Water → 2-(bromomethyl)-5-fluoro-7-(methylsulfonyl)-4H-1,3-benzodioxine

HRID 452468Notes

Reaction equation

HRID 452468 reaction equation
[F:1][C:2]1[C:3]([CH2:13][OH:14])=[C:4]([OH:12])[CH:5]=[C:6]([S:8]([CH3:11])(=[O:10])=[O:9])[CH:7]=1.[Br:15][CH2:16][CH:17](OC)OC.OS(O)(=O)=O.O>C1COCC1>[Br:15][CH2:16][CH:17]1[O:12][C:4]2[CH:5]=[C:6]([S:8]([CH3:11])(=[O:10])=[O:9])[CH:7]=[C:2]([F:1])[C:3]=2[CH2:13][O:14]1

Participants

6

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 816722-Bromo-1,1-dimethoxyethaneHCID 668875163-Fluoro-2-(hydroxymethyl)-5-(methylsulfonyl)phenol

Product 1

HCID 668876212-(bromomethyl)-5-fluoro-7-(methylsulfonyl)-4H-1,3-benzodioxineYield 43.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

3-fluoro-2-(hydroxymethyl)-5-(methylsulfonyl)phenol (0.11 g, 0.52 mmol) was dissolved in THF (dry) (5 ml). 2-bromo-1,1-dimethoxyethane (0.63 ml, 5.2 mmol) was added followed by concentrated H2SO4 (1 ml). The mixture was heated at 60° C. for 1 h. Water was added and the mixture extracted with EtOAc twice. The combined extracts were washed with brine and concentrated. Purification by flash column chromatography (isooctane/EtOAc) gave the title compound (0.073 g). MS m/z (rel. intensity, 70 eV) 326 (M+, 8), 324 (M+, 8), 231 (17), 202 (bp), 139 (21), 95 (42), 75 (34).

Workup

  1. extractionthe mixture extracted with EtOAc twice
  2. washThe combined extracts were washed with brine
  3. concentrationconcentrated
  4. customPurification by flash column chromatography (isooctane/EtOAc)

Sources & evidence

ORD record
ord-919018b17fff4f24a466ce087ab54cd3
Source dataset
uspto-grants-2013_07
Patent number
US08492372B2

Reaction notes

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