4-Fluoro-3-(morpholine-4-sulfonyl)benzoic acid → 4-Mercapto-3-(morpholine-4-sulfonyl)-benzoic Acid

HRID 277572Notes

Reaction equation

HRID 277572 reaction equation
O.[SH-:2].[Na+].F[C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][C:6]=1[S:14]([N:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1)(=[O:16])=[O:15]>CN(C=O)C>[SH:2][C:5]1[CH:13]=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[CH:7][C:6]=1[S:14]([N:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1)(=[O:16])=[O:15]

Participants

4

Reactant 2

HCID 6927164-Fluoro-3-(morpholine-4-sulfonyl)benzoic acidHCID 16211346Sodium hydrosulfide hydrate

Product 1

HCID 226290394-Mercapto-3-(morpholine-4-sulfonyl)-benzoic AcidYield 89.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

Sodium hydrosulfide monohydrate (237 mg, 4.3 mmol) was added to a solution of 4-fluoro-3-(morpholine-4-sulfonyl)-benzoic acid (Example 6, 350 mg, 1.2 mmol) in DMF (15 mL) and the reaction mixture was heated at 60° C. for 20 hours under N2. After cooling to room temperature and quenching with 2M HCl, the reaction mixture was partitioned between ethyl acetate and water. Further extraction of the aqueous layer with ethyl acetate, combination of all organic layers, drying and concentration provided a white powder (326 mg, 89% yield): 1HNMR DMSO-d6) δ2.99 (t, J=4 Hz, 4H), 3.58 (t, J=4. Hz, H), 7.48 (d, J=8 Hz,1H), 7.87 (dd, J=8, 2 Hz, 1H), 8.29 (d, J=2 Hz, 1H), 13.20 (s, 1H): MS (ESI) [M−H]− m/z 304.

Workup

  1. temperatureAfter cooling to room temperature
  2. customquenching with 2M HCl
  3. customthe reaction mixture was partitioned between ethyl acetate and water
  4. extractionFurther extraction of the aqueous layer with ethyl acetate, combination of all organic layers
  5. customdrying
  6. concentrationconcentration

Sources & evidence

ORD record
ord-e294ca167e124d8e8f95b243a2f7dcb4
Source dataset
uspto-grants-2002_03
Patent number
US06355633B1

Reaction notes

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