Sulfuric Acid → 2-(bromomethyl)-7-(methylsulfonyl)-4H-1,3-benzodioxine

HRID 452448Notes

Reaction equation

HRID 452448 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:5][C:4]=1[OH:13].[Br:14][CH2:15][CH:16](OC)OC.C1COCC1.OS(O)(=O)=O>O.CCOC(C)=O>[Br:14][CH2:15][CH:16]1[O:13][C:4]2[CH:5]=[C:6]([S:9]([CH3:12])(=[O:10])=[O:11])[CH:7]=[CH:8][C:3]=2[CH2:2][O:1]1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 8028TetrahydrofuranHCID 816722-Bromo-1,1-dimethoxyethaneHCID 668871582-(Hydroxymethyl)-5-(methylsulfonyl)phenol

Product 1

HCID 668864402-(bromomethyl)-7-(methylsulfonyl)-4H-1,3-benzodioxineYield 179.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

2-(hydroxymethyl)-5-(methylsulfonyl)phenol (3.3 g, 16.3 mmol), 2-bromo-1,1-dimethoxyethane (19.0 ml, 163 mmol), dry THF (30 ml) and concentrated H2SO4 (5 ml) were heated at 55° C. for 1 h. The reaction mixture was brought to ambient temperature and EtOAc and water were added. The phases were separated and the aqueous phase was extracted twice with EtOAc. The combined organic phases were dried (Na2SO4), filtered and evaporated to dryness to give an oil (9.0 g). The oil was crystallizing upon cooling. The product was washed with EtOAc, EtOH and DEE and afforded the pure title compound (4.0 g, 80%). MS m/z (rel. intensity, 70 eV) 308 (M+, 11), 306 (M+, 10), 213 (45), 184 (bp), 77 (35).

Workup

  1. customwas brought to ambient temperature
  2. customThe phases were separated
  3. extractionthe aqueous phase was extracted twice with EtOAc
  4. dry with materialThe combined organic phases were dried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated to dryness

Sources & evidence

ORD record
ord-1574c1ec7cd944f68096c2b86b47e47f
Source dataset
uspto-grants-2013_07
Patent number
US08492372B2

Reaction notes

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