Stannous chloride dihydrate → 3-(3-Chloropropoxy)-4-methoxyaniline

HRID 1593762Notes

Reaction equation

HRID 1593762 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:11]=[C:10]([N+:12]([O-])=O)[CH:9]=[CH:8][C:7]=1[O:15][CH3:16].O.O.[Sn](Cl)Cl.C(=O)(O)[O-].[Na+]>C(OCC)(=O)C>[Cl:1][CH2:2][CH2:3][CH2:4][O:5][C:6]1[CH:11]=[C:10]([CH:9]=[CH:8][C:7]=1[O:15][CH3:16])[NH2:12]

Participants

5

Reactant 3

HCID 61436Stannous chloride dihydrateHCID 516892Sodium BicarbonateHCID 133001802-(3-Chloropropoxy)-1-methoxy-4-nitrobenzene

Product 1

HCID 693135373-(3-Chloropropoxy)-4-methoxyanilineYield 39.8%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

A mixture of 2-(3-chloropropoxy)-1-methoxy-4-nitrobenzene (2.15 g, 8.77 mmol) and tin (II) chloride dihydrate (6.1 g, 27.11 mmol) in 50 mL of ethyl acetate was heated at reflux for 6.5 hours. The reaction mixture was cooled to room temperature and poured into 250 mL of saturated aqueous sodium bicarbonate. After stirring for 40 minutes, additional ethyl acetate was added and the layers were separated. The organic layer was washed with saturated sodium bicarbonate and water then dried over magnesium sulfate and filtered. The solution was concentrated in vacuo and purified by flash column chromatography, eluting with 1:1 hexane: ethyl acetate, to provide 753 mg of 3-(3-chloropropoxy)-4-methoxyaniline as a dark brown oil; 1H NMR (400 MHz, DMSO-d6) δ 2.13 (m, 2H), 3.62 (s, 3H), 3.78 (t, J=6 Hz, 2H), 3.96 (t, J=6 Hz, 2H), 4.77 (br s, 2H), 6.10 (dd, J=8, 2 Hz, 1H), 6.29 (d, J=2 Hz, 1H), 6.66 (d, J=8 Hz, 1H); MS (ES) m/z216.1, 218.1 (M+H)+.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 6.5 hours
  3. customthe layers were separated
  4. washThe organic layer was washed with saturated sodium bicarbonate and water
  5. dry with materialthen dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe solution was concentrated in vacuo
  8. custompurified by flash column chromatography
  9. washeluting with 1:1 hexane

Sources & evidence

ORD record
ord-50af13d003f945b3aa2ebc5ad11bf795
Source dataset
uspto-grants-2007_11
Patent number
US07297795B2

Reaction notes

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