Journal article

Publication year: 2017

Pages: 2407-2413

Journal: The Journal of Organic Chemistry

Volume number: 82

Issue number: 5

ISSN: 0022-3263

DOI Link: https://doi.org/10.1021/acs.joc.6b02829

Publisher: American Chemical Society

Abstract: 

We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25–30 °C using N-hydroxyphthalimide
(NHPI) as radical initiator and commercially available
trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic
amounts of CBr₄ reduced the reaction times considerably due to the formation of chain-carrying ·CBr₃
radicals. Benzylic C–H chlorination affords moderate to good yields for
arenes carrying electron-withdrawing (50–85%) or weakly
electron-donating groups (31–73%); cyclic aliphatic substrates provide
low yields (24–38%). The products could be synthesized on a gram scale
followed by simple purification via distillation. We report the first
direct side-chain chlorination of 3-methylbenzoate affording methyl
3-(chloromethyl)benzoate, which is an important building block for the
synthesis of vasodilator taprostene.

Harvard Citation style: Combe, S., Hosseini, A., Parra, A. and Schreiner, P. (2017) Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid, The Journal of Organic Chemistry, 82(5), pp. 2407-2413. https://doi.org/10.1021/acs.joc.6b02829

APA Citation style: Combe, S., Hosseini, A., Parra, A., & Schreiner, P. (2017). Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid. The Journal of Organic Chemistry. 82(5), 2407-2413. https://doi.org/10.1021/acs.joc.6b02829