Nitration Of Anisole Research Articles

The Synthesis of Phenyl Acetylene Phenols for Development of New Explosives

The purpose of this research is to produce derivatives of simple phenols as “raw material” for the synthesis of new phenolic explosives. A big number of valuable products is synthesized from phenol and its homologues including well-known explosives - picric acid, methyl picrate, cresolite, etc. In general, a structural modification of well-known explosives’ molecules is the most important among the methods for the synthesis of new explosives. This method can be used in certain modifications. For example, the synthesis of methyl picrate is possible not only to replace picric acid’s hydroxyl with metoxyl, but with nitration of anisole as well, i. e, by the reciprocating synthesis. Thus, to produce the new analogues of well-known phenolic explosives, the preliminary modification of simple phenols’ molecules and further nitration, presumably by a formation of dinitro derivatives may be performed. The alkylation of phenol, anisole and m – cresol by the secondary phenyl acetylene alcohols in the presence of concentrated phosphoric acid was carried out. Para-substituted alkynyl phenols with high yields were developed. The chemical transformations were carried out by a participation of their molecules’ active centres. The corresponding ethers, esters and saturated isologues have been synthesized. The article describes the conditions of a synthesis of 14 new phenyl acetylenes’ substances that may be used as substrates in a nitration reaction.

Ternary liquid–liquid equilibrium: Nitric acid–water–anisole/4-methyl anisole

Nitration of anisole and 4-methyl anisole with aqueous nitric acid involves liquid–liquid two phase (organic phase and aqueous acid phase) mixtures of nitric acid–water–anisole/4-methyl anisole. Nitric acid is not dissociated completely into nitronium ion, which is the nitrating agent and knowledge of its concentration in both phases is very important to study nitration reaction. The e-NRTL model modified for incomplete dissociation of nitric acid for predicting concentrations of nitronium ion, undissociated nitric acid, and water and anisole/4-methyl anisole in both phases has been used. Computations of phase split, extent of ionization of nitric acid were calculated by minimizing Gibbs free energy with modified Nelder–Mead procedure. Equilibrium data of liquid–liquid binary and ternary systems were collected experimentally and interaction parameters were obtained by fitting these data. LLE data for the studied systems, ionization equilibria of nitric acid, i.e. the concentration of nitronium ion in both phases and also methods for phase equilibria, which are not reported earlier are presented.

ChemInform Abstract: Two-Phase Nitration of Phenols. Part 3. The Nitration of Anisole.

Abstract The two-phase nitration procedure previously described for phenols can be modified to lead to successful nitration of anisole but through a different mechanism. The addition of N(III) species is unnecessary and the reaction is not supressed by nitrous acid traps, the presence of which alters the ortho:para ratio.

15N-CIDNP Investigations during Nitration of Anisole with Nitric Acid and Sulfuric Acid in Acetic Acid.

15N-CIDNP Investigations during Nitration of Anisole with Nitric Acid and Sulfuric Acid in Acetic Acid.

ChemInform Abstract: Nitrosation and Nitrous Acid‐catalysed Nitration of Anisole and 2,6‐Dimethylanisole.

AbstractThe nitrosation of (I) and (IV) is studied in order to elucidate a nitrosationoxidation pathway leading to nitroanisole (VII) under nitration conditions.

Reactions of cerium(IV) ammonium nitrate with aromatic compounds in acetonitrile. Part 2. Nitration; comparison with reactions of nitric acid

The nitration of benzene and a number of alkylbenzenes by cerium(IV) ammonium nitrate in acetonitrile shows the same intra- and inter-molecular selectivity as nitration with nitric acid under the same conditions but the extent of the other products formed in the two sets of reactions is very different. Nitration, by cerium(IV) ammonium nitrate (but not side-chain substitution) is suppressed by the addition of water. The results suggest that these nitration reactions by cerium(IV) ammonium nitrate occur through the intermediate formation of a nitronium ion from the cerium(IV) complex but the order with respect to the aromatic compound shows that this nitronium ion must then be formed in the presence of the aromatic substrate as a ‘ spectator’. The relative reactivities with respect to benzene in the nitration of anisole and naphthalene are much greater than those observed in nitration by nitric acid and, with both, the isomer proportions are also anomalous.

Electrophilic aromatic substitution. Part 16. The nitration of anisole, o-methylanisole, and p-methylanisole in aqueous sulphuric acid

In the quantitative mononitration of anisole in 54–82% sulphuric acid at 25° the o : p ratio varies from 1.8 to 0.7. It is suggested that the rate-limiting step is the formation of an encounter pair between the nitronium ion and an anisole molecule which is hydrogen-bonded to a hydronium ion. The change in the o : p ratio may be due to competition between direct formation of Wheland intermediates from the hydrogen-bonded encounter pair, and loss of the hydronium ion to give a nitroniurn ion–anisole encounter pair, with subsequent formation of Wheland intermediates. With o- and p-methylanisole the products, and changes in product ratios with acidity are interpreted by considering the fates of the ipso-Wheland intermediates formed at C–Me. 4-Methyl-2-nitrophenol is an important product of the nitration of p-methylanisole, and results from ipso-attack by nitronium at C–Me, followed by attack of water and loss of methoxy.

Marked deviations from the additivity principle in the products of nitration of substituted anilinium ions

Product compositions have been determined for the nitration of several substituted anilinium ions activated by a methoxy-group or by two methyl groups. Kinetic studies have been carried out on two compounds with a methoxy-substituent. The results have been shown to deviate markedly from those predicted by the additivity principle but to be understandable on the assumption that the substituents exert independent directing effects which are not necessarily the same as those shown in the corresponding monosubstituted benzenes. In particular, the nitrogen pole appears to deactivate all positions in the ring to a very similar extent and the methoxy-group appears to be much more ortho-directing than is observed in the nitration of anisole. These results are shown to accord with other results in the literature and to lead to a reassessment of the apparently anomalous orientation of electrophilic substitution in meta-nitroanisole.

The ortho—para Ratio in Electrophilic Aromatic Substitution. Evidence for a Linear Coordination Effect in Nitration of Anisole1

The ortho—para Ratio in Electrophilic Aromatic Substitution. Evidence for a Linear Coordination Effect in Nitration of Anisole¹

The Mechanism of the Nitration of Anisole

The Mechanism of the Nitration of Anisole

131. The nitration of anisole

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