Water → 6-Fluoro-3-methyl-4-trifluoromethane-sulfonyloxynaphthalene-2-carboxylic acid methyl ester

HRID 1644746Notes

Reaction equation

HRID 1644746 reaction equation
FC(F)(F)S([O:6][S:7]([C:10]([F:13])([F:12])[F:11])(=[O:9])=[O:8])(=O)=O.[CH3:16][O:17][C:18]([C:20]1[C:29]([CH3:30])=[C:28](O)[C:27]2[C:22](=[CH:23][CH:24]=[C:25]([F:32])[CH:26]=2)[CH:21]=1)=[O:19].N1C=CC=CC=1.O>ClCCl.CCCCCC.C(OCC)(=O)C>[CH3:16][O:17][C:18]([C:20]1[C:29]([CH3:30])=[C:28]([O:6][S:7]([C:10]([F:11])([F:12])[F:13])(=[O:8])=[O:9])[C:27]2[C:22](=[CH:23][CH:24]=[C:25]([F:32])[CH:26]=2)[CH:21]=1)=[O:19]

Participants

8

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 593265736-Fluoro-4-hydroxy-3-methyl-naphthalene-2-carboxylic acid methyl ester

Product 1

HCID 593508186-Fluoro-3-methyl-4-trifluoromethane-sulfonyloxynaphthalene-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Trifluoromethanesulfonic anhydride (3.52 mL, 20.8 mmol) was added drop-wise over a period of 30 minutes to a 0° C. solution of 6-fluoro-4-hydroxy-3-methyl-naphthalene-2-carboxylic acid methyl ester (3.75 g, 16.0 mmol) in dichloromethane (120 mL) and pyridine (1.95 mL, 24.2 mmol). The resulting mixture was allowed to warm slowly to room temperature with stirring, and the reaction mixture was stirred at room temperature for 3.5 hours. After this time, the reaction mixture was cooled to 0° C. Water (150 mL) was added, and the organic phase was separated. The organic phase was dried over Na2SO4, filtered, and concentrated to afford a brown solid. Flash chromatography (Aspire FlashReady™, 50 μm, 10%-18% ethyl acetate in hexane) gave 6-fluoro-3-methyl-4-trifluoromethane-sulfonyloxynaphthalene-2-carboxylic acid methyl ester as 4.52 g (77%) of a yellow, crystalline solid. HRMS (EI+) cald. for C14H10F4O5S [M+] 366.0185, obsd. 366.0186.

Workup

  1. stirringthe reaction mixture was stirred at room temperature for 3.5 hours
  2. temperatureAfter this time, the reaction mixture was cooled to 0° C
  3. customthe organic phase was separated
  4. dry with materialThe organic phase was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto afford a brown solid

Sources & evidence

ORD record
ord-03c195f8445846a1a039e753df7bd3c4
Source dataset
uspto-grants-2012_02
Patent number
US08124629B2

Reaction notes

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