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

HRID 63816

反応式

HRID 63816 の反応式
[OH:1][C@:2]([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])[CH2:3][CH2:4][C:5]1[C:6]([CH2:14][CH2:15][CH3:16])=[C:7]([OH:13])[CH:8]=[C:9]([CH3:12])[C:10]=1[OH:11].C(#N)C.C(Cl)Cl.O=[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+]>O>[OH:1][C@:2]([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])[CH2:3][CH2:4][C:5]1[C:10](=[O:11])[C:9]([CH3:12])=[CH:8][C:7](=[O:13])[C:6]=1[CH2:14][CH2:15][CH3:16]

参加物

6

反応物 4

HCID 6342AcetonitrileHCID 6344DichloromethaneHCID 180504Ceric ammonium nitrateHCID 58771174(R,R,R)-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-2-propyl-benzene-1,4-diol

生成物 1

HCID 58771205(R,R,R)-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-2-propyl-[1,4]benzoquinone収率 45.2%

試薬・触媒・溶媒 1

HCID 962Water溶媒2 回

反応条件

温度
0 °C

実験手順

A 50 mL RBF flask was charged with (R,R,R)-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-2-propyl-benzene-1,4-diol (Ex-1E-5) (110 mg, 0.24 mmol), ACN (15 mL) and DCM (2 mL), then cooled to 0° C. A solution of CAN (269 mg, 0.49 mmol) in water (1 mL) was added dropwise over 1 min to the reaction resulting in a bright orange solution. The reaction was stirred for 15 min then was diluted with water (5 mL). The aqueous layer was washed with DCM (3×30 mL). The combined DCM layers were dried over Na2SO4, filtered and concentrated by rotary evaporation to yield an orange oil. The oil was purified by column chromatography (gradient—hept to 20:1 hept.:EtOAc) to yield (R,R,R)-3-(3-hydroxy-3,7,11,15-tetramethyl-hexadecyl)-5-methyl-2-propyl-[1,4]benzoquinone (Ex-1E-6) as an orange oil (50 mg, 44%). 1H NMR (400 MHz, CDCl3) δ (ppm): 6.56 (s, 1H), 2.58-2.54 (m, 2H), 2.45 (t, J=7.9 Hz, 2H), 2.04 (s, 3H), 1.55-1.04 (m, 26H), 1.00 (t, J=7.4 Hz, 3H), 0.89-0.85 (m, 15H).

後処理

  1. customresulting in a bright orange solution
  2. washThe aqueous layer was washed with DCM (3×30 mL)
  3. dry with materialThe combined DCM layers were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation
  6. customto yield an orange oil
  7. customThe oil was purified by column chromatography (gradient—hept to 20:1 hept.:EtOAc)

出典と根拠

ORDレコード
ord-5de81179670f4ecc883b0ca55a248205
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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