Methanol → 4-Heptylbicyclo[3.3.0]octan-7-one

HRID 1789555Notes

Reaction equation

HRID 1789555 reaction equation
Cl[C:2]1(Cl)[C:8](=[O:9])[CH:7]2[CH:3]1[CH2:4][CH2:5][CH:6]2[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].[N+](=[CH2:20])=[N-].CO.CCOCC>C(O)(=O)C.[Zn]>[CH2:10]([CH:6]1[CH2:5][CH2:4][CH:3]2[CH:7]1[CH2:20][C:8](=[O:9])[CH2:2]2)[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]

Participants

7

Reactant 4

HCID 887MethanolHCID 3283Diethyl EtherHCID 9550DiazomethaneHCID 139240677,7-Dichloro-4-heptylbicyclo[3.2.0]heptan-6-one

Product 1

HCID 142041024-Heptylbicyclo[3.3.0]octan-7-one

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent3×

Conditions

Temperature
70 °C

Procedure

The procedure followed is the same as that described in Example 29 substituting the starting material from Example 34, 6,6-dichloro-2-(hept-1-yl)bicyclo[3.2.0]heptan-7-one {7,7-dichloro-4-heptylbicyclo[3.2.0]heptan-6-one} and isomers (14.2 g, 0.051 moles), an etheral diazomethane solution (175 ml), methanol (5 ml), and acetic acid (15 ml). After the acetic acid is added the solvent is removed under vacuum leaving a clear yellow oil. The crude product is then dissolved in acetic acid (100 ml) and stirred while zinc powder (29 g) is slowly added. The reaction is heated in a 70° C. water bath for 1 hour, after which time ether (500 ml) is added and the solution filtered. The filtrate is washed with brine (100 ml) and then with a solution of saturated bicarbonate. The ether layer is separated and dried over anhydrous sodium sulfate. The solvent is removed under vacuum leaving a clear yellow oil. The crude product is chromatographed on silica gel and subsequently kugelrohred under vacuum leaving a clear, colorless oil (4.3 g, 0.015 moles).

Workup

  1. customis removed under vacuum
  2. customleaving a clear yellow oil
  3. additionis slowly added
  4. filtrationthe solution filtered
  5. washThe filtrate is washed with brine (100 ml)
  6. customThe ether layer is separated
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe solvent is removed under vacuum
  9. customleaving a clear yellow oil
  10. customThe crude product is chromatographed on silica gel

Sources & evidence

ORD record
ord-c403607f8ccd43679d3b8e809a75d37e
Source dataset
uspto-grants-1987_08
Patent number
US04689345

Reaction notes

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