Acetic Anhydride → HCID 67733949, compound

HRID 1589991Notes

Reaction equation

HRID 1589991 reaction equation
O[C:2]1([C:12]#[C:13]/[C:14](/[CH3:18])=[CH:15]\[CH2:16][OH:17])[C:7]([CH3:9])([CH3:8])[CH2:6][C:5](=[O:10])[CH2:4][CH:3]1[CH3:11].[C:19](OC(=O)C)(=[O:21])[CH3:20].OS([O-])(=O)=O.[K+].C([O-])(O)=O.[Na+]>CCCCCC.C(O)(=O)C>[C:19]([O:17]/[CH:16]=[CH:15]\[CH:14]([CH3:18])[C:13]#[C:12][C:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][C:5](=[O:10])[CH2:4][C:3]=1[CH3:11])(=[O:21])[CH3:20]

Participants

7

Reactant 4

HCID 7918Acetic AnhydrideHCID 516892Sodium Bicarbonate2×HCID 516920Potassium bisulfateHCID 86746694HCID 86746694, compound

Product 1

HCID 67733949HCID 67733949, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8058HexaneSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of (Z)-4-hydroxy-4-(5-hydroxy-3-methylpent-3-en-1-ynyl)-3,5,5-trimethylcyclohexanone 795 mg, 3.1 mmol), glacial acetic acid (5 mL), acetic anhydride (5 mL), and KHSO4 (440 mg, 3.2 mmol) was heated to 70° C. under argon for 5 h. Then the mixture was cooled to room temperature and slowly added to a chilled (ice bath) and stirred mixture of hexane and saturated NaHCO3. More saturated NaHCO3 was added until the pH of the aqueous phase was about 6-7. The organic and aqueous layers were then separated, and the aqueous layer was extracted with hexane. The combined hexane layers were washed with saturated NaHCO3, H2O, and dried over anhydrous Na2SO4. Removal of solvent gave a yellow oil (737 mg) which on purification by flash column chromatography using 75% ether+25% hexane as solvent gave compound (3) (600 mg, 70%) as a yellow oil, ir: 1730 (strong, broad) cm-1; 1H nmr d: 5.77 (ddq, J=7.0, 7.0, 1.5 Hz, 1H, =CH), 4.76 (dd, J=7.0, 1.0 Hz, 2H CH2O), 2.90 (broad s, 2H, CH2), 2.39 (s, 2H, CH2), 2.03 (s, 3H, CH3COO), 1.94 and 1.93 (2m, 6H, 2 vinyl CH3), 1.16 (s, 6H, 2CH3); ms m/z: 274 (M+, 30), 214 (100).

Workup

  1. temperatureThen the mixture was cooled to room temperature
  2. additionslowly added to
  3. temperaturea chilled (ice bath)
  4. customThe organic and aqueous layers were then separated
  5. extractionthe aqueous layer was extracted with hexane
  6. washThe combined hexane layers were washed with saturated NaHCO3, H2O
  7. dry with materialdried over anhydrous Na2SO4
  8. customRemoval of solvent

Sources & evidence

ORD record
ord-0c5234089ea14f53b8d46cff615cc7ad
Source dataset
uspto-grants-1993_04
Patent number
US05201931

Reaction notes

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