Chlorotrimethylsilane → 2-(2,4-Dichloro-6-methoxyphenyl)ethanamine

HRID 1021348Notes

Reaction equation

HRID 1021348 reaction equation
[BH4-].[Li+].Cl[Si](C)(C)C.[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([O:16][CH3:17])[C:10]=1[CH:18]=[CH:19][N+:20]([O-])=O>O1CCCC1>[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([O:16][CH3:17])[C:10]=1[CH2:18][CH2:19][NH2:20]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 4148881Lithium borohydrideHCID 670808981,5-Dichloro-3-methoxy-2-(2-nitrovinyl)benzene

Product 1

HCID 670803092-(2,4-Dichloro-6-methoxyphenyl)ethanamineYield 96.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred suspension of lithium borohydride (0.20 g; 9.0 mmol) in 15 mL tetrahydrofuran at ambient temperature was added chlorotrimethylsilane, dropwise over 2 minutes. Gas was evolved and the mixture warmed slightly. After stirring for 20 minutes, gas evolution had ceased, and argon gas was bubbled through the mixture for 2 minutes to remove the remaining trimethylsilane that had formed. A solution of 1,5-dichloro-3-methoxy-2-(2-nitrovinyl)benzene (0.56 g; 2.3 mmol) in 10 mL THF was then added dropwise with stirring at ambient temperature over 4 minutes. The resulting mixture was then stirred and heated to reflux. After 90 minutes, the heat was removed, and after cooling to ambient temperature, the mixture was cooled in an ice bath and carefully quenched with 15 mL of methanol. The solvent was evaporated, and the residue was partitioned between 30 mL of 20% KOH and 15 mL of dichloromethane. The organic layer was dried over sodium sulfate and evaporated to give 0.49 g of 2-(2,4-dichloro-6-methoxyphenyl)ethanamine as a cloudy yellow oil. MS (apci, pos) m/z=220.

Workup

  1. temperaturethe mixture warmed slightly
  2. customargon gas was bubbled through the mixture for 2 minutes
  3. customto remove the remaining trimethylsilane that
  4. customhad formed
  5. stirringwith stirring at ambient temperature over 4 minutes
  6. stirringThe resulting mixture was then stirred
  7. temperatureheated to reflux
  8. waitAfter 90 minutes
  9. customthe heat was removed
  10. temperaturethe mixture was cooled in an ice bath
  11. customcarefully quenched with 15 mL of methanol
  12. customThe solvent was evaporated
  13. customthe residue was partitioned between 30 mL of 20% KOH and 15 mL of dichloromethane
  14. dry with materialThe organic layer was dried over sodium sulfate
  15. customevaporated

Sources & evidence

ORD record
ord-29b9d4d5de7c4d2986b70718f83aab9a
Source dataset
uspto-grants-2014_05
Patent number
US08716498B2

Reaction notes

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