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Open AccessArticle

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

1
Department of Chemical and Molecular Engineering, Hanyang University,Ansan-si, Gyeonggi-do 15588, Korea
2
Korea Conformity Laboratories, Seoul 08503, Korea
3
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
*
Authors to whom correspondence should be addressed.
Int. J. Mol. Sci. 2019, 20(16), 4026; https://doi.org/10.3390/ijms20164026
Received: 28 June 2019 / Revised: 12 August 2019 / Accepted: 16 August 2019 / Published: 18 August 2019
(This article belongs to the Special Issue Solution Chemical Kinetics 2019)
A kinetic study was carried out on the solvolysis of o-nitrobenzyl bromide (o-isomer, 1) and p-nitrobenzyl bromide (p-isomer, 3), and o-nitrobenzoyl chloride (o-isomer, 2) in a wide range of solvents under various temperatures. In all of the solvents without aqueous fluoroalcohol, the reactions of 1 were solvolyzed at a similar rate to those observed for 3, and the reaction rates of 2 were about ten times slower than those of the previously studied p-nitrobenzoyl chloride (p-isomer, 4). For solvolysis in aqueous fluoroalcohol, the reactivity of 2 was kinetically more reactive than 4. The l/m values of the extended Grunwald–Winstein (G–W) equation for solvolysis of 1 and 2 in solvents without fluoroalcohol content are all significantly larger than unity while those in all the fluoroalcohol solvents are less than unity. The role of the ortho-nitro group as an intramolecular nucleophilic assistant (internal nucleophile) in the solvolytic reaction of 1 and 2 was discussed. The results are also compared with those reported earlier for o-carbomethoxybenzyl bromide (5) and o-nitrobenzyl p-toluenesulfonate (7). From the product studies and the activation parameters for solvolyses of 1 and 2 in several organic hydroxylic solvents, mechanistic conclusions are drawn. View Full-Text
Keywords: o-nitrobenzyl bromide; o-nitrobenzoyl chloride; ortho nitro group; Grunwald–Winstein equation; intramolecular nucleophilic assistance; solvolysis; nucleophilicity; ionizing power o-nitrobenzyl bromide; o-nitrobenzoyl chloride; ortho nitro group; Grunwald–Winstein equation; intramolecular nucleophilic assistance; solvolysis; nucleophilicity; ionizing power
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Park, K.-H.; Rhu, C.J.; Kyong, J.B.; Kevill, D.N. The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides. Int. J. Mol. Sci. 2019, 20, 4026.

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