Ethyl Acetate → HCID 9947947, compound

HRID 1582868Notes

Reaction equation

HRID 1582868 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:9]=[C:10]2[C:15](=[CH:16][CH:17]=1)[CH:14]=[C:13]([O:18][CH3:19])[C:12]([O:20][CH3:21])=[CH:11]2.[N:22]([O-])=O.[Na+].C(OCC)(=O)C>Br.O.[Cu]>[CH3:19][O:18][C:13]1[C:12]([O:20][CH3:21])=[CH:11][C:10]2[C:15]([CH:14]=1)=[CH:16][CH:17]=[C:8]1[C:9]=2[N:22]=[N:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]1=2

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 22716427HCID 22716427, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 9947947HCID 9947947, compoundYield 18%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 260Hydrogen BromideSolventHCID 962WaterSolvent

Procedure

6-(2-Aminophenyl)-2,3-dimethoxynaphthalene (5, 70 mg, 0.25 mmol) was dissolved in 48% hydrobromic acid (4.25 mL), cooled in ice-salt bath, and treated dropwise with stirring with sodium nitrite (0.13 g) in water (2.2 mL). Stirring was continued for 0.5 h., and to the cold solution was then added with stirring freshly precipitated copper (0.5 g). The mixture was allowed to rise slowly to room temperature and left overnight. The solid was filtered off and washed with hot chloroform. The chloroform solution was washed with diluted sodium hydroxide solution, then with water, dried (anhydrous Na2SO4) and rotaevaporated to give the crude product. Chromatography on silica gel using 50:50 hexanes:ethyl acetate afforded the title compound (13 mg) in 18% yield; 1H NMR (CDCl3) d 4.11(3H, s), 4.24(3H, s), 7.37(1H, s), 7.89˜7.94 (2H, m), 8.14(1H, d, J=8.9), 8.41(1H, d, J=8.8), 8.61˜8.66(1H, m), 8.75˜8.80(1H, m), 9.24(1H, s); 13C NMR d 56.1, 56.4, 104.0, 107.3, 112.3, 116.5, 118.5, 121.7, 126.7, 128.6, 128.8, 131.1, 131.2, 131.9, 141.5, 146.3, 150.9, 151.0.

Workup

  1. additiontreated dropwise
  2. additionto the cold solution was then added
  3. customto rise slowly to room temperature
  4. waitleft overnight
  5. filtrationThe solid was filtered off
  6. washwashed with hot chloroform
  7. washThe chloroform solution was washed with diluted sodium hydroxide solution
  8. dry with materialwith water, dried (anhydrous Na2SO4)
  9. customto give the crude product

Sources & evidence

ORD record
ord-4fe878391c994de596421a1419aaa20a
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

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