Ammonium cerium-nitrate → (S)-(+)-5-(3,4-dihydroxy-3-methyl-1-butyl)-2,3,6-trimethyl-p-benzoquinone

HRID 262057Notes

Reaction equation

HRID 262057 reaction equation
[N+]([O-])([O-])=[O:2].[NH4+].[Ce].CO[C:9]1([CH3:29])[C:14]([CH3:15])=[C:13]([O:16]C)[C:12]([CH3:18])=[C:11]([CH2:19][CH2:20][C@@:21]2([CH3:28])[CH2:25][O:24]C(C)(C)[O:22]2)[CH2:10]1>O.C(#N)C>[OH:22][C@:21]([CH3:28])([CH2:25][OH:24])[CH2:20][CH2:19][C:11]1[C:10](=[O:2])[C:9]([CH3:29])=[C:14]([CH3:15])[C:13](=[O:16])[C:12]=1[CH3:18]

Participants

5

Reactant 2

HCID 57418452Ammonium cerium-nitrateHCID 70593036(S)-4-(3,5-dimethoxy-3,4,6-trimethyl-phenylethyl)-2,2,4-trimethyl-1,3-dioxolan

Product 1

HCID 13100536(S)-(+)-5-(3,4-dihydroxy-3-methyl-1-butyl)-2,3,6-trimethyl-p-benzoquinoneYield 41.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

While stirring for 2 minutes at room temperature, 2.01 g of cerium ammonium nitrate in 7.5 ml of water were added dropwise to a solution of 550 mg of (S)-4-(3,5-dimethoxy-3,4,6-trimethyl-phenylethyl)-2,2,4-trimethyl-1,3-dioxolan in 7.5 ml of acetonitrile. After 2 minutes of additional stirring, the reaction mixture was extracted three times with 20 ml of chloroform each time. The combined organic extracts were dried over sodium sulfate, whereafter the solvent was removed. After chromatography of the obtained residue on silica gel with benzene/ethyl acetate (2:1 parts by volume) and ethyl acetate, there were obtained 266 mg of (S)-(+)-2,3,6-trimethyl-5-(2,2,4-trimethyl-1,3-dioxolan-4-ethyl)-p-benzoquinone and 177 mg of (S)-(+)-5-(3,4-dihydroxy-3-methyl-1-butyl)-2,3,6-trimethyl-p-benzoquinone in the form of yellow needles with a melting point of 111°-112°.

Workup

  1. waitAfter 2 minutes of additional stirring
  2. extractionthe reaction mixture was extracted three times with 20 ml of chloroform each time
  3. dry with materialThe combined organic extracts were dried over sodium sulfate, whereafter the solvent
  4. customwas removed

Sources & evidence

ORD record
ord-cda46522b62f43ce85fa6f88c66430e4
Source dataset
uspto-grants-1979_05
Patent number
US04153614

Reaction notes

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