Methyl iodide → Diazene, 1-(4-methoxyphenyl)-2-(4-nitrophenyl)-

HRID 218296Notes

Reaction equation

HRID 218296 reaction equation
[OH-].[K+].[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([N:12]=[N:13][C:14]2[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=2)=[CH:8][CH:7]=1)([O-:5])=[O:4].[CH3:21]I>C(Cl)Cl>[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([N:12]=[N:13][C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)=[CH:8][CH:7]=1)([O-:5])=[O:4]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 14797Potassium HydroxideHCID 150354-[(4-Nitrophenyl)azo]phenol

Product 1

HCID 34576Diazene, 1-(4-methoxyphenyl)-2-(4-nitrophenyl)-Yield 52%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Aqueous KOH (0.3 M, 6 mL) was added to a solution of 14 (0.21 g, 1 mmol) in CH2Cl2 (50 mL). After stirring for 10 min, the precipitate was filtered, washed with cold H2O (10 mL), and dried. The resulting solid was suspended in CH2Cl2 (50 mL) and MeI (150 μL, 2 mmol) was added (see FIG. 25). The mixture was heated for 40 h under reflux and Ar. After cooling to ambient temperature, the mixture was washed with water (20 mL). The organic layer was dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography [SiO2: hexanes/CH2Cl2 (1:1)] resulting in 11 (0.10 g, 52%) as an orange solid. mp=151° C.; FABMS: m/z=258 [M+H]+; 1H-NMR (400 MHz, chloroform-d): δ=3.88 (3H, s), 6.99-7.01 (2H, m), 7.93-7.95 (4H, m), 8.30-8.33 (2H, m); 13C-NMR (100 MHz, CDCl3): δ=55.9, 114.7, 123.3, 124.9, 125.8, 147.2, 148.5, 156.2, 163.5.

Workup

  1. filtrationthe precipitate was filtered
  2. washwashed with cold H2O (10 mL)
  3. customdried
  4. temperatureThe mixture was heated for 40 h
  5. temperatureunder reflux
  6. washthe mixture was washed with water (20 mL)
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customthe solvent was evaporated under reduced pressure
  9. customThe residue was purified by column chromatography [SiO2: hexanes/CH2Cl2 (1:1)]

Sources & evidence

ORD record
ord-2aec4b66f2354eaca78663de1cfeacb0
Source dataset
uspto-grants-2012_06
Patent number
US08198436B2

Reaction notes

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