Water → (1S,3R,4R,6R)-4-Bromo-3,7,7-trimethylbicyclo[4.1.0]heptan-3-ol

HRID 1821128Notes

Reaction equation

HRID 1821128 reaction equation
[CH:1]12[C:7]([CH3:9])([CH3:8])[CH:6]1[CH2:5][CH:4]=[C:3]([CH3:10])[CH2:2]2.C([O-])([O-])=O.[Ca+2].[Br:16]N1C(=O)CCC1=O.[OH2:24]>O1CCOCC1>[Br:16][C@@H:4]1[CH2:5][C@@H:6]2[C@@H:1]([C:7]2([CH3:9])[CH3:8])[CH2:2][C@@:3]1([CH3:10])[OH:24]

Participants

6

Reactant 4

HCID 962Water2×HCID 10112Calcium CarbonateHCID 260493-CareneHCID 67184N-bromobutanimide

Product 1

HCID 13860085(1S,3R,4R,6R)-4-Bromo-3,7,7-trimethylbicyclo[4.1.0]heptan-3-ol

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a suspension of (+)-3-carene (82 g, 0.6 mol) and CaCO3 (80 g, 0.8 mol) in water (300 mL) and dioxan (600 mL) is added N-bromosuccinimide (142 g, 0.8 mol). The mixture is stirred at rt for 1 h, diluted with water (1500 mL) and extracted with diethyl ether (500 mL). The organic extract is washed with water (3×1000 mL) and 5% aq. Na2S2O3 (2×500 mL), and dried over Na2SO4. The solvent is removed under reduced pressure and the crude product is purified by column chromatography on silica gel eluting with hexane/EA 4:1 to yield (1S,3R,4R,6R)-4-bromo-3,7,7-trimethyl-bicyclo[4.1.0]heptan-3-ol (48.3 g) as a beige solid. 1H NMR (CDCl3): δ 4.05 (dd, J=7.6, 10.6 Hz, 1H), 2.48-2.36 (m, 2H), 2.20 (dd, J=10.0, 14.7 Hz, 1H), 1.42-1.38 (m, 1H), 1.36 (s, 3H), 1.02 (s, 3H), 0.98 (s, 3H), 0.90-0.80 (m, 1H), 0.72-0.66 (m, 1H).

Workup

  1. extractionextracted with diethyl ether (500 mL)
  2. extractionThe organic extract
  3. washis washed with water (3×1000 mL) and 5% aq. Na2S2O3 (2×500 mL)
  4. dry with materialdried over Na2SO4
  5. customThe solvent is removed under reduced pressure
  6. customthe crude product is purified by column chromatography on silica gel eluting with hexane/EA 4:1

Sources & evidence

ORD record
ord-6ac11fca1a72426aaf30b8fdba3ab2ec
Source dataset
uspto-grants-2009_10
Patent number
US07605269B2

Reaction notes

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