Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfinates

Abstract

In reactions with sodium sulfi nates of N-substituted 1,4-benzoquinone monoimines with the quinoid ring having free positions 2 and/or 6 the fraction of products of 1,4-addition of the sulfi nate ion grows in the series ArSO 2 → MeSO 2 → CF 3 SO 2 . In the case of 2,6-dimethyl derivatives the 1,6-addition is preferable, and the amount of products of 6,1-addition decreases.

Reaction of some N-substituted 1,4-benzoquinone imines with sodium arenesulfinates

“…7 2014 975 glets from 3-H and 6-H at δ 6.78-6.80 and 7.82-7.83 ppm, respectively, which unambiguously confirmed their structure as 1,4-addition products. Mixtures of 1,6-and 6,1-addition products XXVIa/ XXXIIa and XXVIb/XXXIIb showed in the spectra two sets of signals from three protons in the aminophenol fragment, which were assigned on the basis of the data in [4][5][6]. In the 1 H NMR spectra of 1,6-addition products, signals from protons in the aminophenol fragment appeared in a weaker field relative to the corresponding signals of 6,1-adducts.…”

“…In the other cases, the product ratio was determined from the intensity ratio of the singlet signals from the MeO and Me protons in the arenesulfonyl fragment, taking into account that their positions were different for the 1,4-, 6,1-and 1,6-addition products. For instance, the chemical shifts of the methoxy protons in the arylsulfonyl group were as follows, δ, ppm: 1,6-addition, 3.87-3.89 (DMSO-d 6 The structure of 1,4-addition products XIIIa, XIVa, XVa, XVIb, XVIIb, XVIId, XIXb, and XXb was additionally confirmed by their oxidation with lead tetraacetate in glacial acetic acid to the corresponding quinone imines X XX III-XXX VI, XXX VIIa, XXXVIIb, XXXVIII, and XXXIX (Scheme 2), for the 1 H NMR spectra of the latter were more informative. The 1 H NMR spectra of quinone imines XXXIII and XXXV contained a very downfield singlet from the 6-H proton (δ 9.03 ppm), and in the spectra of XXXIV and XXXVI we observed two sets of signals from the Z and E isomers, which unambiguously indicated that the hydrogen atoms are attached to C 2 and C 6 of the quinoid ring.…”

“…We previously studied in detail reactions of N-aryl-2,6-dialkyl [1], N-aroyl, N-arylsulfonyl, N-[arylsulfonylimino(phenyl)methyl]-2,6(3,5, or 2,5)-dialkyl [2][3][4][5], and N-aryl(alkyl, trifluoromethyl)sulfonyl [6] derivatives of 1,4-benzoquinone imine with sodium arenesulfinates. Depending on the initial quinone imine structure, 1,4-, 6,3-, 1,6-, or 6,1-addition products were obtained.…”

“…In all other cases, the corresponding 1,4-addition products predominated. Signals in the 1 H NMR spectra of the addition products were assigned taking into account our previous data [4][5][6]. In the 1 H NMR spectra of 1,4-addition products XIIIa-XIIIc, the 6-H proton in the aminophenol fragment resonated as a singlet at δ 7.08-7.18 ppm, the 2-H and 6-H protons of XIVa-XIVc gave doublets at δ 7.13-7.22 and 7.38-7.45, and the 3-H and 6-H signals of XVa-XVc were doublets in the regions δ 6.68-6.80 and 7.22-7.46 ppm.…”

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…The electron-withdrawing group on the panisidine moiety was well-tolerated rather than electrondonating substituent on p-anisidine. Similarly, Konovalova and co-workers [300][301][302] employed the nucleophilic addition of the quinone imine ketal intermediate with sodium arenesulnates to furnish 1,4-, 1,6-, and 6,1-addition products of N-arylsulfonyl, N-aroyl, and N-[arylsulfonylimino(phenyl)methyl] derivatives.…”