2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 12000074, compound

HRID 1910651Notes

Reaction equation

HRID 1910651 reaction equation
COC1C=C(C=CC=1OC)C[O:7][CH2:8][C@@H:9]([O:14][CH2:15]/[CH:16]=[C:17](/[CH3:39])\[CH2:18][CH2:19]/[CH:20]=[CH:21]/[C:22]([CH3:38])([CH3:37])[CH2:23][CH2:24][C:25](=[CH2:36])[CH2:26]/[CH:27]=[C:28](\[CH3:35])/[CH2:29][CH2:30][CH:31]=[C:32]([CH3:34])[CH3:33])[C:10]([O:12][CH3:13])=[O:11].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C([O-])(O)=O.[Na+]>ClCCl.P([O-])([O-])([O-])=O>[OH:7][CH2:8][C@@H:9]([O:14][CH2:15]/[CH:16]=[C:17](/[CH3:39])\[CH2:18][CH2:19]/[CH:20]=[CH:21]/[C:22]([CH3:38])([CH3:37])[CH2:23][CH2:24][C:25](=[CH2:36])[CH2:26]/[CH:27]=[C:28](\[CH3:35])/[CH2:29][CH2:30][CH:31]=[C:32]([CH3:33])[CH3:34])[C:10]([O:12][CH3:13])=[O:11]

Participants

6

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 516892Sodium BicarbonateHCID 67255149HCID 67255149, compound

Product 1

HCID 12000074HCID 12000074, compoundYield 61%

Reagents, catalysts & solvents 2

HCID 1061PhosphateSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of methyl (R)-3-(3,4-dimethoxybenzyloxy)-2-[(2Z,6E,13E)-3,8,8,14,18-pentamethyl-11-methylene-nonadeca-2,6,13,17-tetraen-1-yloxy]-propanoate (10) (9.00 mg, 14.7 μmol, 1.00 eq.) in dichloromethane (2.00 mL) and phosphate buffer (0.20 mL, pH=7) was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.00 mg, 22.1 μmol, 1.50 eq.) at 5° C. After being stirred at the same temperature for 1 h, the reaction mixture was diluted with dichloromethane and treated with saturated aq. NaHCO3 at 0° C. The reaction mixture was extracted with two portions of dichloromethane. The combined extract was washed with saturated aq. NaHCO3, brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (hexane:diethyl ether=89:11) to give methyl (R)-3-hydroxy-2-[(2Z,6E,13E)-3,8,8,14,18-pentamethyl-11-methylene-nonadeca-2,6,13,17-tetraen-1-yloxy]-propanoate (11) (4.10 mg, 8.89 μmol, 61%) as a colorless oil and recover (10) (3.10 mg, 5.12 μmol, 34%).

Workup

  1. extractionThe reaction mixture was extracted with two portions of dichloromethane
  2. extractionThe combined extract
  3. washwas washed with saturated aq. NaHCO3, brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography (hexane:diethyl ether=89:11)

Sources & evidence

ORD record
ord-121c5749cc82499fb0a7984e63c57ca7
Source dataset
uspto-grants-2013_12
Patent number
US08604004B2

Reaction notes

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