Acetonitrile → (R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-[1,4]benzoquinone

HRID 63814

Reaktionsgleichung

Reaktionsgleichung von HRID 63814
[CH2:1]([C:4]1[C:13]([OH:14])=[CH:12][C:11]([CH3:15])=[C:10]2[C:5]=1[CH2:6][CH2:7][C@@:8]([CH3:32])([CH2:16][CH2:17][CH2:18][C@H:19]([CH3:31])[CH2:20][CH2:21][CH2:22][C@H:23]([CH3:30])[CH2:24][CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[O:9]2)[CH:2]=[CH2:3].C(#N)C.[O:36]=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+].CCOC(C)=O>O>[CH2:1]([C:4]1[C:13](=[O:14])[CH:12]=[C:11]([CH3:15])[C:10](=[O:9])[C:5]=1[CH2:6][CH2:7][C@@:8]([OH:36])([CH3:32])[CH2:16][CH2:17][CH2:18][C@H:19]([CH3:31])[CH2:20][CH2:21][CH2:22][C@H:23]([CH3:30])[CH2:24][CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[CH:2]=[CH2:3]

Komponenten

6

Edukt 4

HCID 6342AcetonitrileHCID 8857Ethyl AcetateHCID 180504Ceric ammonium nitrateHCID 58771206(R,R,R)-5-allyl-2,8-dimethyl-2-(4,8,12-trimethyl-tridecyl)-chroman-6-ol

Produkt 1

HCID 58771177(R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-[1,4]benzoquinoneAusbeute 96 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A 50 mL RBF flask was charged with (R,R,R)-5-allyl-2,8-dimethyl-2-(4,8,12-trimethyl-tridecyl)-chroman-6-ol (Ex-1E-3) (280 mg, 0.63 mmol) and ACN (14 mL), then cooled to 0° C. A solution of CAN (710 mg, 1.30 mml) in water (2 mL) was added dropwise over 1 min to the reaction resulting in a bright orange solution. After 15 min, the reaction was deemed complete (TLC—5:1 hept:EtOAc). The reaction was extracted with MTBE (3×15 mL). The combined MTBE layers were dried over Na2SO4, filtered and concentrated by rotary evaporation to yield (R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-[1,4]benzoquinone (Ex-1E-4) as an orange oil (270 mg, 96%). 1H NMR (400 MHz, CDCl3) δ (ppm): 6.59 (d, J=1.4 Hz, 1H), 5.82 (ddt, 1H), 5.10-5.06 (m, 2H), 3.27 (d, J=6.2 Hz, 2H), 2.60-2.56 (m, 2H), 2.06 (s, 6H), 1.59-1.04 (m, 21H), 0.89-0.85 (m, 15H).

Aufarbeitung

  1. customresulting in a bright orange solution
  2. extractionThe reaction was extracted with MTBE (3×15 mL)
  3. dry with materialThe combined MTBE layers were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation

Quellen und Nachweise

ORD-Eintrag
ord-2605ea47746649268423c2744f944bd1
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09447006B2

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