The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halidesopen access
- Authors
- Park, Kyoung-Ho; Rhu, Chan Joo; Kyong, Jin Burm; Kevill, Dennis N.
- Issue Date
- Aug-2019
- Publisher
- Multidisciplinary Digital Publishing Institute (MDPI)
- Keywords
- o-nitrobenzyl bromide; o-nitrobenzoyl chloride; ortho nitro group; Grunwald-Winstein equation; intramolecular nucleophilic assistance; solvolysis; nucleophilicity; ionizing power
- Citation
- International Journal of Molecular Sciences, v.20, no.16, pp.1 - 12
- Indexed
- SCIE
SCOPUS
- Journal Title
- International Journal of Molecular Sciences
- Volume
- 20
- Number
- 16
- Start Page
- 1
- End Page
- 12
- URI
- https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/2383
- DOI
- 10.3390/ijms20164026
- ISSN
- 1661-6596
- Abstract
- 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.
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