Pyridine → Acetic Acid 7-isopropylidene-2,5-dimethyl-bicyclo[2.2.1]hept-5-en-2-ylmethyl Ester

HRID 1828675Notes

Reaction equation

HRID 1828675 reaction equation
[C:1](=[C:4]1[CH:8]2[C:9]([CH3:11])=[CH:10][CH:5]1[C:6]([CH2:13][OH:14])([CH3:12])[CH2:7]2)([CH3:3])[CH3:2].N1C=CC=CC=1.[C:21](Cl)(=[O:23])[CH3:22]>CN(C1C=CN=CC=1)C.ClCCl.O>[C:1](=[C:4]1[CH:8]2[C:9]([CH3:11])=[CH:10][CH:5]1[C:6]([CH2:13][O:14][C:21](=[O:23])[CH3:22])([CH3:12])[CH2:7]2)([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 1049PyridineHCID 6367Acetyl chlorideHCID 22057677(7-Isopropylidene-2,5-dimethyl-bicyclo[2.2.1]hept-5-en-2-yl)-methanol

Product 1

HCID 69037269Acetic Acid 7-isopropylidene-2,5-dimethyl-bicyclo[2.2.1]hept-5-en-2-ylmethyl EsterYield 80.6%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of (7-Isopropylidene-2,5-dimethyl-bicyclo[2.2.1]hept-5-en-2-yl)-methanol (4.32 g, 22.5 mmol), pyridine (3.55 g, 45 mmol) and DMAP (50 mg) in dichloromethane (50 ml) was added acetyl chloride (2.47 g, 31.5 mmol) with cooling. The mixture was stirred at room temperature for 1 h and was then diluted with water and extracted with pentane (3×80 ml). the organic phase was washed with 1N HCl, water and brine, dried (MgSO4) and concentrated in vacuo. The residue was purified by chromatography on silica gel (hexane:MTBE=9:1) to yield 4.25 g of a colorless oil as a mixture of isomers. Odor description: cedarwood oil, carrot, verdyl, musky. 1H-NMR (CDCl3, 400 MHz): 5.93–5.72 (m, 1H), 3.94–3.73 (m, 2H), 3.10–2.78 (m, 2H), 2.09–2.03 (m, 3H), 1.85–1.53 (m, 9H1.50–1.15 (m, 2H), 1.09/0.97/0.92/0.89 (4s, 3H) ppm. GC/MS (EI): main isomer: 234 (M+, trace), 159 (3), 120 (100), 105 (46), 91 (11), 77 (7), 43 (15), IR (atr): 2927m, 2726w, 1741s, 1446m, 1369m, 1233vs, 1031s, 986m, 802m cm−1.

Workup

  1. temperaturewith cooling
  2. extractionextracted with pentane (3×80 ml)
  3. washthe organic phase was washed with 1N HCl, water and brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by chromatography on silica gel (hexane:MTBE=9:1)

Sources & evidence

ORD record
ord-4e05dd502d1a4d1280fee23f3c6e20cb
Source dataset
uspto-grants-2006_06
Patent number
US07060664B2

Reaction notes

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