128080-60-4

Upstream product

• 823-37-0 1-methyl-2-nitropyrrole 
• 87013-25-0 Chloromethyl phenyl sulfone anion 
• 128080-56-8 1-Methyl-2-nitro-5-deuteriopyrrole 
• 7205-98-3 chloromethyl phenyl sulfone 

Relevant academic research and scientific papers

Reactions of nitroheteroarenes with carbanions: Bridging aromatic, heteroaromatic and vinylic electrophilicity

The relative rate constants for the vicarious nucleophilic substitution (VNS) of the anion of chloromethyl phenyl sulfone (1-) with a variety of nitroheteroarenes, for example, nitropyridines, nitropyrroles, nitroimidazoles, 2-nitrothiophene, and 4-nitropyrazole, have been determined by competition experiments. It was shown that nitropyridines are approximately four orders of magnitude more reactive than nitrobenzene. Among the five-membered heterocycles 2-nitrothiophene is the most active followed by nitroimidazoles and 4-nitropyrazole. Nitropyrroles are the least electrophilic nitroheteroarenes with reactivities comparable to nitrobenzene. Quantum chemically calculated methyl anion affinities (B3LYP/6-311 G(d,p)//B3LYP/ 6-31G(d)) of the nitroarenes correlated only moderately with the partial relative rate constants. The correlation of these activities with the LUMO energies of nitroarenes is even worse. By measuring the second-order rate constants of the addition of 1" to nitroarenes and to diethyl arylidenemalonates 10, it was possible to link the electrophilic reactivities of nitroheteroarenes with the comprehensive electrophilicity scale based on the linear-free-energyrelationship log k(20°C) = s(N + E).

Vicarious nucleophilic substitution of hydrogen in nitroderivatives of five-membered heteroaromatic compounds

Nitro derivatives of thiophene, furan and pyrrole react with carbanions containing leaving groups giving products of replacement of hydrogen with functionalized alkyl substituents. Many specific features of this reaction are discussed.

UNUSUAL ORIENTATION IN VICARIOUS NUCLEOPHILIC SUBSTITUTION OF HYDROGEN IN NITROPYRROLES

The vicarious nucleophilic substitution of hydrogen in N-substituted 2-nitropyrrole with carbanion of chloromethyl phenyl sulfone occurs at position 5- or 3- depending upon electronic effects of the N-protecting group.