Acetonitrile → (R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5,6-dimethyl-[1,4]benzoquinone

HRID 63812

반응식

HRID 63812 반응식
[CH2:1]([C:4]1[C:13]([OH:14])=[C:12]([CH3:15])[C:11]([CH3:16])=[C:10]2[C:5]=1[CH2:6][CH2:7][C@@:8]([CH3:33])([CH2:17][CH2:18][CH2:19][C@H:20]([CH3:32])[CH2:21][CH2:22][CH2:23][C@H:24]([CH3:31])[CH2:25][CH2:26][CH2:27][CH:28]([CH3:30])[CH3:29])[O:9]2)[CH:2]=[CH2:3].C(#N)C.[O:37]=[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.CC(OC)(C)C.C(Cl)Cl>[CH2:1]([C:4]1[C:13](=[O:14])[C:12]([CH3:15])=[C:11]([CH3:16])[C:10](=[O:9])[C:5]=1[CH2:6][CH2:7][C@@:8]([OH:37])([CH3:33])[CH2:17][CH2:18][CH2:19][C@H:20]([CH3:32])[CH2:21][CH2:22][CH2:23][C@H:24]([CH3:31])[CH2:25][CH2:26][CH2:27][CH:28]([CH3:30])[CH3:29])[CH:2]=[CH2:3]

참가 물질

8

반응물 4

HCID 6342AcetonitrileHCID 8857Ethyl AcetateHCID 180504Ceric ammonium nitrateHCID 58771198(R,R,R)-5-allyl-2,7,8-trimethyl-2-(4,8,12-trimethyl-tridecyl)-chroman-6-ol

생성물 1

HCID 58771193(R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5,6-dimethyl-[1,4]benzoquinone수율 81.4%

시약·촉매·용매 3

HCID 962Water용매2회HCID 6344Dichloromethane용매HCID 15413tert-Butyl methyl ether용매

반응 조건

온도
0 °C

실험 절차

A 50 mL RBF flask was charged with (R,R,R)-5-allyl-2,7,8-trimethyl-2-(4,8,12-trimethyl-tridecyl)-chroman-6-ol (Ex-1D-3) (120 mg, 0.26 mmol) and ACN (20 mL), then cooled to 0° C. A solution of CAN (285 mg, 0.52 mmol) in water (1 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—9:1 hept:EtOAc). The reaction was diluted with MTBE (10 mL) and water (10 mL). The aqueous layer was washed with MTBE (3×10 mL). The combined, MTBE layers were washed with brine (5 mL), dried over MgSO4, filtered and concentrated by rotary evaporation to yield an orange oil. The oil was dissolved in DCM (10 mL) and passed through a silica plug. The DCM eluent was concentrated by rotary evaporation to yield (R,R,R)-2-allyl-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5,6-dimethyl-[1,4]benzoquinone (Ex-1D-4) as an orange oil (100 mg, 80%). 1H NMR (400 MHz, CDCl3) δ (ppm): 5.83 (ddt, 1H), 5.10-5.05 (m, 2H), 3.29 (d, J=6.2 Hz, 2H), 2.59-2.45 (m, 2H), 2.04 (s, 6H), 1.56-1.00 (m, 24H), 1.25 (s, 3H), 0.89-0.85 (m, 12H).

후처리

  1. customresulting in a bright orange solution
  2. washThe aqueous layer was washed with MTBE (3×10 mL)
  3. washMTBE layers were washed with brine (5 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated by rotary evaporation
  7. customto yield an orange oil
  8. concentrationThe DCM eluent was concentrated by rotary evaporation

출처 및 근거

ORD 기록
ord-95959e4b29cd4ca8bee5240e647969f6
출처 데이터셋
uspto-grants-2016_09
특허 번호
US09447006B2

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