Synthesis of o-Nitroarylamines via Ipso Nucleophilic Substitution of Sulfonic Acids

Abstract

A mild, efficient, and eco-friendly method for the synthesis of o-nitroarylamine from o-nitroaryl sulfonic acid via ipso nucleophilic aryl substitution by amine is described. The products have been obtained with good yields at room temperature without the assistance of any metal, activating agent, or toxic oxidant. This method is useful for racemization-free synthesis of N-aryl amino acid esters.

Unprecedented C–C Bond Formation via Ipso Nucleophilic Substitution of 2,4-Dinitrobenzene Sulfonic Acid with Active Methylene Compounds

“…However, Cs 2 CO 3 performed better than K 2 CO 3 (entry 14). Nitrogenous bases may substitute the sulfonic acid group . Yield of this reaction increased with temperature till 80 °C (entries 14–18).…”

“…Nitrogenous bases may substitute the sulfonic acid group. 15 Yield of this reaction increased with temperature till 80 °C (entries 14 −18). Two equivalents of the base and dimethyl malonate were required for the highest efficiency.…”

“…Previously, we have developed an efficient method for synthesizing arylamine from sulfonic acid analogues via ipso nucleophilic substitution of sulfonic acid by amine [ Scheme 1 i]. 15 In this communication, we describe the new carbon–carbon bond formation via ipso nucleophilic substitution of sulfonic acid of 2-nitrobenzene sulfonic acid analogues by active methylene compounds [ Scheme 1 ii]. In this ipso nucleophilic substitution reaction, the sulfonic acid group acts as a leaving group.…”

Synthesis of various 1‐alkylbenzimidazole derivatives directly from 2‐alkylaminonitroarenes via a two‐step, one‐pot procedure

“…The following nitroanilines were obtained according to the published procedures: 1a [15], 1b [15], 1c [12f], 1d [16], 1j [17], 1 k [18], and 1o [12d]. Nitroanilines 1i and 1l were commercial.…”

Arenesulfenyl Fluorides: Synthesis, Structure, and Reactivity

“…Finally, taking advantage of the electron-deficient nature of the aryl thioethers prepared by our procedure, we proposed that the arene could be efficiently removed by nucleophilic aromatic substitution, allowing for the installation of other sulfur functional groups. [55][56][57][58][59] After oxidation of alkyne-derived adduct 7i to the sulfone, treatment with piperidine at room temperature resulted in rapid dearylation to form the fluorinated sulfinate, which was identified by 19 F NMR spectroscopy (δ = -97.0 ppm) but not isolated. Through addition of an appropriate electrophile, either NFSI or the combination of NCS with a secondary amine, this sulfinate could be transformed into a sulfonyl fluoride or sulfonamide, retaining the previously installed fluorine and its stereochemical relationships.…”