Mono- and dinitration of pentafluorosulfanylbenzenes with [NO2][BF4], and substrate selectivity (PhSF5 vs PhCF3 and PhSF5 vs PhNO2) in competitive nitration | Health & Environmental Research Online (HERO)

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HERO ID

2844214

Reference Type

Journal Article

Title

Mono- and dinitration of pentafluorosulfanylbenzenes with [NO2][BF4], and substrate selectivity (PhSF5 vs PhCF3 and PhSF5 vs PhNO2) in competitive nitration

Author(s)

Okazaki, T; Laali, KK

Year

2014

Is Peer Reviewed?

Yes

Journal

Journal of Fluorine Chemistry
ISSN: 0022-1139
EISSN: 1873-3328

Volume

165

Page Numbers

96-100

Language

English

DOI

10.1016/j.jfluchem.2014.06.024

Web of Science Id

WOS:000341347800015

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-84904799800&doi=10.1016%2fj.jfluchem.2014.06.024&partnerID=40&md5=be2874fbf5cb586732fcc88dac7ee163
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Abstract

PhSF5 1 reacts with NO2+BF4-/TfOH in CH2Cl2 (DCM) at room temperature to give 1-nitro-3-(pentafluorosulfanyl)benzene 2 in near quantitative yield. The dinitro derivative 4 is synthesized from 2 by reaction with NO2+BF4-/TfOH at 70 degrees C. The p-MeC6H4SF5 is mononitrated at room temperature with NO2+BF4--/DCM and dinitrated with NO2+BF4-/TfOH. Substrate selectivity (k(PhSF5)/k(RPh)) in competitive nitration for PhSF5/PhCF3 and PhSF5/PhNO2 with NO2+BF4- in DCM at room temperature was determined at 21.3 and similar to 1 respectively. Relative stability of the corresponding benzenium ions were gauged by DFT from the isodesmic proton transfer reaction SF5-C6H6+ + R-C6H5 -> SF5-C6H5 + R-C6H6+ (R = CF3 and NO2). These studies indicate that reactivity of ArSF5 in SEAr is similar to ArNO2. (C) 2014 Elsevier B.V. All rights reserved.

Keywords

SF5-aromatics; Mono- and dinitration; NO2+BF4-/TfOH; Competitive nitration; Substrate selectivity; Isodesmic proton transfer