tert-Butyl hydroperoxide → Z-4-(5-acetoxy-3-methyl-pent-3-en-1-ynyl)-3,4-epoxy-3,5,5-trimethylcyclohexan-1-ol

HRID 440222

Reaktionsgleichung

Reaktionsgleichung von HRID 440222
[C:1]([O:4][CH2:5]/[CH:6]=[C:7](/[CH3:20])\[C:8]#[C:9][C:10]1[C:15]([CH3:17])([CH3:16])[CH2:14][CH:13]([OH:18])[CH2:12][C:11]=1[CH3:19])(=[O:3])[CH3:2].C([O:25]O)(C)(C)C.OS([O-])=O.[Na+]>C1(C)C=CC=CC=1.C/C(/O)=C\C(C)=O.C/C(/O)=C\C(C)=O.O=[V]>[C:1]([O:4][CH2:5]/[CH:6]=[C:7](/[CH3:20])\[C:8]#[C:9][C:10]12[O:25][C:11]1([CH3:19])[CH2:12][CH:13]([OH:18])[CH2:14][C:15]2([CH3:17])[CH3:16])(=[O:3])[CH3:2]

Komponenten

6

Edukt 3

HCID 6410tert-Butyl hydroperoxideHCID 23665763Sodium BisulfiteHCID 88390003Z-4-(5-acetoxy-3-methyl-pent-3-en-1-ynyl)-3,5,5-trimethylcyclohex-3-en-1-ol

Produkt 1

HCID 22406461Z-4-(5-acetoxy-3-methyl-pent-3-en-1-ynyl)-3,4-epoxy-3,5,5-trimethylcyclohexan-1-olAusbeute 104,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 16217092Bis(2,4-pentanedionato)vanadium(IV) OxideKatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a solution of Z-4-(5-acetoxy-3-methyl-pent-3-en-1ynyl)-3,5,5-trimethylcyclohex-3-en-1-ol (42 mg, 0.15 mmol) in toluene (6 mL) was added t-butyl hydroperoxide (3M solution in 2,2,4-trimethylpentane, 0.07 mL, 0.21 mmol) and vanadyl acetylacetonate (3 mg, 0.01 mmol). The reaction mixture, which was reddish orange in color, was stirred under argon at room temperature for 20 min. and then was heated to 70° C. for 30 min. The color of the mixture changed to yellow. After cooling to room temperature, saturated NaHSO3 was added with stirring until there was no peroxide as indicated by peroxide test tapes. The organic and aqueous layers were separated. The aqueous layer was extracted three times with ether. The combined organic layers were washed with H2O, saturated NaHCO3, H2O and dried over anhydrous Na2SO4. Evaporation of solvent gave yellow oil (46 mg) which was purified using the Chromatotron™ sold by Harrison Scientific and with 75% ether+25% hexane as solvent to give compound (4) as a colorless oil (17 mg, 38%), ir: 3620 (weak, sharp, OH), 3500 (weak, broad, OH), 1740 (strong, sharp, C=O) cm-1; 1H nmr d: 5.80 (ddq, J=6.9, 6.9, 1.6 Hz, 1H, =CH), 4.71 (dd, 6.9, 1.0 Hz, 2H, CH2O), 3.83 (m, 1H, CHOH), 2.19 (ddd, J=14.7, 6.8, 1.5 Hz, 1H, CH2), 2.03 (s, 3H, CH3COO), 1.89 (m, 3H, vinyl CH3), 1.81 (dd, J=14.7, 8.9 Hz, 1H, CH2), 1.47 (s, CH3), 1.37 (ddd, J=12.7, 4.0, 1.5 Hz, 1H, CH2), 1.18 (s, 6H, 2CH3); ms (isobutane CI) m/z: 293 (M+1), 331 (M+39); (NH4Cl CI): 310 (M+18), 275 (M-17), 233 (M-59).

Aufarbeitung

  1. temperaturewas heated to 70° C. for 30 min
  2. temperatureAfter cooling to room temperature
  3. stirringwith stirring until there
  4. customThe organic and aqueous layers were separated
  5. extractionThe aqueous layer was extracted three times with ether
  6. washThe combined organic layers were washed with H2O, saturated NaHCO3, H2O
  7. dry with materialdried over anhydrous Na2SO4
  8. customEvaporation of solvent

Quellen und Nachweise

ORD-Eintrag
ord-1398b95f82154de9aae0dae2f4b60dae
Quelldatensatz
uspto-grants-1996_05
Patentnummer
US05518995

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