Nucleophilic Substitution Reactions of 2,4‐Dinitrophenyl X‐Substituted‐Benzenesulfonates and Y‐Substituted‐Phenyl 4‐Nitrobenzenesulfonates with Azide Ion: Regioselectivity and Reaction Mechanism

Moon, Ji‐Hyun; Kim, Min-young; Han, Sang M.; Um, Ik‐Hwan

doi:10.1002/bkcs.10259

Cited by 3 publications

(9 citation statements)

References 62 publications

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“…A similar result has been reported for the reactions of 1a–1f with weakly basic

; e.g ., reactions of substrates possessing an EWG produced mainly the SO bond fission products, while those of substrates bearing an EDG yielded mostly the CO bond fission products . In contrast, we have previously reported that the corresponding reactions with strongly basic C 2 H 5 O  in anhydrous ethanol proceed exclusively through the SO bond fission .…”

Section: Introductionmentioning

confidence: 77%

“…The

values calculated in this way are summarized in Tables and for the reactions of 1a–1f and 2a–2g , respectively. The

values reported previously for the corresponding reactions with weakly basic

are also listed for comparison.…”

Section: Resultsmentioning

confidence: 99%

“…The reactions of 1a–1f with a weakly basic

have been suggested to proceed through the SO and CO bond fission competitively . The fraction of the CO bond fission has been reported to increase significantly as the substituent X in the benzenesulfonyl moiety changes from a strong EWG to an EDG ( e.g ., the percentage of C–O bond fission increases from 16 to 87% as X changes from 4‐NO 2 to 4‐MeO, respectively) . Accordingly, the CO bond fission becomes the major reaction pathway when the substituent X is an EDG.…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Figure , the Yukawa–Tsuno plot for the reactions of 1a–1f with OH  exhibits excellent linearity ( R 2 = 0.9998) with ρ X = 2.09 and r = 0.41. A similar linear Yukawa–Tsuno plot has been reported for the corresponding reactions with

( e.g ., R 2 = 0.999, ρ X = 1.72 and r = 0.40)

\log k^{X} true/ k^{H} = ρ_{X} ([], σ_{X}^{o} + r ((), σ_{X}^{+} - σ_{X}^{o}))

…”

Section: Resultsmentioning

confidence: 99%

“…Our study has now been extended to alkaline hydrolysis of 1a–1f and Y‐substituted phenyl 4‐nitrobenzenesulfonates ( 2a–2g ) in 80 mol% H 2 O/20 mol% DMSO at 25.0 ± 0.1 °C to obtain further information on the reaction mechanism (Scheme ). The kinetic results obtained from the current study have been compared with those reported recently for the corresponding reactions with weakly basic

to investigate effects of changing the nucleophile from the azide ion to the hydroxide ion on reactivity and TS structures. Nucleophilic substitution reactions of 1a–1f and 2a–2g with strongly basic C 2 H 5 O  in anhydrous ethanol have previously been carried out to investigate the effects of the alkali metal ions on reactivity ( e.g ., catalysis or inhibition) .…”

Section: Introductionmentioning

confidence: 99%

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