Benzoic acid, 4-fluoro-, ethyl ester → 4-[(1,1-Dimethylethyl)thio]benzoic acid

HRID 2204214Notes

Reaction equation

HRID 2204214 reaction equation
F[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8]CC)=[O:7])=[CH:4][CH:3]=1.[C:13]([S:17][Na])([CH3:16])([CH3:15])[CH3:14]>CN(C)C=O>[C:13]([S:17][C:2]1[CH:3]=[CH:4][C:5]([C:6]([OH:8])=[O:7])=[CH:11][CH:12]=1)([CH3:16])([CH3:15])[CH3:14]

Participants

4

Reactant 2

HCID 67976Benzoic acid, 4-fluoro-, ethyl esterHCID 178455544HCID 178455544, compound

Product 1

HCID 222172344-[(1,1-Dimethylethyl)thio]benzoic acid

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

Ethyl 4-fluorobenzoate (1.5 g, 8.9 mmol) and tert-butylsulfanylsodium (2.00 g, 17.8 mmol) were combined in N,N-dimethylformamide (10 mL). The reaction mixture was heated at 80° C. for 2 hours. A large amount of precipitate formed and an additional 15 mL of N,N-dimethylformamide was added and the reaction mixture was stirred for an additional 20 hours at 80° C. The reaction mixture was partitioned between ethyl acetate (100 mL) and water (100 mL). The organic layer was discarded, and the water layer was made acidic with 4M hydrochloric acid. The water layer was extracted two times with ethyl acetate. The combined extracts were dried over sodium sulfate, filtered, and evaporated to dryness to yield 4-(tert-butylthio)benzoic acid as a colorless oil. ESI-MS m/z calc. 210.3, found 211.1 (M+1)+. Retention time: 1.74 minutes (3 min run).

Workup

  1. customA large amount of precipitate formed
  2. customThe reaction mixture was partitioned between ethyl acetate (100 mL) and water (100 mL)
  3. extractionThe water layer was extracted two times with ethyl acetate
  4. dry with materialThe combined extracts were dried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated to dryness

Sources & evidence

ORD record
ord-ea0fcff4645b49949e6cf8f8018e0bbe
Source dataset
uspto-grants-2016_06
Patent number
US09365588B2

Reaction notes

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