30332-87-7

Upstream product

• 3535-67-9 2,6-dinitroanisole 
• 108-91-8 cyclohexylamine 

Relevant academic research and scientific papers

REACTIONS OF NITROANISOLES. PART 6. REACTION OF 2,6-DINITROANISOLE WITH CYCLOHEXYLAMINE IN MIXED SOLVENTS. SOLVENT EVIDENCE FOR THE 'DIMER' MECHANISM

The reaction of 2,6-dinitroanisole with cyclohexylamine in methanol and benzene-methanol was studied at several amine concentrations.Althrough the reaction rate in methanol is higher than in benzene, addition of small amounts of methanol to the benzene solution diminishes the rate of reaction (which is of third order in amine), reaching a minimum value at nearly 30percent methanol, after which the rate increases almost linearly with the methanol content.These and other results, here described, are satisfactorily explained by a previously proposed reaction scheme, in which the dimer of the amine is operating.

Reaction of 2,6-Dinitroanisole with Cyclohexylamine in Toluene-Octanol Binary Solvents. Further Support for the 'Dimer Nucleophile Mechanism' in Aromatic Nucleophilic Substitution

The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene, octanol and toluene-octanol mixtures has been studied at several amine concentrations.The reactions in toluene and in octanol-toluene mixtures up to 30percent octanol show a third-order kinetic dependence on .Although the reaction rates in toluene and octanol are very similar, addition of small amounts of octanol to the toluene solution diminishes the rate of reaction, reaching a minimum values at 30-50percent octanol, after which the rate increases almost linearly with the octanol content.These and other results, here described, are satisfactorily explained by the previously proposed 'dimer nucleophile mechanism'.Previously reported similar observations in methanol-benzene mixtures were criticised as being due to the reversibility of the reaction.The present results confirm the previously reported mechanism and the irreversibility of the reaction under the reaction conditions.

The Effect of a Hydrogen Bond Acceptor Catalyst on the Dimer Mechanism in Aromatic Nucleophilic Substitution

The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations.In pure toluene and toluene-DMSO mixtures of low DMSO content (/= 1percent) third-order kinetics with respect to the amine are observed.These results are interpreted as a consequence of the aggregation of the nucleophile (dimer) in low-polarity solvents.Association of DMSO with the amine ('mixed dimer') in a solute-solvent hydrogen-bond interaction can be responsible for the observed catalytic effect of DMSO.At higher DMSO contents behaviour typical for amine catalysis was found which is related to considerable additional stabilization of the intermediate complex through solvation by DMSO.

Reactions of Nitroanisoles. 4. Reaction of 2,4- and 2,6-Dinitroanisole with Cyclohexylamine. Evidence of a "Dimer" Nucleophile

The reactions of 2,4- and 2,6-dinitroanisole (DNA) with cyclohexylamine in benzene and in cyclohexane were studied at three temperatures.Two unusual facts were observed: the overall reaction rate is of third order with respect to the amine concentration, and an inverse temperature effect is found for the reaction of 2,4-DNA in cyclohexane.Both experimental findings and some other "anomalous" results reported in the literature are satisfactorily accommodated in a reaction scheme in which the dimer of the amine is operating.