Dihydrocoumarin → Cyclohexadienone, hydroxy-

HRID 2198945Notes

Reaction equation

HRID 2198945 reaction equation
[CH:1]1[CH:2]=[CH:3]C2O[C:9](=[O:10])[CH2:8]C[C:5]=2[CH:6]=1.[Cl-:12].[NH4+:13].[CH:14](Cl)(Cl)Cl.[O:18]1[CH2:22][CH2:21][CH2:20][CH2:19]1>>[Cl:12][CH:1]1[CH2:2][CH2:3][N:13]([CH3:14])[CH2:5][CH2:6]1.[O:10]=[C:9]1[CH:8]=[CH:19][CH:20]=[CH:21][CH:22]1[OH:18]

Participants

6

Reactant 4

HCID 660DihydrocoumarinHCID 6212ChloroformHCID 8028TetrahydrofuranHCID 25517Ammonium Chloride

Product 2

HCID 793424-chloro-N-methylpiperidineHCID 440554Cyclohexadienone, hydroxy-Yield 46%

Procedure

The Grignard reagent of 4-chloro-N-methylpiperidine (60 g, 0.47 moles) is prepared as in Example 3A. To this is added a solution of 23 g (0.155 moles) dihydrocoumarin in 100 ml tetrahydrofuran over 20 minutes (reaction refluxed). Refluxed for 31/2 hours. The flask is cooled in an ice bath and saturated ammonium chloride solution is added (200 ml). The layers are separated and the aqueous extracted with tetrahydrofuran. The organics are dried (magnesium sulfate) and evaporated. The residue, after an acid-base extraction, yield 13 g from the organics. Carbon dioxide is bubbled through the aqueous which is then extracted with dichloromethane. These organics are dried and evaporated to yield 26 g. Chromatography (basic alumina, activity III, chloroform) afforded 17.7 g (46%) crystalline keto-phenol.

Workup

  1. custom(reaction refluxed)
  2. temperatureRefluxed for 31/2 hours
  3. temperatureThe flask is cooled in an ice bath
  4. customThe layers are separated
  5. extractionthe aqueous extracted with tetrahydrofuran
  6. dry with materialThe organics are dried (magnesium sulfate)
  7. customevaporated
  8. extractionThe residue, after an acid-base extraction, yield 13 g from the organics
  9. customCarbon dioxide is bubbled through the aqueous which
  10. extractionis then extracted with dichloromethane
  11. customThese organics are dried
  12. customevaporated
  13. customto yield 26 g

Sources & evidence

ORD record
ord-0f82544e211e492cbc4e80f9ec0d324c
Source dataset
uspto-grants-1982_11
Patent number
US04360532

Reaction notes

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