Acetonitrile → HCID 58838595, compound

HRID 2113999Notes

Reaction equation

HRID 2113999 reaction equation
[C:1]([C:5]1[C:6](=[O:14])[C:7]([CH3:13])=[C:8]([CH3:12])[C:9](=[O:11])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[C:15](O)(=O)[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20]C.C(#N)C>[N+]([O-])([O-])=O.[Ag+].O.CCCCCCC>[C:1]([C:5]1[C:6](=[O:14])[C:7]([CH3:13])=[C:8]([CH3:12])[C:9](=[O:11])[C:10]=1[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 3

HCID 6342AcetonitrileHCID 8094Heptanoic AcidHCID 58838600HCID 58838600, compound

Product 1

HCID 58838595HCID 58838595, compoundYield 8.6%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×HCID 8900HeptaneSolvent

Conditions

Temperature
70 °C

Procedure

To a 250 ml round bottom flask equipped with a stir-bar was added 5-tert-butyl-2,3-dimethyl-[1,4]benzoquinone (213; 0.68 g, 3.5 mmole), heptanoic acid (0.49 g, 3.7 mmole), AgNO3 (0.64 g, 3.8 mmole), acetonitrile (50 ml) and water (50 ml). The fully homogenous solution was heated to 70° C. under argon while an aqueous solution of K2S2O8 (0.91 g, 4.1 mmole in 30 ml water) was added dropwise 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 heptane (100 ml) and water (100 ml). The organic layer was separated and washed with saturated NaHCO3 (1×50 ml) followed by brine (2×100 ml). The organic layer was dried over sodium sulfate and concentrated to a yellow oil. The crude product was further purified by preparative TLC (silica gel: 200×200×2 mm; 100% heptane loading; 5% EtOAc:heptane elution). The fastest running bands, as visualized by UV, were excised, extracted from the silica gel with methyl tert-butyl ether, and the extract concentrated to a yellow oil to give a yellow oil. The residue was further purified by flash chromatography [silica gel: 40 g; 0-20% 100% heptane loading; 0-20% EtOAc/heptane gradient elution] to give pure 2-tert-butyl-3-hexyl-5,6-dimethyl-[1,4]benzoquinone (214; 83 mg, 8.4%) as a yellow oil. 1H NMR (400 MHz; C6D6; ppm): 2.71-2.67 (m, 2H), 1.67-1.66 (m, 6H), 1.51-1.24 (m, 8H), 1.37 (s, 9H), 0.88 (t, J=7.2 Hz, 3H).

Workup

  1. customTo a 250 ml round bottom flask equipped with a stir-bar
  2. additionwas added dropwise over 2.5 hours
  3. temperaturecooled to room temperature
  4. customThe organic layer was separated
  5. washwashed with saturated NaHCO3 (1×50 ml)
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. concentrationconcentrated to a yellow oil
  8. customThe crude product was further purified by preparative TLC (silica gel: 200×200×2 mm; 100% heptane loading; 5% EtOAc:heptane elution)
  9. extractionextracted from the silica gel with methyl tert-butyl ether
  10. concentrationthe extract concentrated to a yellow oil
  11. customto give a yellow oil
  12. customThe residue was further purified by flash chromatography [silica gel: 40 g; 0-20% 100% heptane loading; 0-20% EtOAc/heptane gradient elution]

Sources & evidence

ORD record
ord-2f454e93c6b540bbbf3957f36caf3624
Source dataset
uspto-grants-2008_10
Patent number
US07432305B2

Reaction notes

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