2,6-Pyridinedicarboxylic acid → AA 863

HRID 1074572Notes

Reaction equation

HRID 1074572 reaction equation
[CH3:1][C:2]1[C:3]([O:27]C)=[C:4]([O:25][CH3:26])[C:5]([O:23][CH3:24])=[C:6]([O:21]C)[C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][C:12]#[C:13][CH2:14][CH2:15][CH2:16][C:17]#[C:18][CH2:19][OH:20].N1C(C(O)=O)=CC=CC=1C(O)=O>C(#N)C.O>[CH3:24][O:23][C:5]1[C:6](=[O:21])[C:7]([CH2:8][CH2:9][CH2:10][CH2:11][C:12]#[C:13][CH2:14][CH2:15][CH2:16][C:17]#[C:18][CH2:19][OH:20])=[C:2]([CH3:1])[C:3](=[O:27])[C:4]=1[O:25][CH3:26]

Participants

5

Reactant 2

HCID 103672,6-Pyridinedicarboxylic acidHCID 20495942HCID 20495942, compound

Product 1

HCID 133543AA 863Yield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent2×

Procedure

In a mixed solvent of acetonitrile (6 ml) and water (3 ml) were dissolved 5-methyl-1,2,3,4-tetramethoxy-6-(12-hydroxy-5,10-dodecadiynyl)benzene (II, 0.50 g, 1.29 mmole) and pyridine-2,6-dicarboxylic acid (0.65 g, 1.29×3 mmole), and the solution was stirred under cooling with ice, followed by adding dropwise and ice-cooled solution of ceric ammonium nitrate (2.12 g) in acetonitrile (4.5 ml) and water (4.5 ml) over a 15-minute period. The reaction was allowed to proceed under the same conditions for 15 minutes and further at room temperature for 15 minutes. After the completion of the reaction, the insolubles were filtered out, and the acetonitrile was distilled off under reduced pressure. By adding isopropyl ether (20 ml) and water (20 ml) to the residue, the product was extracted. The organic layer was washed with aqueous sodium bicarbonate solution and aqueous sodium chloride solution, successively, dried (over MgSO4) and concentrated under reduced pressure, resulting in a residue. The residue was chromatographed on a column of silica gel developing with a mixed solvent of isopropyl ether and ethyl acetate to give 2,3-dimethoxy-5-methyl-6-(12-hydroxy-5,10-dodecadiynyl)-1,4-benzoquinone (I, 0.42 g, 91%, oil).

Workup

  1. temperatureunder cooling with ice
  2. additionby adding dropwise
  3. customAfter the completion of the reaction
  4. filtrationthe insolubles were filtered out
  5. distillationthe acetonitrile was distilled off under reduced pressure
  6. additionBy adding isopropyl ether (20 ml) and water (20 ml) to the residue
  7. extractionthe product was extracted
  8. washThe organic layer was washed with aqueous sodium bicarbonate solution and aqueous sodium chloride solution
  9. dry with materialsuccessively, dried (over MgSO4)
  10. concentrationconcentrated under reduced pressure
  11. customresulting in a residue
  12. customThe residue was chromatographed on a column of silica gel developing with a mixed solvent of isopropyl ether and ethyl acetate

Sources & evidence

ORD record
ord-30d50bbf0d2641778d7d3ab4fd2af403
Source dataset
uspto-grants-1983_07
Patent number
US04393075

Reaction notes

Loading…