Potassium Carbonate → HCID 19432041, compound

HRID 1077622Notes

Reaction equation

HRID 1077622 reaction equation
[C:1]([O:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])(OC(C)(C)C)=O.C([O-])([O-])=O.[K+].[K+].[O:22]=[C:23]1[C:29]([CH3:31])([CH3:30])[CH2:28]C(=O)[CH:25]=[C:24]1[CH3:32]>O1CCCC1.C1OCCOCCOCCOCCOCCOC1>[C:12]([O:11][C:9]([O:8][C:1]1[CH:25]=[C:24]([CH3:32])[C:23](=[O:22])[C:29]([CH3:31])([CH3:30])[CH:28]=1)=[O:10])([CH3:13])([CH3:14])[CH3:15]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 62374KetoisophoroneHCID 90495Di-tert-butyl dicarbonate

Product 1

HCID 19432041HCID 19432041, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 2855718-Crown-6CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

A solution of 23.2 g (106.3 mmol) of di-tert.-butyl dicarbonate in 25 ml of tetrahydrofuran was added dropwise to a suspension, stirred at 24° C., of 20.0 g (144.7 mmol) of K2CO3, 20 ml of tetrahydrofuran, 1.1 g (4.2 mmol) of 18-crown-6 and 15.2 g (100 mmol) of ketoisophorone. The suspension was stirred at 60° C. for 5 hours, then the brown reaction mixture was filtered and finally the solvent was evaporated. The brown residue (26.6 g) was dissolved in 200 ml of dichloromethane and the solution was extracted with saturated NaHCO3 solution and with water. The organic phase was dried over Na2SO4, filtered and evaporated. The brown residue (22.6 g) was chromatographed over 150 g of silica gel (n-hexane/ether 2/1). There were obtained 20.4 g (81%) of 4-tert.-butyloxycarbonyloxy-2,6,6-trimethylcyclohexa-2,4-dienone as a yellow oil; anal. calc. for C14H20O4 (252.31): C 66.65, H 7.99; found: C 66.46, H 8.08.1H-NMR (250 MHz, CDCl3): 1.25 (s, 2 CH3 --C(6)); 1.54 (s, (CH3)3C--O); 1.91 (s, CH3 --C(2); 5.88-5.89 (d, H--C(5)); 6.71-6.74 (m, H--C(5)

Workup

  1. filtrationthe brown reaction mixture was filtered
  2. customfinally the solvent was evaporated
  3. dissolutionThe brown residue (26.6 g) was dissolved in 200 ml of dichloromethane
  4. extractionthe solution was extracted with saturated NaHCO3 solution and with water
  5. dry with materialThe organic phase was dried over Na2SO4
  6. filtrationfiltered
  7. customevaporated
  8. customThe brown residue (22.6 g) was chromatographed over 150 g of silica gel (n-hexane/ether 2/1)

Sources & evidence

ORD record
ord-bb72fb1d27c8430abba011d9a3fd1d1c
Source dataset
uspto-grants-1996_08
Patent number
US05543559

Reaction notes

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