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Synlett 2020; 31(20): 2046-2048
DOI: 10.1055/s-0040-1707291
DOI: 10.1055/s-0040-1707291
letter
Unexpected Substitution Reaction of 1,1-Dichloro-2,2,2-trifluoroethane (HCFC-123) with Phenolates
We thank the Chinese Academy of Science, the National Natural Science Foundation of China (21032006), and the 973 Program of China (2012CBA01200) for the financial support.
Abstract
An unexpected substitution reaction of HCFC-123 with phenolates is reported. During the reaction, fluorine atoms in HCFC-123 are removed one by one in the presence of phenolates.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707291.
- Supporting Information
Publication History
Received: 06 August 2020
Accepted after revision: 26 August 2020
Article published online:
22 September 2020
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- 19 (2,2-Dichloro-1,1-difluoroethoxy)benzene (2a): Typical Procedure A 20 mL Schlenk tube was charged with DMF (10 mL) and 1a (5 mmol, 470 mg). KOH (5 mmol, 280 mg) was added, and the mixture was stirred at 40 °C until the KOH disappeared. The mixture was then cooled to r.t. Precooled HCFC-123 (10 mmol, 1.52 g) was added to the solution, and the mixture was stirred at 90 °C for 2 h, then cooled to r.t. The mixture was then poured into Et2O (100 mL), washed with H2O, dried (Na2SO4), and concentrated by rotary evaporation under vacuum. The residue was purified by flash column chromatography [silica gel, PE–CH2Cl2 (20:1)] to give a colorless oil; yield: 994 mg (88%). 1H NMR (300 MHz, CDCl3): δ = 7.35–7.40 (m, 2 H), 7.21–7.29 (m, 3 H), 5.91 (t, J = 4.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 149.5, 129.6, 126.4, 121.7, 119.7 (t, J = 270 Hz), 67.8 (t, J = 42 Hz). 19F NMR (282 MHz, CDCl3): δ = –80.2 (d, J = 5.8 Hz). MS (EI): m/z (%) = 226 (M+, 21.51), 77 (100), 143 (50.87), 65 (38.96), 94 (30.34), 226 (21.51).