Acetic Acid → Isolongifolanone- parent

HRID 2424266Notes

Reaction equation

HRID 2424266 reaction equation
[CH3:1][C:2]1([CH3:15])[CH:8]2[CH:9]3[CH2:12][CH2:13][CH:7]2[C:6]([CH3:14])([C:10]3=[CH2:11])[CH2:5][CH2:4][CH2:3]1.C(O)(=[O:18])C>C1(C)C=CC=CC=1>[CH3:9][C:10]1([CH3:11])[CH:12]2[C:3]3([CH2:14][CH:6]1[CH2:5][CH2:4]3)[C:2]([CH3:15])([CH3:1])[CH2:8][CH2:7][C:13]2=[O:18]

Participants

4

Reactant 2

HCID 176Acetic AcidHCID 2891514,8,8-Trimethyl-9-methylidenedecahydro-1,4-methanoazulene

Product 1

HCID 90978Isolongifolanone- parent

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In a 2 L four-necked flask, 500 g of longifolene (manufactured by Yasuhara Chemical Co., Ltd.) and 250 mL of acetic acid were placed, to which 250 mL of boron trifluoride-diethyl etherate was added dropwise at 20° C. over 4 hours with stirring to carry out the isomerization. The reaction mixture was washed with ice water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and then refined by distillation. Thereafter, the refined product was mixed to 1,800 mL of methylene chloride and 900 mL of 0.5 N aqueous sodium hydrogen carbonate solution, to which 400 g of 3-chloroperbenzoic acid was slowly added at a temperature of 10° C. or less. After completion of the reaction, the reaction mixture was washed with 1 N aqueous sodium hydroxide solution and with water and concentrated in vacuo. The thus obtained crude product was dissolved in 3 L of toluene, to which 260 mL of boron trifluoride-diethyl etherate was slowly added dropwise at 5° C. or less. After completion of the reaction, the reaction mixture was washed with water and then refined by distillation to obtain 270 g of 1,1,5,5-tetramethyl-hexahydro-2,4a-methano-naphthalene-8-one. This was added dropwise at 5° C. or less to 640 mL of 2.1 N diethyl ether solution of methyllithium to carry out the alkylation. After completion of the reaction, the reaction mixture was washed with saturated aqueous ammonium chloride solution and with water and, then, charged in a 1 L autoclave together with 30 g of a nickel/diatomaceous earth hydrogenation catalyst (N-113, manufactured by Nikki Chemical Co., Ltd.) and was hydrogenated (hydrogen pressure: 6 MPa, reaction temperature: 250° C., reaction time: 6 hours).

Workup

  1. additionwas added dropwise at 20° C. over 4 hours
  2. washThe reaction mixture was washed with ice water
  3. distillationa saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and then refined by distillation
  4. additionThereafter, the refined product was mixed to 1,800 mL of methylene chloride and 900 mL of 0.5 N aqueous sodium hydrogen carbonate solution, to which 400 g of 3-chloroperbenzoic acid
  5. additionwas slowly added at a temperature of 10° C. or less
  6. customAfter completion of the reaction
  7. washthe reaction mixture was washed with 1 N aqueous sodium hydroxide solution and with water
  8. concentrationconcentrated in vacuo
  9. customThe thus obtained crude product
  10. additionwas slowly added dropwise at 5° C. or less
  11. customAfter completion of the reaction
  12. washthe reaction mixture was washed with water
  13. distillationrefined by distillation

Sources & evidence

ORD record
ord-a1d3059fcd89480583d51c201c58a79d
Source dataset
uspto-grants-2011_06
Patent number
US07964540B2

Reaction notes

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