Salicylic Acid → HCID 10058953, compound

HRID 1595060Notes

Reaction equation

HRID 1595060 reaction equation
[C:1]([O:4][CH2:5]/[CH:6]=[C:7](/[CH2:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])\[CH3:8])(=[O:3])[CH3:2].C([O:19]O)(C)(C)C.C(O)(=O)C1C(=CC=CC=1)O>[Al].C1(C)C=CC=CC=1.C(Cl)Cl.O=[Mn]=O>[CH3:8]/[C:7](/[CH2:9][CH2:10]/[CH:11]=[C:12](\[CH3:14])/[CH:13]=[O:19])=[CH:6]\[CH2:5][O:4][C:1]([CH3:2])=[O:3]

Participants

8

Reactant 3

HCID 338Salicylic AcidHCID 6410tert-Butyl hydroperoxideHCID 1549026Geranyl acetate2×

Product 1

HCID 10058953HCID 10058953, compoundYield 51%

Reagents, catalysts & solvents 4

HCID 14801Manganese dioxideCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×HCID 5359268AluminumSolvent

Procedure

Geranyl acetate was oxidized as described previously with some modification (21). Forty milliliters (0.36 mol) of 90% tert-butyl hydroperoxide was added to a stirred suspension of 1.11 g (0.01 mol) of SeO2, 1.4 g (0.01 mol) of salicylic acid, and 75 ml of CH2Cl2 in a 250 ml round bottom flask covered in aluminum foil. The resulting solution was allowed to stir to homogeneity at room temperature before being placed at 0° C. After ten minutes, 21.5 ml (0.10 mol) of geranyl acetate (4) was introduced dropwise. The mixture was stirred for 5 h at 0° C., and then for 20 h at rt. TLC analysis indicated the presence of starting material and two oxidized products (Rf 0.38 aldehyde, Rf 0.19 alcohol). The solution was diluted with 100 ml toluene, and solvents were removed under reduced pressure. The residue was then dissolved in toluene, washed with 5% NaHCO3 to remove H2SeO3, saturated CuSO4, saturated aqueous Na2S2O3 (2×), water, brine, dried over MgSO4 and filtered. The solvent was removed under reduced pressure affording a crude oil, which was dissolved in 100 ml dry CH2Cl2 and cooled to 0° C. 40.95 g (0.47 mol) of activated MnO2 was added, and the suspension was stirred for 5 h at 0° C., then overnight at rt. The mixture was filtered over a short bed of Celite, and washed thoroughly with dry CH2Cl2. Solvent was evaporated under reduced pressure to yield a crude, pale yellow oil which was purified by flash chromatography on silica gel (5% EtOAc in hexane) affording 10.68 g (51 %) of 5 as a colorless oil; 1H NMR (C6H6, 200 MHz) δ9.47 (s, 1H), 5.98 (t, 1H, J=6.9 Hz), 5.48 (t, 1H, J=6.9 Hz), 4.75 (d, 2H, J=6.8 Hz), 2.11 (q, 2H, J=7.3 Hz), 1.92 (t, 2H, J=7.3 Hz), 1.91 (s, 3H), 1.79 (s, 6H), 1.59 (s, 3H); 13C NMR (50.3 MHz) δ195.47, 171.39, 153.70, 140.73, 140.08, 120.01, 61.48, 38.13, 27.33, 21.37, 16.77, 9.62.

Workup

  1. custombefore being placed at 0° C
  2. waitAfter ten minutes
  3. stirringThe mixture was stirred for 5 h at 0° C.
  4. customwere removed under reduced pressure
  5. dissolutionThe residue was then dissolved in toluene
  6. washwashed with 5% NaHCO3
  7. customto remove H2SeO3, saturated CuSO4, saturated aqueous Na2S2O3 (2×), water, brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customThe solvent was removed under reduced pressure
  11. customaffording a crude oil, which
  12. temperaturecooled to 0° C
  13. stirringthe suspension was stirred for 5 h at 0° C.
  14. customovernight
  15. customat rt
  16. filtrationThe mixture was filtered over a short bed of Celite
  17. washwashed thoroughly with dry CH2Cl2
  18. customSolvent was evaporated under reduced pressure
  19. customto yield a crude, pale yellow oil which
  20. customwas purified by flash chromatography on silica gel (5% EtOAc in hexane)

Sources & evidence

ORD record
ord-95809474be774efd9fad6d6cc6a6e4fa
Source dataset
uspto-grants-2001_09
Patent number
US06284910B1

Reaction notes

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