Dimethyl Sulfoxide → HCID 53869744, compound

HRID 2394350Notes

Reaction equation

HRID 2394350 reaction equation
[OH-].[Na+].F[C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][N:5]=1.[C:13]([O:17][C:18](=[O:27])[CH2:19]SC1C=CC=CC=1)([CH3:16])([CH3:15])[CH3:14].C[S:29]([CH3:31])=O>>[N+:10]([C:7]1[C:6]([CH2:19][C:18]([O:17][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:27])=[N:5][C:4]([S:29][C:31]2[CH:4]=[CH:9][CH:8]=[CH:7][CH:6]=2)=[CH:9][CH:8]=1)([O-:12])=[O:11]

Participants

5

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 14798Sodium HydroxideHCID 952642-Fluoro-5-nitropyridineHCID 546353Acetic acid, (phenylthio)-, 1,1-dimethylethyl ester

Product 1

HCID 53869744HCID 53869744, compoundYield 11%

Procedure

To a mechanically stirred slurry of pulverized sodium hydroxide (16.0 g, 400 mmol) in DMSO (75 mL) was added dropwise a solution of 2-fluoro-5-nitropyridine (prepared as described by Finger and Starr, J. Am Chem. Soc., 81, 2674 (1959)) (5.7 g, 40 mmol) and t-butyl(phenylthio)acetate (9.0 g, 40 mmol) in DMSO (75 mL) while maintaining the temperature of the reaction mixture below 30° C. The mixture was allowed to stir at room temperature overnight and was then poured into ice/water. After adjustment of the pH to bout 2 with 1N HCl solution, the mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried (MgSO4) and concentrated in vacuo. The oily residue was subjected to flash chromatography on silica gel using 2:1 chloroform/hexane as eluant. Fractions containing the desired product were combined and concentrated to leave a yellow solid which was triturated with ether to leave t-butyl (3-nitro-6-phenylthio-2-pyridyl)acetate (1.5 g, 11%), m.p. 104°-107°.

Workup

  1. temperaturewhile maintaining the temperature of the reaction mixture below 30° C
  2. extractionAfter adjustment of the pH to bout 2 with 1N HCl solution, the mixture was extracted with ethyl acetate
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. additionFractions containing the desired product
  7. concentrationconcentrated
  8. customto leave a yellow solid which
  9. customwas triturated with ether

Sources & evidence

ORD record
ord-3d647a6d73214c049f4351a54437d2e8
Source dataset
uspto-grants-1998_09
Patent number
US05811432

Reaction notes

Loading…