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J. Su et al.
Letter
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the rough findings of this idea before the optimization. In the
patent, the activation of NCS using CuCl2·2H2O, AlCl3, ZnCl2 or
FeCl3 (1–5 equiv) and the chlorination reactions to afford 2a, 2c,
and 2d are described, however, optimized reaction conditions
for full conversion of the starting materials are not specified.
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coumarin with either NCS or CuCl2 alone in refluxing acetoni-
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(26) 3,7-Dichloro-2H-chromen-2-one (2b) – Typical Procedure
To a 50 mL round-bottom flask, 7-chloro coumarin (180.6 mg, 1
mmol), NCS (935.2 mg, 7 mmol), CuCl2·2H2O (2387 mg, 14
mmol), and 20 mL anhydrous MeCN were added and refluxed
until the reaction completed. The cooled mixture was concen-
trated in vacuum, dispensed in 25 mL 5% NaHSO3 aqueous solu-
tion and extracted with 25 mL EtOAc for three times. The
organic layer was combined, washed with 10 mL water and
dried over anhydrous Na2SO4. After the solvent was removed,
the crude product was purified by silica gel column chromatog-
raphy to afford 96.2 mg 2b (44.9%).
(12) Kim, K. M.; Chung, K. H.; Kim, J. N.; Ryu, E. K. Synthesis 1993,
283.
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Synth. Commun. 2009, 39, 215.
3,7-Dichloro-2H-chromen-2-one (2b)
White solid, mp 123–124 ℃ (acetone/PE, 2:1, V/V). 1H NMR (600
MHz, CDCl3): δ = 7.84 (s, 1 H), 7.40 (d, J = 8.3 Hz, 1 H), 7.38 (d, J =
1.9 Hz, 1 H), 7.30 (dd, J = 8.3, 1.9 Hz, 1 H). 13C NMR (151 MHz,
CDCl3): δ = 156.6, 152.9, 139.3, 137.9, 128.0, 125.7, 122.5, 117.4,
117.2, 100.0. IR (KBr): νmax = 3103, 3061, 3040, 1736, 1720,
1702, 1604, 1484, 1403, 1348, 1318, 1245, 1206, 1144, 1123,
1077, 998, 969, 939, 916, 865, 825, 752, 681, 617, 595, 462 cm–1
.
HRMS (ESI): m/z calcd for C9H5Cl2O2 [M + H] (35Cl): 214.9661;
found: 214.9661.
(18) Racys, D. T.; Sharif, S. A. I.; Pimlott, S. L.; Sutherland, A. J. Org.
Chem. 2016, 81, 772.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E