1037-31-6

Basic information

• Product Name: 4-nitrophenyl 4-nitrobenzoate
• Synonyms: benzoic acid, 4-nitro-, 4-nitrophenyl ester; Phenol, p-nitro-, p-nitro-benzoate
• CAS NO: 1037-31-6
• Molecular Formula: C₁₃H₈N₂O₆
• Molecular Weight: 288.2124
• Mol File: 1037-31-6.mol

Chemical Properties

• Boiling Point: 496.9°C at 760 mmHg
• Flash Point: 233.3°C
• Density: 1.466g/cm³
• Vapor Pressure: 5.18E-10mmHg at 25°C
• Refractive Index: 1.642
• CAS DataBase Reference: 4-nitrophenyl 4-nitrobenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: 4-nitrophenyl 4-nitrobenzoate(1037-31-6)
• EPA Substance Registry System: 4-nitrophenyl 4-nitrobenzoate(1037-31-6)

Safety Data

• Hazardous Substances Data: 1037-31-6(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
4-nitrophenyl 4-nitrobenzoate is used as a reagent for the synthesis of various organic compounds, including pharmaceuticals and agrochemicals. Its ability to generate nitrophenyl radicals makes it a valuable intermediate in a range of chemical reactions.
Used in Chemical Kinetics and Reaction Mechanisms Research:
In the field of chemical kinetics, 4-nitrophenyl 4-nitrobenzoate serves as a model compound to study reaction rates and mechanisms. Its decomposition and subsequent reactions provide insights into the behavior of similar compounds under various conditions.
Used in Dyes and Pigments Formulation:
4-nitrophenyl 4-nitrobenzoate is also utilized in the formulation of dyes and pigments due to its color-producing properties. Its presence contributes to the development of specific hues and shades in various applications.
Used in Safety and Handling Protocols:
Due to its potentially hazardous nature, 4-nitrophenyl 4-nitrobenzoate is used as a case study in the development of safety and handling protocols for chemical compounds. Proper storage and handling procedures are essential to minimize risks associated with its use in laboratories and industrial settings.

Upstream product

• 100-02-7 4-nitro-phenol 
• 62-23-7 4-nitro-benzoic acid 
• 122-04-3 4-nitro-benzoyl chloride 
• 824-78-2 4-nitrophenol sodium salt 
• 53639-34-2 p-nitrobenzoic tert-butylcarbonic anhydride 
• 7693-46-1 4-Nitrophenyl chloroformate 
• 555-16-8 4-nitrobenzaldehdye 

Downstream Products

• 100-02-7 4-nitro-phenol 
• 64026-23-9 N-dodecyl-p-nitrobenzamide 
• 62-23-7 4-nitro-benzoic acid 
• 51207-98-8 N-butyl-4-nitrobenzamide 
• 1854-15-5 N-dodecyl-4-methoxybenzamide 
• 99-77-4 ethyl 4-nitrobenzoate 
• 14609-74-6 p-nitrophenolate 
• 7511-31-1 4-chlorophenyl 4-nitrobenzoate 
• 1429-05-6 phenyl 4-nitrobenzoate 
• 2906-29-8 4-nitrobenzoate 
• 78196-53-9 p-nitrobenzoylglycylglycine 
• 1613-76-9 4-nitrobenzohydroxamic acid 
• 636-97-5 N-amino-(4-nitrophenyl)carboxamide 
• 50445-50-6 N-ethyl-4-nitrobenzamide 

Relevant articles and documents

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).

Synthesis and structure-activity relationships of small-molecular di-basic esters, amides and carbamates as flaviviral protease inhibitors

Inhibitors of the flaviviral serine proteases, which are crucial for the replication of dengue and West-Nile virus, have attracted much attention over the last years. A dibasic 4-guanidinobenzoate was previously reported as inhibitor of the dengue protease with potency in the low-micromolar range. In the present study, this lead structure was modified with the intent to explore structure-activity relationships and obtain compounds with increased drug-likeness. Substitutions of the guanidine moieties, the aromatic rings, and the ester with other functionalities were evaluated. All changes were accompanied by a loss of inhibition, indicating that the 4-guanidinobenzoate scaffold is an essential element of this compound class. Further experiments indicate that the target recognition of the compounds involves the reversible formation of a covalent adduct.

Sodium cyanide-promoted copper-catalysed aerobic oxidative synthesis of esters from aldehydes

A simple and efficient copper-catalysed procedure for oxidative esterification of aldehydes with alcohols and phenols mediated by sodium cyanide, using air as a clean oxidant, is described. A variety of aromatic aldehydes and structurally different alcohols and phenols reacted efficiently, and the product esters were obtained in good to excellent yields under normal atmospheric and solvent-free conditions.

Olefins from biomass feedstocks: Catalytic ester decarbonylation and tandem Heck-type coupling

With the goal of avoiding the need for anhydride additives, the catalytic decarbonylation of p-nitrophenylesters of aliphatic carboxylic acids to their corresponding olefins, including commodity monomers like styrene and acrylates, has been developed. The reaction is catalyzed by palladium complexes in the absence of added ligands and is promoted by alkali/alkaline-earth metal halides. Combination of catalytic decarbonylation and Heck-type coupling with aryl esters in a single pot process demonstrates the viability of employing a carboxylic acid as a "masked olefin" in synthetic processes. This journal is

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.

5,5′-Dimethyl-3,3′-azoisoxazole as a new heterogeneous azo reagent for esterification of phenols and selective esterification of benzylic alcohols under Mitsunobu conditions

5,5′-Dimethyl-3,3′-azoisoxazole is used as a new efficient heterogeneous azo reagent for the highly selective esterification of primary and secondary benzylic alcohols and phenols with aliphatic and aromatic carboxylic acids via Mitsunobu protocols. The reaction is highly selective for primary benzylic alcohols versus secondary ones, aliphatic alcohols and also phenols. The isoxazole hydrazine byproduct can be simply isolated by filtration and recycled to its azoisoxazole by oxidation.

Effective esterification of carboxylic acids using (6-oxo-6H-pyridazin-1-yl)phosphoric acid diethyl ester as novel coupling agents

(6-Oxo-6H-pyridazin-1-yl)phosphoric acid diethyl esters (3) are efficient and selective coupling agents for equimolar esterification of carboxylic acids and alcohols. Esterification of aliphatic and aromatic carboxylic acids with aliphatic and aromatic alcohols using 3 afforded the corresponding esters chemoselectively in good to excellent yield.

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.