Sodium Hydroxide → 2-Methoxy-5-(1-methyl-cyclopropyl)-benzene-1,3-diamine

HRID 1374956Notes

Reaction equation

HRID 1374956 reaction equation
O.O.[Sn](Cl)Cl.[CH3:6][O:7][C:8]1[C:13]([N+:14]([O-])=O)=[CH:12][C:11]([C:17]2([CH3:20])[CH2:19][CH2:18]2)=[CH:10][C:9]=1[N+:21]([O-])=O.[OH-].[Na+]>C(OCC)(=O)C>[CH3:6][O:7][C:8]1[C:13]([NH2:14])=[CH:12][C:11]([C:17]2([CH3:20])[CH2:19][CH2:18]2)=[CH:10][C:9]=1[NH2:21]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 179730712-Methoxy-5-(1-methyl-cyclopropyl)-1,3-dinitro-benzene

Product 1

HCID 179730872-Methoxy-5-(1-methyl-cyclopropyl)-benzene-1,3-diamineYield 52%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Tin(II)chloride dihydrate (11.9 g, 52.6 mmol) was added to a solution of 2-methoxy-5-(1-methyl-cyclopropyl)-1,3-dinitro-benzene (2.21 g, 8.76 mmol) in ethyl acetate (30 mL). The mixture was heated to reflux for 0.25 h upon which the solution became red in color. The solution was cooled to rt and poured onto aqueous 2.0 M NaOH. The aqueous phase was extracted with ethyl acetate and the combined organic layers were washed with saturated NaHCO3. The organic layers were dried over sodium sulfate, eluted through a plug of silica gel (1% ammonium hydroxide in methylene chloride), and the filtrate was concentrated. The residue was redissolved in Et2O and extracted (3×) with 1.0 M HCl. The pH of the combined aqueous layers was adjusted to pH=12 with 2.0M NaOH and extracted with methylene chloride. The combined organic layers were dried over sodium sulfate, filtered and concentrated to provide 2-methoxy-5-(1-methyl-cyclopropyl)-benzene-1,3-diamine (860 mg, 52%) as a red oil. ESI MS (m/z 193, M+H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 0.25 h upon which the solution
  3. extractionThe aqueous phase was extracted with ethyl acetate
  4. washthe combined organic layers were washed with saturated NaHCO3
  5. dry with materialThe organic layers were dried over sodium sulfate
  6. washeluted through a plug of silica gel (1% ammonium hydroxide in methylene chloride)
  7. concentrationthe filtrate was concentrated
  8. dissolutionThe residue was redissolved in Et2O
  9. extractionextracted (3×) with 1.0 M HCl
  10. extractionextracted with methylene chloride
  11. dry with materialThe combined organic layers were dried over sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-7ba2e898abb84726a52d0f28cc1a354f
Source dataset
uspto-grants-2007_01
Patent number
US07166628B2

Reaction notes

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