Water → HCID 58972213, compound

HRID 922075Notes

Reaction equation

HRID 922075 reaction equation
O.[C:2]([O:5][CH2:6][CH2:7][CH2:8][CH2:9]/[C:10](/[CH3:26])=[CH:11]/[CH2:12][C:13]1[C:18]([CH3:19])=[C:17]([O:20]C)[C:16]([CH3:22])=[C:15]([CH3:23])[C:14]=1[O:24]C)(=[O:4])[CH3:3].CCOC(C)=O>C(C#N)(C)=O>[C:2]([O:5][CH2:6][CH2:7][CH2:8][CH2:9]/[C:10](/[CH3:26])=[CH:11]/[CH2:12][C:13]1[C:14](=[O:24])[C:15]([CH3:23])=[C:16]([CH3:22])[C:17](=[O:20])[C:18]=1[CH3:19])(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 962Water2×HCID 8857Ethyl AcetateHCID 58972222HCID 58972222, compound

Product 1

HCID 58972213HCID 58972213, compoundYield 36.3%

Reagents, catalysts & solvents 1

HCID 694302-OxopropiononitrileSolvent2×

Conditions

Temperature
0 °C

Procedure

Ceric ammonium nitrate (270 mg, 0.498 mmol) was dissolved into H2O (0.75 mL) and AcCN (1.5 mL) and the solution chilled to 0° C. 77.9 mg of (E)-7-(2,5-dimethoxy-3,4,6-trimethylphenyl)-5-methylhept-5-enyl acetate (0.223 mmol) in AcCN (1.5 mL) was added over 2 minutes and the dark orange solution stirred for 0.5 h. H2O (3 mL) and EtOAc (3 mL) were then added, the layers separated and the organics washed 2×2 mL H2O. The combined aqueous phase was back extracted 3×5 mL EtOAc and the combined organics washed 2×5 mL saturated NaCl solution and dried over anhydrous Na2SO4. The resulting yellow liquid was concentrated to a yellow oil and subjected to flash chromatography, which yielded 25.8 mg of (E)-5-methyl-7-(2,4,5-trimethyl-3,6-dioxocyclohexa-1,4-dienyl)hept-5-enyl acetate as a bright yellow oil (36.2%). 1H NMR (400 MHz, CDCl3) d 4.95 (t, J=6.4 Hz, 1H), 4.02 (t, J=6.8 Hz, 2H), 3.19 (d, J=6.8 Hz, 2H), 2.01 (m, 11H), 1.73 (s, 3H), 1.55 (m, 2H) 1.42 (m, 2H). 13C NMR (100 MHz, CDCl3) d 187.9, 187.0, 171.1, 143.0, 140.4, 140.3, 136.7, 119.9, 64.4, 39.1, 28.1, 25.6, 24.1, 20.9, 16.1, 12.3, 12.1.

Workup

  1. customthe layers separated
  2. washthe organics washed 2×2 mL H2O
  3. extractionThe combined aqueous phase was back extracted 3×5 mL EtOAc
  4. washthe combined organics washed 2×5 mL saturated NaCl solution
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationThe resulting yellow liquid was concentrated to a yellow oil

Sources & evidence

ORD record
ord-3d53eb2490494337abd279d5e08ec759
Source dataset
uspto-grants-2016_03
Patent number
US09278085B2

Reaction notes

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