Acetonitrile → HCID 66935830, compound

HRID 2113997Notes

Reaction equation

HRID 2113997 reaction equation
[CH3:1][C:2]1[C:3](=[O:11])[CH:4]=[C:5]([CH3:10])[C:6](=[O:9])[C:7]=1[CH3:8].[C:12](O)(=O)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19]/[CH:20]=[CH:21]\[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]CC.[C:32](#N)C>[N+]([O-])([O-])=O.[Ag+].O.CC(OC)(C)C>[CH2:10]([C:5]1[C:6](=[O:9])[C:7]([CH3:8])=[C:2]([CH3:1])[C:3](=[O:11])[C:4]=1[CH3:32])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH:18]=[CH:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

7

Reactant 3

HCID 6342AcetonitrileHCID 702912,5-Cyclohexadiene-1,4-dione, 2,3,5-trimethyl-HCID 445639Oleic Acid

Product 1

HCID 66935830HCID 66935830, compoundYield 2%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
70 °C

Procedure

To a 250 ml round bottom flask was added 2,3,5-trimethyl-[1,4]benzoquinone (0.51 g, 3.4 mmole), oleic acid (1.0 g, 3.5 mmole), and silver nitrate (0.62 g, 3.6 mmole) in a 1:1 mixture of water and acetonitrile (100 ml). The solution was heated to 70° C. under argon and an aqueous solution of K2S2O8 (0.86 g, 3.9 mmole in 50 ml water) was added dropwise to the homogenous mixture over 2.5 hours using a syringe pump. The reaction was stirred at 70° C. for an additional 30 minutes after addition, then cooled to room temperature. To the reaction mixture was added MTBE (200 ml) and water (100 ml). The organic layer was separated, washed with water (2×100 ml), then brine (2×100 ml). The solution was dried over sodium sulfate and concentrated to a yellow oil. The crude product was further purified by silica gel chromatography (120 g, 0-30% EtOAc:heptane) to give pure 2-heptadec-8-enyl-3,5,6-trimethyl-[1,4]benzoquinone (211; 25.2 mg, 2%) as a yellow oil. 1H NMR (400 MHz; d6-DMSO; ppm): 5.32-5.30 (m 2H), 2.42-2.38 (m, 2H), 1.98-1.93 (m, 4H), 1.95 (s, 3H), 193 (s, 6H), 1.40-1.22 (m, 22H), 0.84 (t, J=7.2 Hz, 3H).

Workup

  1. additionafter addition
  2. temperaturecooled to room temperature
  3. customThe organic layer was separated
  4. washwashed with water (2×100 ml)
  5. dry with materialThe solution was dried over sodium sulfate
  6. concentrationconcentrated to a yellow oil
  7. customThe crude product was further purified by silica gel chromatography (120 g, 0-30% EtOAc:heptane)

Sources & evidence

ORD record
ord-d2e0851c430b467690aee020561738e8
Source dataset
uspto-grants-2008_10
Patent number
US07432305B2

Reaction notes

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