Water → 6-fluoro-2,2-dimethyl-8-[(phenylmethyl)oxy]-4H-1,3-benzodioxine

HRID 253278Notes

Reaction equation

HRID 253278 reaction equation
[F:1][C:2]1[CH:13]=[C:12]([OH:14])[C:5]2[O:6][C:7]([CH3:11])([CH3:10])[O:8][CH2:9][C:4]=2[CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:21](Br)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.O>CN(C=O)C>[F:1][C:2]1[CH:13]=[C:12]([O:14][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:5]2[O:6][C:7]([CH3:11])([CH3:10])[O:8][CH2:9][C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 668906486-Fluoro-2,2-dimethyl-4H-1,3-benzodioxin-8-ol

Product 1

HCID 668895716-fluoro-2,2-dimethyl-8-[(phenylmethyl)oxy]-4H-1,3-benzodioxineYield 74.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 6-fluoro-2,2-dimethyl-4H-1,3-benzodioxin-8-ol (21.4 g, 108 mmol) in DMF (200 mL) was treated with cesium carbonate (70.4 g, 216 mmol) and benzyl bromide (14.1 mL, 119 mmol) for 1 h 45 min at rt. Water was added and the resulting aqueous mixture was extracted twice with ethyl acetate. The organic extracts were combined, washed with brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was recrystallized from ethanol. The recovered white crystalline product was rinsed with hexanes providing 6-fluoro-2,2-dimethyl-8-[(phenylmethyl)oxy]-4H-1,3-benzodioxine (23.04 g, 80 mmol, 74% yield). 1H NMR (400 MHz, CDCl3): δ7.43-7.29 (m, 5H), 6.51 (dd, 1H), 6.31 (dd, 1H), 5.15 (s, 2H), 4.80 (s, 2H), 1.59 (s, 6H); GCMS for C17H17FO3: 288 (M+).

Workup

  1. extractionthe resulting aqueous mixture was extracted twice with ethyl acetate
  2. washwashed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was recrystallized from ethanol
  7. washThe recovered white crystalline product was rinsed with hexanes

Sources & evidence

ORD record
ord-3abe555692124da0ab1de6f5fc70d927
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

Loading…