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

HRID 2261427ノート

反応式

HRID 2261427 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-ca6fd665971f4b37a415754f560237dc
出典データセット
uspto-grants-2010_12
特許番号
US07846964B2

反応ノート

読み込み中…