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]=1A 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.
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