Hydrazine hydrate (1:1) → tert-Butyl 2-(7-amino-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl(methyl)carbamate

HRID 424535Notes

Reaction equation

HRID 424535 reaction equation
[CH3:1][N:2]([CH2:10][CH2:11][N:12]1[CH2:17][CH2:16][S:15][C:14]2[CH:18]=[C:19]([N+:22]([O-])=O)[CH:20]=[CH:21][C:13]1=2)[C:3](=[O:9])[O:4][C:5]([CH3:8])([CH3:7])[CH3:6].O.NN>CO.[Ni]>[NH2:22][C:19]1[CH:20]=[CH:21][C:13]2[N:12]([CH2:11][CH2:10][N:2]([CH3:1])[C:3](=[O:9])[O:4][C:5]([CH3:6])([CH3:7])[CH3:8])[CH2:17][CH2:16][S:15][C:14]=2[CH:18]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 59144159tert-Butyl methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)carbamate

Product 1

HCID 59144160tert-Butyl 2-(7-amino-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl(methyl)carbamateYield 98%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

To a solution of tert-butyl methyl(2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethyl)carbamate (0.8811 g, 2.493 mmol) in MeOH (20 mL) was added Raney-Nickel (slurry in water; 0.5 g, 2.493 mmol) followed by hydrazine hydrate (1.213 mL, 24.93 mmol). The mixture was then immersed in a preheated oil bath and refluxed for 5 minutes The solution was cooled to room temperature and filtered through a pad of Celite. The filter pad was washed with MeOH, and the crude material was concentrated. The crude material was then filtered through a silica plug (70% EtOAc/hexanes). The collected fractions were concentrated to give brown oil (0.78 g, 98%). 1H NMR (CDCl3) δ 6.64-6.58 (m, 1H), 6.45 (d, J=2.4 Hz, 1H), 6.39 (d, J=8.4 Hz, 1H), 3.53-3.50 (m, 2H), 3.39-3.28 (m, 4H), 3.01-2.98 (m, 2H), 2.90 (s, 3H), 1.45 (s, 9H); ESI-MS (m/z, %): 326, 324 (MH+, 95), 268 (100).

Workup

  1. customThe mixture was then immersed in a preheated oil bath
  2. temperaturerefluxed for 5 minutes The solution
  3. filtrationfiltered through a pad of Celite
  4. washThe filter pad was washed with MeOH
  5. concentrationthe crude material was concentrated
  6. filtrationThe crude material was then filtered through a silica plug (70% EtOAc/hexanes)
  7. concentrationThe collected fractions were concentrated

Sources & evidence

ORD record
ord-826b5c7554fe4d86bd4703c57bd2ce6e
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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