Hydrazine hydrate (1:1) → 4-(2-(Dimethylamino)ethyl)-3,4-dihydro-2H-benzo[b][1,4]thiazin-7-amine

HRID 424531Notes

Reaction equation

HRID 424531 reaction equation
[CH3:1][N:2]([CH3:18])[CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][S:8][C:7]2[CH:11]=[C:12]([N+:15]([O-])=O)[CH:13]=[CH:14][C:6]1=2.O.NN>CO.[Ni]>[CH3:1][N:2]([CH3:18])[CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][S:8][C:7]2[CH:11]=[C:12]([NH2:15])[CH:13]=[CH:14][C:6]1=2

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 59144138N,N-Dimethyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine

Product 1

HCID 591441264-(2-(Dimethylamino)ethyl)-3,4-dihydro-2H-benzo[b][1,4]thiazin-7-amineYield 99%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

To a solution of N,N-dimethyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine (0.9695 g, 3.63 mmol) in MeOH (20 mL) was added Raney-Nickel (slurry in water; ˜0.1 g, 3.63 mmol) followed by hydrazine hydrate (1.82 mL, 37.4 mmol). The mixture was immersed in a preheated oil bath and refluxed for 20 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 filtered through a plug of silica gel (2.5:97.5 (2M NH3 in MeOH):CH2Cl2). The collected fractions gave brown viscous oil (0.84 g, 99%). 1H NMR (CDCl3) δ 6.58 (d, J=8.7 Hz, 1H), 6.45 (d, J=2.7 Hz, 1H), 6.40 (dd, J=2.7, 8.7 Hz, 1H), 3.51-3.48 (m, 2H), 3.30 (t, J=7.2 Hz, 2H), 3.03-3.00 (m, 2H), 2.48 (t, J=7.5 Hz, 2H), 2.27 (s, 6H); ESI-MS (m/z, %): 240, 238 (MH+, 100).

Workup

  1. customThe mixture was immersed in a preheated oil bath
  2. temperaturerefluxed for 20 minutes
  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 filtered through a plug of silica gel (2.5:97.5 (2M NH3 in MeOH):CH2Cl2)

Sources & evidence

ORD record
ord-a5153755057246cab3f3b55561ca1ff4
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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