Reactions of aryl 5-substituted-2-thiophenecarboxylates promoted by 4-Z-C6H4O-/4-Z-C6H4OH in 20 mol % DMSO(aq). Effect of nucleophile on acyl-transfer reaction

Sang Yong Pyun; Kyu Cheol Paik; Man So Han; Bong-Rae Cho

doi:10.1002/bkcs.10567

Reactions of aryl 5-substituted-2-thiophenecarboxylates promoted by 4-Z-C₆H₄O-/4-Z-C₆H₄OH in 20 mol % DMSO(aq). Effect of nucleophile on acyl-transfer reaction

Sang Yong Pyun, Kyu Cheol Paik, Man So Han, Bong-Rae Cho

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

Nucleophilic substitution reactions of 5-XC₄H₂(S)C(O)OC₆H₃-2-Y-4-NO₂ (1) promoted by 4-Z-C₆H₄O-/4-Z-C₆H₄OH in 20 mol % dimethyl sulfoxide (DMSO)(aq) have been studied kinetically. The reactions exhibited second-order kinetics with β_acyl = -2.52 to -2.83, ρ(x) = 2.81-3.16, β_nuc = 0.88-0.04 and β_lg = -0.94, respectively. The results have been interpreted with an addition-elimination mechanism in which the nucleophilic attack occurs in the rate-determining step. Comparison with existing data reveals that the ratedetermining step changes from the second to the first step by the change in the nucleophile from R₂NH/R₂NH₂ ⁺ to 4-Z-C₆H₄O-/4-Z-C₆H₄OH.

Original language	English
Pages (from-to)	2810-2814
Number of pages	5
Journal	Bulletin of the Korean Chemical Society
Volume	36
Issue number	12
DOIs	https://doi.org/10.1002/bkcs.10567
Publication status	Published - 2015 Dec 1

Keywords

Bronsted and hammett plots
Concerted and stepwise mechanism
Nucleophilic substitution

ASJC Scopus subject areas

Chemistry(all)

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10.1002/bkcs.10567

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Reactions of aryl 5-substituted-2-thiophenecarboxylates promoted by 4-Z-C₆H₄O-/4-Z-C₆H₄OH in 20 mol % DMSO(aq). Effect of nucleophile on acyl-transfer reaction. / Pyun, Sang Yong; Paik, Kyu Cheol; Han, Man So; Cho, Bong-Rae.

In: Bulletin of the Korean Chemical Society, Vol. 36, No. 12, 01.12.2015, p. 2810-2814.

Research output: Contribution to journal › Article › peer-review

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abstract = "Nucleophilic substitution reactions of 5-XC4H2(S)C(O)OC6H3-2-Y-4-NO2 (1) promoted by 4-Z-C6H4O-/4-Z-C6H4OH in 20 mol % dimethyl sulfoxide (DMSO)(aq) have been studied kinetically. The reactions exhibited second-order kinetics with βacyl = -2.52 to -2.83, ρ(x) = 2.81-3.16, βnuc = 0.88-0.04 and βlg = -0.94, respectively. The results have been interpreted with an addition-elimination mechanism in which the nucleophilic attack occurs in the rate-determining step. Comparison with existing data reveals that the ratedetermining step changes from the second to the first step by the change in the nucleophile from R2NH/R2NH2 + to 4-Z-C6H4O-/4-Z-C6H4OH.",

keywords = "Bronsted and hammett plots, Concerted and stepwise mechanism, Nucleophilic substitution",

author = "Pyun, {Sang Yong} and Paik, {Kyu Cheol} and Han, {Man So} and Bong-Rae Cho",

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AU - Pyun, Sang Yong

AU - Paik, Kyu Cheol

AU - Han, Man So

AU - Cho, Bong-Rae

PY - 2015/12/1

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N2 - Nucleophilic substitution reactions of 5-XC4H2(S)C(O)OC6H3-2-Y-4-NO2 (1) promoted by 4-Z-C6H4O-/4-Z-C6H4OH in 20 mol % dimethyl sulfoxide (DMSO)(aq) have been studied kinetically. The reactions exhibited second-order kinetics with βacyl = -2.52 to -2.83, ρ(x) = 2.81-3.16, βnuc = 0.88-0.04 and βlg = -0.94, respectively. The results have been interpreted with an addition-elimination mechanism in which the nucleophilic attack occurs in the rate-determining step. Comparison with existing data reveals that the ratedetermining step changes from the second to the first step by the change in the nucleophile from R2NH/R2NH2 + to 4-Z-C6H4O-/4-Z-C6H4OH.

AB - Nucleophilic substitution reactions of 5-XC4H2(S)C(O)OC6H3-2-Y-4-NO2 (1) promoted by 4-Z-C6H4O-/4-Z-C6H4OH in 20 mol % dimethyl sulfoxide (DMSO)(aq) have been studied kinetically. The reactions exhibited second-order kinetics with βacyl = -2.52 to -2.83, ρ(x) = 2.81-3.16, βnuc = 0.88-0.04 and βlg = -0.94, respectively. The results have been interpreted with an addition-elimination mechanism in which the nucleophilic attack occurs in the rate-determining step. Comparison with existing data reveals that the ratedetermining step changes from the second to the first step by the change in the nucleophile from R2NH/R2NH2 + to 4-Z-C6H4O-/4-Z-C6H4OH.

KW - Bronsted and hammett plots

KW - Concerted and stepwise mechanism

KW - Nucleophilic substitution

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