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

HRID 424504Notes

Reaction equation

HRID 424504 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-amine

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

A dark mixture of N,N-dimethyl-2-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)ethanamine (1.0 g, 3.74 mmol) in methanol (10 mL) under an argon atmosphere was treated with Raney Nickel (˜0.22 g, 3.74 mmol) and hydrazine hydrate (1.82 mL, 37.4 mmol). The reaction was transferred to a pre-heated oil bath at 65° C. After 50 minutes, the mixture was allowed to cool to room temperature and then poured over a pad of Celite. The Celite pad was rinsed with methanol (20 mL). The filtrate was concentrated, and the crude material was subjected to a short column on silica gel (1:9 (2M NH3 in MeOH):CH2Cl2). The resulting brown residue was carried on to the next step. 1H-NMR (DMSO-d6) δ 6.49 (d, J=9.0 Hz, 1H), 6.27-6.23 (m, 2H), 4.42 (brs, 2H), 3.40-3.30 (m, 2H), 3.18 (t, J=7.2 Hz, 2H), 2.98-2.94 (m, 2H), 2.36 (t, J=7.2 Hz, 2H), 2.16 (s, 6H); ESI-MS (m/z, %): 238 (MH+, 100), 193 (56), 147 (58).

Workup

  1. customThe reaction was transferred to a pre-heated oil bath at 65° C
  2. additionpoured over a pad of Celite
  3. washThe Celite pad was rinsed with methanol (20 mL)
  4. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-d7a4492d340f484cb1830e0eebbdc7f8
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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