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

HRID 63816

Reaction equation

HRID 63816 reaction equation
[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]

Participants

6

Reactant 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

Product 1

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

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-5de81179670f4ecc883b0ca55a248205
Source dataset
uspto-grants-2016_09
Patent number
US09447006B2

Linked notes

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