Sodium Hydroxide → HCID 19064631, compound

HRID 481978Notes

Reaction equation

HRID 481978 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[S:9][CH:8]=[C:7]([CH2:10][CH2:11][N:12]([CH3:14])[CH3:13])[C:6]=2[CH:15]=1.C([Li])CCC.C1(P([N:35]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[H-].COCCO[Al+]OCCOC.[Na+].[H-].[H-].[OH-].[Na+]>O1CCCC1.O>[NH2:35][C:2]1[CH:3]=[CH:4][C:5]2[S:9][CH:8]=[C:7]([CH2:10][CH2:11][N:12]([CH3:14])[CH3:13])[C:6]=2[CH:15]=1

Participants

9

Reactant 6

HCID 14798Sodium HydroxideHCID 31583HCID 31583, compoundHCID 166653HydrideHCID 199401P,P-Diphenylphosphinic azideHCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydrideHCID 178418339Butyllithium

Product 1

HCID 19064631HCID 19064631, compoundYield 18%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of 0.193 gm (0.68 mMol) 5-bromo-3-(N',N'-dimethyl-2-aminoethyl)benzothiophene in 10 mL tetrahydrofuran was cooled to -78° C. and then to it were added 0.425 mL (0.68 mMol) n-butyllithium (1.6M in hexane). The reaction mixture was stirred at -78° C. for 10 minutes and then this solution was cannulated into a solution of 0.18 mL (0.83 mMol) diphenylphosphoryl azide in 10 mL tetrahydrofuran at -78° C. The reaction mixture was maintained at this temperature for 2 hours and then 1 mL (3.56 mmol) sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al) was added and the reaction mixture warmed to 0° C. The reaction mixture was maintained at this temperature for 30 minutes and then at room temperature for 30 minutes. The reaction mixture was cooled again to 0° C. and water added to decompose excess hydride reagent. The pH of the solution was adjusted to about 12 by the addition of 2N sodium hydroxide and was then extracted first with ethyl acetate and then with dichloromethane. The combined organic extracts were dried over sodium sulfate and then concentrated under reduced pressure. The residue was subjected to flash silica gel chromatography, eluting with dichloromethane containing 6% methanol and 0.5% ammonium hydroxide. Fractions containing the desired product were combined and concentrated under reduced pressure to provide 0.027 gm (18%) of 5-amino-3-(N',N'-dimethyl-2-aminoethyl)benzothiophene. The oxalate salt was formed to provide the title compound.

Workup

  1. temperatureThe reaction mixture was maintained at this temperature for 2 hours
  2. temperaturethe reaction mixture warmed to 0° C
  3. temperatureThe reaction mixture was maintained at this temperature for 30 minutes
  4. waitat room temperature for 30 minutes
  5. temperatureThe reaction mixture was cooled again to 0° C.
  6. extractionwas then extracted first with ethyl acetate
  7. dry with materialThe combined organic extracts were dried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. washeluting with dichloromethane containing 6% methanol and 0.5% ammonium hydroxide
  10. additionFractions containing the desired product
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4fdfb7775a154bca841d5a4e9de83d90
Source dataset
uspto-grants-1998_08
Patent number
US05792763

Reaction notes

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