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Orientation in Aromatic Nitration Reactions

Roberts, John D. and Sanford, Janet K. and Sixma, F. L. J. and Cerfontain, H. and Zagt, R. (1954) Orientation in Aromatic Nitration Reactions. Journal of the American Chemical Society, 76 (18). pp. 4525-4534. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20151022-083817789

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Abstract

The isotope dilution method has been employed to determine isomer distributions in the nitration of chloro-, bromo- and iodobenzenes and the relative reactivity of iodobenzene with respect to benzene. For nitration at 25º, the following isomer distributions were found: chlorobenzene, ortho 29.6 ± 1.7%, meta 0.9 ± 0.0%, and para 69.5 ± 1.7%; bromobenzene, ortho 36.5 ± 1.7%, meta 1.2 ± 0.l%, and para 62.4 ± 2.8%; iodobenzene, ortho 38.3 ± 2.0%, meta 1.8 ± 0.3%, and para 59.7 ± 2.0%. The reactivity of iodobenzene relative to benzene at 25º was 0.13 in acetic anhydride and 0.22 in nitromethane. The degree of correlation of the nitration reactivities of benzene derivatives with Hammett σ-constants is discussed. Deviations from the Hammett relationship are interpreted in terms of important contributions of transition-state resonance.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja01647a005DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja01647a005PublisherArticle
Additional Information:© 1954 American Chemical Society. Received March 8, 1954. Supported in part by the joint program of the Office of Naval Research and the U. S. Atomic Energy Commission; also supported in part by a grant from the van't Hoff Fund of the Koninklijke Ned. Akademie van Wetenschappen. Presented before the Division of Organic Chemistry at the New York meeting of the American Chemical Society, September 13, 1954.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
Atomic Energy CommissionUNSPECIFIED
Koninklijke Ned. Akademie van Wetenschappen van't Hoff fundUNSPECIFIED
Record Number:CaltechAUTHORS:20151022-083817789
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151022-083817789
Official Citation:Orientation in Aromatic Nitration Reactions John D. Roberts, Janet K. Sanford, F. L. J. Sixma, H. Cerfontain, and R. Zagt Journal of the American Chemical Society 1954 76 (18), 4525-4534 DOI: 10.1021/ja01647a005
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61405
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Oct 2015 18:00
Last Modified:22 Oct 2015 18:00

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