrophenyl substituted benzoates with hydroxide and p-chlorophenoxide

The Hammett plots obtained for the title-reactions exhibit a break, i.e. ρ acyl values decrease from 2.21 ~ 2.44 to 1.45 ~ 1.52 as the acyl substituent becomes a strong electron withdrawing group (σ > 0.6). Such a break in the Hammett plots is suggestive of a change in the reaction mechanism and strong evidence of a stepwise mechanism for the acyl-transfer reaction.

Imidazole-Catalyzed Hydrolysis of Substituted Benzoate Esters. A Detailed Kinetic and Mechanistic Study

Kinetic and mechanistic details of the imidazole-catalyzed hydrolysis of substituted phenyl benzoates in 10percent acetonitrile in water (V/V) were examined.The following 4 ester series were studied: p-nitrophenyl p-X-benzoates (X = CH3, H, Cl, CN, NO2, series I), p-Y-phenyl p-nitrobenzoates (Y = CH3, H, Cl, CN, NO2, series II), 2,4-dinitrophenyl p-X-benzoates (X = CH3O, H, Cl, CN, NO2, series III) and p-Y-phenyl 2,4-dinitrobenzoates (Y = CH3, H, Cl, CN, NO2, series IV).Based on: catalytic rate constants, activation parameters, kinetic solvent isotope effects, Hammett (ρ) values and the spectroscopic detection of the reaction intermediates, the following conclusions were reached: a) imidazole acts as a nucleophilic catalyst, i.e., the hydrolysis occurs via the intermediate formation of acylimidazole; b) the leaving group is the phenoxide ion; c) the rate limiting step is the decomposition of the tetrahedral intermediate that precedes the acylimidazole (series I, II and IV) or the attack of imidazole on the acyl group of the ester (series III). Keywords: Acylimidazoles / Catalysis / Chemical Kinetics / Isotope Effects / Reaction Mechanism