Water → (E)-2-(7-chloro-3-methylhept-2-enyl)-3,5,6-trimethylcyclohexa-2,5-diene-1,4-dione

HRID 922067Notes

Reaction equation

HRID 922067 reaction equation
O=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+].O.[Cl:29][CH2:30][CH2:31][CH2:32][CH2:33]/[C:34](/[CH3:50])=[CH:35]/[CH2:36][C:37]1[C:42]([CH3:43])=[C:41]([O:44]C)[C:40]([CH3:46])=[C:39]([CH3:47])[C:38]=1[O:48]C.CCOC(C)=O>C(C#N)(C)=O.O>[Cl:29][CH2:30][CH2:31][CH2:32][CH2:33]/[C:34](/[CH3:50])=[CH:35]/[CH2:36][C:37]1[C:38](=[O:48])[C:39]([CH3:47])=[C:40]([CH3:46])[C:41](=[O:44])[C:42]=1[CH3:43]

Participants

7

Reactant 4

HCID 962Water2×HCID 8857Ethyl AcetateHCID 180504Ceric ammonium nitrate3×HCID 58972215(E)-1-(7-Chloro-3-methylhept-2-enyl)-2,5-dimethoxy-3,4,6-trimethylbenzene

Product 1

HCID 58972230(E)-2-(7-chloro-3-methylhept-2-enyl)-3,5,6-trimethylcyclohexa-2,5-diene-1,4-dioneYield 19%

Reagents, catalysts & solvents 2

HCID 962WaterCatalystHCID 694302-OxopropiononitrileSolvent2×

Conditions

Temperature
0 °C

Procedure

CAN (709 mg, 1.29 mmol) was dissolved into AcCN (7 mL) and water (3 mL) then cooled to 0° C. In a separate flask, (E)-1-(7-Chloro-3-methylhept-2-enyl)-2,5-dimethoxy-3,4,6-trimethylbenzene (175 mg, 0.53 mmol) was dissolved into AcCN (2 mL) and 1 drop of H2O and transferred to the stirring CAN solution. Stirring was maintained for 1 h, after which time an additional charge of CAN (350 mg) was added and let stir for 1 h. Water (10 mL) and EtOAc (10 mL) were added, the layers separated and the combined organics washed H2O (2×5 mL). The combined aqueous phases were back extracted using EtOAc (2×5 mL) and the combined organics washed with brine (2×5 mL), dried over anhydrous Na2SO4 and concentrated to a yellow oil. Flash chromatography (SiO2) yielded 29.7 mg of (E)-2-(7-chloro-3-methylhept-2-enyl)-3,5,6-trimethylcyclohexa-2,5-diene-1,4-dione as a yellow oil (18.7%). 1H NMR (400 MHz, CDCl3) δ4.95 (t, J=6.8 Hz, 1H), 3.50 (t, J=6.8 Hz, 2H), 3.19 (d, J=6.8 Hz, 2H), 2.00 (m, 11H), 1.71 (m, 5H), 1.51 (m, J=7.2 Hz, 2H).

Workup

  1. temperaturewas maintained for 1 h
  2. additionwas added
  3. stirringlet stir for 1 h
  4. customthe layers separated
  5. washthe combined organics washed H2O (2×5 mL)
  6. extractionThe combined aqueous phases were back extracted
  7. washthe combined organics washed with brine (2×5 mL)
  8. dry with materialdried over anhydrous Na2SO4
  9. concentrationconcentrated to a yellow oil

Sources & evidence

ORD record
ord-68d35fbe5032415093bb63c18a52166f
Source dataset
uspto-grants-2016_03
Patent number
US09278085B2

Reaction notes

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