TY - JOUR

T1 - Bromination of quinolin-2(1H)-ones fluorinated on the benzene moiety

AU - Verkhov, Fyodor K.

AU - Skolyapova, Alexandrina D.

AU - Krasnov, Vyacheslav I.

AU - Bagryanskaya, Irina Yu

AU - Andreev, Rodion V.

AU - Karpova, Elena V.

AU - Kalizhnikova, Evgenya E.

AU - Selivanova, Galina A.

N1 - The authors thank the Multi-Access Chemical Service Center SB RAS for spectral and analytical measurements, and Ministry of Science and Higher Education of the Russian Federation (Project FWUE-2022-0002 ) for financial support. The authors thank Ludmila Filatova for conducting a literary search. Публикация для корректировки.

PY - 2023/5

Y1 - 2023/5

N2 - Bromination of ten known fluorinated quinolin-2(1H)-ones by the KBrO3/HBr system is investigated. If there is no F atom in the position 6 of substrate, the Br atom is introduced into position 3 or 6 to form monobromo derivative, the second Br atom is introduced into the same positions leading to 3,6-dibromo product. If a F atom is in position 6, the 3-bromo product is initially obtained, which gives a 3,5-dibromo or 3,8-dibromo derivatives upon further bromination depending on the F atoms positions. In this case, when both positions 5 and 8 of 3-bromoquinolin-2(1H)-one are unsubstituted, the second Br atom is introduced into position 8. If there are more than two F atoms in the benzene moiety, the sole 3-bromo product is obtained. Relative (ΔE) energies of the considered σ−complexes estimated by DFT calculations for the reactions in question are consistent with the experimentally observed regioselectivity.

AB - Bromination of ten known fluorinated quinolin-2(1H)-ones by the KBrO3/HBr system is investigated. If there is no F atom in the position 6 of substrate, the Br atom is introduced into position 3 or 6 to form monobromo derivative, the second Br atom is introduced into the same positions leading to 3,6-dibromo product. If a F atom is in position 6, the 3-bromo product is initially obtained, which gives a 3,5-dibromo or 3,8-dibromo derivatives upon further bromination depending on the F atoms positions. In this case, when both positions 5 and 8 of 3-bromoquinolin-2(1H)-one are unsubstituted, the second Br atom is introduced into position 8. If there are more than two F atoms in the benzene moiety, the sole 3-bromo product is obtained. Relative (ΔE) energies of the considered σ−complexes estimated by DFT calculations for the reactions in question are consistent with the experimentally observed regioselectivity.

KW - Bromination

KW - Bromofluoroquinolin-2-(1H)-ones

KW - Fluorinated quinolin-2(1H)-ones

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85152885941&origin=inward&txGid=6f28541c51de92ac3687490412c252bd

UR - https://www.mendeley.com/catalogue/5e1d50fc-7de7-3cf2-b7a4-68266086d6bb/

U2 - 10.1016/j.jfluchem.2023.110132

DO - 10.1016/j.jfluchem.2023.110132

M3 - Article

VL - 268

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

SN - 0022-1139

M1 - 110132

ER -