Hydrazine → HCID 69435001, compound

HRID 916180Notes

Reaction equation

HRID 916180 reaction equation
[N+:1]([C:4]1[CH:24]=[CH:23][C:7]([CH2:8][N:9]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:11]=[C:10]2[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:6][CH:5]=1)([O-])=O.NN>C(O)C.[Ni]>[NH2:1][C:4]1[CH:5]=[CH:6][C:7]([CH2:8][N:9]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:11]=[C:10]2[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:23][CH:24]=1

Participants

5

Reactant 2

HCID 9321HydrazineHCID 15090439Ethyl 1-[(4-nitrophenyl)methyl]-1H-indole-2-carboxylate

Product 1

HCID 69435001HCID 69435001, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

A large excess of Raney® nickel was added in portions to a stirred solution of ethyl 1-(4-nitrobenzyl)-1H-indole-2-carboxylate (0.65 g, 2 mmol), hydrazine (0.5 mL, 16 mmol) in 25 mL of ethanol. After stirring at room temperature for 2 hours the catalyst was then removed by filtering through a short pad of Celite®521. The filtrate was concentrated to give ethyl 1-(4-aminobenzyl)-1H-indole-2-carboxylate (MS (ESI) m/z 294.2 (MH+) as a gummy solid. The gummy solid was then dissolved in 15 mL of methylene chloride. To the solution was added diisopropylethylamine (0.5 mL, 2.9 mmol) and biphenyl 4-sulfonyl chloride (0.5 g, 1.0 mmol). After being stirred at room temperature overnight the reaction was concentracted and the residue was re-dissolved in 15 mL of 2:1:1 THF/MeOH/water. Lithium hydroxide monohydrate (0.2 g, 4.8 mmol) was added and the mixture was stirred at room temperature overnight. Most of the organic solvents was removed and the reaction mixture was made acidic (pH 6) with glacial acetic acid, and the solid was collected and purified by semi-preparative HPLC. The product was collected based on UV absorption and concentrated to give the title compound as a brown solid (0.11 g, 22%): 1H NMR (DMSO-d6) δ 5.75 (s, 2H), 6.93 (d, J=8.9 Hz, 2H), 7.01 (d, J=8.9 Hz, 2H), 7.09 (t, J=8.0 Hz, 1H), 7.43 (t, J=8.0 Hz, 1H), 7.49 (s, 1H), 7.40-7.55 (m, 4H); 7.65-7.80 (m, 3H), 7.75-7.82 (m, 4H), 10.30 (s, 1H), 12.93 (s, 1H); HRMS calcd for C28H23N2O4S: 483.1367; found (ESI+): 483.1374; Anal. calcd for C28H22N2O4S .0.2H2O: C, 69.18; H, 4.64; N, 5.76. Found: C, 69.21; H, 4.60; N, 5.78.

Workup

  1. customwas then removed
  2. filtrationby filtering through a short pad of Celite®521
  3. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-53d094c89fb247e9a55ad5846f6d1dc8
Source dataset
uspto-grants-2007_09
Patent number
US07268159B2

Reaction notes

Loading…