Hydrazine hydrate (1:1) → Tert-butyl 4-[(5-amino-1-benzofuran-7-yl)methyl]-3-methylpiperazine-1-carboxylate

HRID 1162053Notes

Reaction equation

HRID 1162053 reaction equation
O.NN.[CH3:4][CH:5]1[N:10]([CH2:11][C:12]2[C:20]3[O:19][CH:18]=[CH:17][C:16]=3[CH:15]=[C:14]([N+:21]([O-])=O)[CH:13]=2)[CH2:9][CH2:8][N:7]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:6]1>[Ni].C(O)C.C1COCC1>[NH2:21][C:14]1[CH:13]=[C:12]([CH2:11][N:10]2[CH2:9][CH2:8][N:7]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:6][CH:5]2[CH3:4])[C:20]2[O:19][CH:18]=[CH:17][C:16]=2[CH:15]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 66893976Tert-butyl 3-methyl-4-[(5-nitro-1-benzofuran-7-yl)methyl]piperazine-1-carboxylate

Product 1

HCID 66892829Tert-butyl 4-[(5-amino-1-benzofuran-7-yl)methyl]-3-methylpiperazine-1-carboxylateYield 127%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 21873804Tetrahydrofuran ethanolSolvent

Procedure

Raney nickel (slurry in ethanol) and hydrazine hydrate (97 μL, 2.0 mmol) were added to tert-butyl 3-methyl-4-[(5-nitro-1-benzofuran-7-yl)methyl]piperazine-1-carboxylate (115 mg, 0.31 mmol; obtained in Step 1) in ethanol:THF (4:1; 5 mL). The resulting mixture was stirred at room temperature for 1.5 h, followed by filtration through Celite. The Celite pad was rinsed several times with ethanol. The solvent was evaporated to give the crude product (136 mg) as a light green solid. This material was used in the next step without further purification. HPLC 98%, RT=1.77 min (System A; 5-60% MeCN over 3 min), 100%, RT=1.50 min (System B; 5-60% MeCN over 3 min). MS (ESI+) for C19H27N3O3 m/z 346 (M+H)+.

Workup

  1. filtrationfollowed by filtration through Celite
  2. washThe Celite pad was rinsed several times with ethanol
  3. customThe solvent was evaporated

Sources & evidence

ORD record
ord-f0df95dfdccc46af8b9e442cab6e37f9
Source dataset
uspto-grants-2010_10
Patent number
US07820675B2

Reaction notes

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