Water → HCID 67516104, compound

HRID 2173398Notes

Reaction equation

HRID 2173398 reaction equation
[CH3:1][S:2][C:3]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:4]=1[C:5](O)=O.[OH2:15].C1[CH2:20][O:19]CC1>CN(C=O)C.O1CCOCC1.[N+]([O-])([O-])=O.[Ag+]>[CH3:1][S:2][C:3]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:4]=1[CH2:5][C:20]([OH:19])=[O:15]

Participants

7

Reactant 3

HCID 962WaterHCID 8028TetrahydrofuranHCID 205008952-(Methylthio)-4-nitrobenzoic acid

Product 1

HCID 67516104HCID 67516104, compound

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 24470Silver NitrateCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-(methylsulfanyl)-4-nitrobenzoic acid (5.3 g, 24.9 mmol) in 50 mL of THF was treated with (CoCL)2 (17.5 ml) and then DMF (2 drops). After stirring at room temperature for 2 hours, the mixture was evaporated. The residue was dissolved in 50 mL of DCM and added a solution of CH2N2 in 80 mL Et2O at 0° C. and stirred overnight. After the reaction was completed, the Et2O was partly evaporated and the product (3.7 g) filtered. A solution of the product (3.7 g, 15.6 mmol) in 90 mL dioxane was treated at 50° C. with 10 mL of water and added over 30 min with a suspension of Ag2O prepared from 3.98 g AgNO3. The mixture was stirred for 30 min at 85° C. and cooled. The precipitated product was filtered. It was decomposed with hydrochloric acid and the released acid was extracted with EtOAc. The combined organic layers were washed with 5% NaHCO3. Then the aqueous layer was acidified to pH=1˜2, extracted with EtOAc. The combined organic phase was washed with brine, dried over anhydrous Na2SO4 and concentrated to afford [2-(methylsulfanyl)-4-nitrophenyl]acetic acid. 1H-NMR (400 MHz, MeOD) δ ppm 8.06˜8.07 (m, 1H), 7.93˜7.96 (m, 1H), 7.44 (d, J=8.6 Hz, 1H), 3.82 (s, 2H), 2.56 (s, 3H).

Workup

  1. customthe mixture was evaporated
  2. dissolutionThe residue was dissolved in 50 mL of DCM
  3. additionadded a solution of CH2N2 in 80 mL Et2O at 0° C.
  4. stirringstirred overnight
  5. customthe Et2O was partly evaporated
  6. filtrationthe product (3.7 g) filtered
  7. additionadded over 30 min with a suspension of Ag2O
  8. stirringThe mixture was stirred for 30 min at 85° C.
  9. temperaturecooled
  10. filtrationThe precipitated product was filtered
  11. extractionthe released acid was extracted with EtOAc
  12. washThe combined organic layers were washed with 5% NaHCO3
  13. extractionextracted with EtOAc
  14. washThe combined organic phase was washed with brine
  15. dry with materialdried over anhydrous Na2SO4
  16. concentrationconcentrated

Sources & evidence

ORD record
ord-02adc51bf83a4f66a481ab68b87a90ea
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

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