Synlett 2020; 31(20): 2046-2048
DOI: 10.1055/s-0040-1707291
letter

Unexpected Substitution Reaction of 1,1-Dichloro-2,2,2-trifluoroethane (HCFC-123) with Phenolates

Xiao-Jun Tang
,
Qing-Yun Chen
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, 200032, P. R. of China   Email: txj_seu@126.com
› Author Affiliations
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



Publication History

Received: 06 August 2020

Accepted after revision: 26 August 2020

Article published online:
22 September 2020

© 2020. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References and Notes

  • 1 Tang X.-J, Chen Q.-Y. Chem. Sci. 2012; 3: 1694
  • 2 Tang X.-J, Chen Q.-Y. J. Fluorine Chem. 2015; 169: 1
  • 3 Long Z.-Y, Chen Q.-Y. J. Fluorine Chem. 1998; 91: 95
  • 4 Lee H, Kim KH, Kim H, Lee SD, Kim HS. J. Fluorine Chem. 2004; 125: 95
  • 5 Tang X.-J, Thomoson CS, Dolbier WR. Jr. Org. Lett. 2014; 16: 4594
  • 6 Stahly GP. J. Fluorine Chem. 1989; 43: 53
  • 7 Xu Y, Dolbier WR, Rong XX. J. Org. Chem. 1997; 62: 1576
  • 8 Tang X.-J, Chen Q.-Y. Org. Lett. 2012; 14: 6214
  • 9 Han E.-J, Sun Y, Shen Q, Chen Q.-Y, Guo Y, Huang YG. Org. Chem. Front. 2015; 2: 1379
  • 10 Zheng J, Chen Q.-Y, Sun K, Huang Y, Guo Y. Tetrahedron Lett. 2016; 57: 5757
  • 11 Han E.-J, Guo Y, Chen Q.-Y. Youji Huaxue 2017; 37: 1714
  • 12 Luo J, Han E.-J, Shen Q, Huang M, Huang Y, Liu H.-M, Wang W, Chen Q.-Y, Guo Y. Org. Process Res. Dev. 2016; 20: 1988
  • 13 Subramanian R, Johnson F. J. Org. Chem. 1985; 50: 5430
  • 14 Li X.-y, Pan H.-q, Jiang X.-k, Zhan Z.-y. Angew. Chem. Int. Ed. 1985; 24: 871
  • 15 Li X.-y, Jiang X.-k, Pan H.-q, Hu J.-s, Fu W.-m. Pure Appl. Chem. 1987; 59: 1015
  • 16 Tarrant P, Brown HC. J. Am. Chem. Soc. 1951; 73: 5831
  • 17 Fukui H, Sanechika K.-i, Watanabe M, Ikeda M. J. Fluorine Chem. 2000; 101: 91
  • 18 Fukui H, Muruta H, Sanechika K.-i, Ikeda M. J. Fluorine Chem. 2000; 103: 129
  • 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).