Octanoic Acid → HCID 16661879, compound

HRID 2114000Notes

Reaction equation

HRID 2114000 reaction equation
[CH:1]([C:4]1[C:9](=[O:10])[C:8]([CH:11]([CH3:13])[CH3:12])=[CH:7][C:6](=[O:14])[C:5]=1[CH3:15])([CH3:3])[CH3:2].[C:16](O)(=O)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]CC.[C:26](#N)C.S(OOS([O-])(=O)=O)([O-])(=O)=O.[K+].[K+]>O.[N+]([O-])([O-])=O.[Ag+]>[CH2:15]([C:5]1[C:6](=[O:14])[C:7]([CH3:26])=[C:8]([CH:11]([CH3:13])[CH3:12])[C:9](=[O:10])[C:4]=1[CH:1]([CH3:3])[CH3:2])[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21]

Participants

7

Reactant 4

HCID 379Octanoic AcidHCID 6342AcetonitrileHCID 24412Potassium PersulfateHCID 59811714HCID 59811714, compound

Product 1

HCID 16661879HCID 16661879, compound

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×

Procedure

To a 100 ml round bottom flask equipped with a stir-bar was added 3,5-diisopropyl-2-methyl-[1,4]benzoquinone (216, see Example 2D; 1.03 g, 5.00 mmol), octanoic acid (83211, 757 mg, 5.24 mmole), silver (I) nitrate (917 mg, 5.40 mmol), acetonitrile (35 ml), and water (25 ml). The solution was heated under balloon-closed ambient atmosphere to 75° C. and was homogenous. Potassium persulfate (1.28 g, 5.75 mmol) in water (30 ml) was then added dropwise over 4 hours via syringe pump. Following complete addition the reaction mixture was heated for a further 2 hours and then the reaction volume reduced by approximately half under reduce pressure on a rotary evaporator. Water (50 ml) was added to the concentrate and the mixture extracted with MTBE (3×50 ml). The combined organics were washed with brine (50 ml), dried (sodium sulfate), and concentrated to a yellow oil (1.2 g). Approx. 75% of the residue was purified in 150-200 mg portions by preparative-TLC [silica gel: 200×200×2 mm; 100% heptane loading; 5% ethyl acetate/heptane elution]. The fastest running bands, as visualized by UV, were combined, extracted from the silica gel with MTBE, and the extract concentrated to a yellow oil (˜300 mg). The residue was further purified by flash chromatography [silica gel: 120 g; 100% heptane loading; 3-6% ethyl acetate/heptane gradient elution] to give the 2-heptyl-3,5-diisopropyl-6-methyl-[1,4]benzoquinone (218) as a bright yellow oil (288 mg, 21% mass yield). 1H NMR (400 MHz; C6D6; ppm): 2.93-2.80 (m, 2H), 2.49-2.46 (m, 2H), 1.84 (s, 3H), 1.43-1.18 (m, 10H), 1.33 (d, J=6.8 Hz, 6H), 1.19 (d, J=6.8 Hz, 6H), 0.88 (t, J=7.2 Hz, 3H).

Workup

  1. customTo a 100 ml round bottom flask equipped with a stir-bar
  2. temperatureThe solution was heated
  3. customunder balloon-closed ambient atmosphere to 75° C.
  4. additionaddition the reaction mixture
  5. temperaturewas heated for a further 2 hours
  6. customon a rotary evaporator
  7. additionWater (50 ml) was added to the
  8. concentrationconcentrate
  9. extractionthe mixture extracted with MTBE (3×50 ml)
  10. washThe combined organics were washed with brine (50 ml)
  11. dry with materialdried (sodium sulfate)
  12. concentrationconcentrated to a yellow oil (1.2 g)
  13. customApprox. 75% of the residue was purified in 150-200 mg portions by preparative-TLC [silica gel: 200×200×2 mm; 100% heptane loading; 5% ethyl acetate/heptane elution]
  14. extractionextracted from the silica gel with MTBE
  15. concentrationthe extract concentrated to a yellow oil (˜300 mg)
  16. customThe residue was further purified by flash chromatography [silica gel: 120 g; 100% heptane loading; 3-6% ethyl acetate/heptane gradient elution]
  17. customto give

Sources & evidence

ORD record
ord-13f088b7d68642c7b6571a9c29f93a97
Source dataset
uspto-grants-2008_10
Patent number
US07432305B2

Reaction notes

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