Acetonitrile → HCID 66935647, compound

HRID 2113996Notes

Reaction equation

HRID 2113996 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].[CH3:12][CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19]/[CH:20]=[CH:21]\[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]CC(O)=O.[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][CH:21]=[CH: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 5280934Linolenic Acid

Product 1

HCID 66935647HCID 66935647, compoundYield 12.3%

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 (1.50 g, 9.98 mmole), linolenic acid (2.94 g, 10.4 mmole), and silver nitrate (1.83 g, 10.8 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 (2.55 g, 11.5 mmole in 50 ml water) was added dropwise to the homogenous solution over 2.5 hours using a syringe pump. The reaction mixture was allowed to stir an additional 30 minutes at 70° C., then cooled to room temperature. To the mixture was added MTBE (200 ml) and water (100 ml). The organic layer was separated and washed with saturated NaHCO3 (100 ml), then brine (2×200 ml). The MTBE solution was dried over sodium sulfate then concentrated to a yellow oil. The crude product, which contained residual unreacted starting quinone by TLC, was further purified by silica gel chromatography (120 g, 0-30% EtOAc:heptane) to give pure 2-heptadeca-8,11-dienyl-3,5,6-trimethyl-[1,4]benzoquinone (210; 0.474 g, 12.3%) as a yellow oil. 1H NMR (400 MHz; d6-DMSO; ppm): 5.36-5.26 (m, 4H), 2.73 (t, J=5.6 Hz, 2H), 2.42-2.38 (m, 2H), 2.02-1.93 (m, 4H). 1.95 (s, 3H), 1.93 (s, 6H). 1.34-1.22 (m, 16H), 0.84 (t, J=7.2 Hz, 3H).

Workup

  1. temperaturecooled to room temperature
  2. customThe organic layer was separated
  3. washwashed with saturated NaHCO3 (100 ml)
  4. dry with materialThe MTBE solution was dried over sodium sulfate
  5. concentrationthen concentrated to a yellow oil
  6. customwas further purified by silica gel chromatography (120 g, 0-30% EtOAc:heptane)

Sources & evidence

ORD record
ord-fc91033210eb4923804660e2e69ddd66
Source dataset
uspto-grants-2008_10
Patent number
US07432305B2

Reaction notes

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