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

A kinetic study was carried out on the solvolysis of -nitrobenzyl bromide ( -isomer, ) and -nitrobenzyl bromide ( -isomer, ), and -nitrobenzoyl chloride ( -isomer, ) in a wide range of solvents under various temperatures. In all of the solvents without aqueous fluoroalcohol, the reactions of were so...

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Bibliographic Details
Published in:International journal of molecular sciences 2019-08, Vol.20 (16), p.4026
Main Authors: Park, Kyoung-Ho, Rhu, Chan Joo, Kyong, Jin Burm, Kevill, Dennis N
Format: Article
Language:English
Subjects:
Acetone
Activation
Binary mixtures
Chloride
Chlorides
Ethanol
Halides
Hydrolysis
Isomers
Nitrobenzenes - chemistry
Sensitivity
Solvents
Solvolysis
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Summary:A kinetic study was carried out on the solvolysis of -nitrobenzyl bromide ( -isomer, ) and -nitrobenzyl bromide ( -isomer, ), and -nitrobenzoyl chloride ( -isomer, ) in a wide range of solvents under various temperatures. In all of the solvents without aqueous fluoroalcohol, the reactions of were solvolyzed at a similar rate to those observed for , and the reaction rates of were about ten times slower than those of the previously studied -nitrobenzoyl chloride ( -isomer, ). For solvolysis in aqueous fluoroalcohol, the reactivity of was kinetically more reactive than . The values of the extended Grunwald-Winstein (G-W) equation for solvolysis of and 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 -nitro group as an intramolecular nucleophilic assistant (internal nucleophile) in the solvolytic reaction of and was discussed. The results are also compared with those reported earlier for -carbomethoxybenzyl bromide ( ) and -nitrobenzyl -toluenesulfonate ( ). From the product studies and the activation parameters for solvolyses of and in several organic hydroxylic solvents, mechanistic conclusions are drawn.
ISSN:1422-0067
1661-6596
1422-0067
DOI:10.3390/ijms20164026