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

HRID 63812

反応式

HRID 63812 の反応式
[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]

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 962Water溶媒2 回HCID 6344Dichloromethane溶媒HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-95959e4b29cd4ca8bee5240e647969f6
出典データセット
uspto-grants-2016_09
特許番号
US09447006B2

関連ノート

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