Citric Acid → HCID 72750593, compound

HRID 1821129Notes

Reaction equation

HRID 1821129 reaction equation
[H-].[Na+].[C:3](OC)(=[O:5])[CH3:4].[CH3:8][C:9]1([CH3:16])[C@@H:14]2[C@H:10]1[CH2:11][C:12](=[O:15])[CH2:13]2.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCOCC1>[C:3]([CH:13]1[C:12](=[O:15])[CH2:11][CH:10]2[CH:14]1[C:9]2([CH3:16])[CH3:8])(=[O:5])[CH3:4]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 6584Methyl AcetateHCID 24758Sodium hydrideHCID 14138962HCID 14138962, compound

Product 1

HCID 72750593HCID 72750593, compoundYield 147.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a suspension of NaH (873 mg 55% dispersion in mineral oil, 20 mmol, washed with dioxane prior to use) in dioxane (15 mL) is added methyl acetate (2.22 g, 30 mmol). The suspension is stirred for 5 min at rt and a solution of (1S,5R)-6,6-dimethyl-bicyclo[3.1.0]hexan-3-one (1.24 g, 10 mmol) in dioxane (5 mL) is added. The reaction mixture is stirred at 65° C. overnight. The mixture is poured onto cold 10% aq. citric acid solution (75 mL) and extracted with DCM (3×75 mL). The organic extracts are washed with water, dried over MgSO4 and evaporated to give crude racemic (1R, 2R, 5R)-2-acetyl-6,6-dimethyl-bicyclo[3.1.0]hexan-3-one (2.45 g, contains dioxane) as a dark yellow liquid. 1H NMR (CDCl3): δ 2.61 (dd, J=7.3, 19.6 Hz, 1H), 2.34-2.20 (m, 1H), 2.01 (s, 3H), 1.72 (d, J=8.2 HZ, 1H), 1.40-1.20 (m, 2H), 1.09 (s, 3H), 0.81 (s, 3H).

Workup

  1. washwashed with dioxane
  2. stirringThe reaction mixture is stirred at 65° C. overnight
  3. extractionextracted with DCM (3×75 mL)
  4. washThe organic extracts are washed with water
  5. dry with materialdried over MgSO4
  6. customevaporated

Sources & evidence

ORD record
ord-d7c81632be004b26b619078c92850c33
Source dataset
uspto-grants-2009_10
Patent number
US07605269B2

Reaction notes

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