Hydrochloric Acid → 6′-Methoxy-9-rubanone

HRID 1742437Notes

Reaction equation

HRID 1742437 reaction equation
C(C1C=CC=CC=1)(=O)C1C=CC=CC=1.[CH3:15][O:16][C:17]1[CH:18]=[CH:19][C:20]2[N:26]=[CH:25][CH:24]=[C:23]([C@@H:27]([OH:38])[C@H:28]3[N:33]4[CH2:34][C@H:35]([CH:36]=[CH2:37])[C@@H:30]([CH2:31][CH2:32]4)[CH2:29]3)[C:21]=2[CH:22]=1.CC(C)([O-])C.[K+].Cl>C1(C)C=CC=CC=1>[CH3:15][O:16][C:17]1[CH:18]=[CH:19][C:20]2[C:21](=[C:23]([C:27]([CH:28]3[N:33]4[CH2:34][CH:35]([CH:36]=[CH2:37])[CH:30]([CH2:31][CH2:32]4)[CH2:29]3)=[O:38])[CH:24]=[CH:25][N:26]=2)[CH:22]=1

Participants

6

Reactant 4

HCID 313Hydrochloric Acid2×HCID 3102BenzophenoneHCID 3034034QuinineHCID 23665647Potassium tert-butoxide

Product 1

HCID 67686′-Methoxy-9-rubanoneYield 102.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of benzophenone (1.12 kg) in toluene (4 L) was treated with quinine (1.00 kg) and potassium t-butoxide (871 g). The resulting mixture was heated to reflux for six hours, then allowed to cool to room temperature. After about 18 hours, this mixture was cooled to a temperature of about 10° C. to about 15° C. This cold mixture was treated with 2 N hydrochloric acid (4 L) at a rate such that the temperature of the mixture was less than 30° C. The resulting mixture was treated with additional 2 N hydrochloric acid (3 L) and the phases separated. The organic phase was extracted with additional 2 N hydrochloric acid (2×2.5 L). The combined aqueous phase was cooled to a temperature of about 5° C. to about 15° C., and the pH adjusted to pH 9-9.5 with the addition of 5 N sodium hydroxide (ca. 2.6 L). The resulting mixture was stirred at about 5° C. to about 20° C. for one hour. The crystalline material was removed by filtration, rinsed with water (2×1 L), and dried in vacuo at 50° C. to give 1.02 kg of quininone.

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureto reflux for six hours
  3. temperaturethis mixture was cooled to a temperature of about 10° C. to about 15° C
  4. customwas less than 30° C
  5. customthe phases separated
  6. extractionThe organic phase was extracted with additional 2 N hydrochloric acid (2×2.5 L)
  7. temperatureThe combined aqueous phase was cooled to a temperature of about 5° C. to about 15° C.
  8. additionthe pH adjusted to pH 9-9.5 with the addition of 5 N sodium hydroxide (ca. 2.6 L)
  9. customThe crystalline material was removed by filtration
  10. washrinsed with water (2×1 L)
  11. customdried in vacuo at 50° C.

Sources & evidence

ORD record
ord-d181ea606e834da7a887c4767d1f1a39
Source dataset
uspto-grants-1994_08
Patent number
US05338851

Reaction notes

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