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

HRID 424544Notes

Reaction equation

HRID 424544 reaction equation
[CH3:1][N:2]([CH3:19])[CH2:3][CH2:4][CH2:5][N:6]1[CH2:11][CH2:10][S:9][C:8]2[CH:12]=[C:13]([N+:16]([O-])=O)[CH:14]=[CH:15][C:7]1=2.O.NN>CO.[Ni]>[CH3:19][N:2]([CH3:1])[CH2:3][CH2:4][CH2:5][N:6]1[CH2:11][CH2:10][S:9][C:8]2[CH:12]=[C:13]([NH2:16])[CH:14]=[CH:15][C:7]1=2

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 59144154N,N-Dimethyl-3-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)propan-1-amine

Product 1

HCID 591440934-(3-(Dimethylamino)propyl)-3,4-dihydro-2H-benzo[b][1,4]thiazin-7-amineYield 99.4%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

A solution of N,N-dimethyl-3-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)propan-1-amine (0.27 g, 0.960 mmol) in dry methanol (10 mL) was treated with hydrazine hydrate (0.349 mL, 9.60 mmol), followed by Raney-Nickel (0.1 g, 0.096 mmol) at room temperature. The resulting mixture was refluxed for 5 minutes in a pre-heated oil bath. The reaction was then brought to room temperature, filtered through a pad of Celite, and washed with methanol (3×10 mL). The combined methanol layers were evaporated, and the crude material was purified by flash column chromatography (5:95 (2 M NH3 in MeOH):CH2Cl2) on silica gel to obtain the title product (0.24 g, 99%) as a syrup. 1H NMR (DMSO-d6) δ 6.50 (dd, 1H, J=2.4, 7.0 Hz), 6.26-6.23 (m, 2H), 4.41 (s, 2H), 3.32-3.30 (m, 2H), 3.09 (t, 2H, J=7.2 Hz), 2.98-2.95 (m, 2H), 2.21 (t, 2H, J=6.9 Hz), 2.11 (s, 6H), 1.63-1.54 (m, 2H); ESI-MS (m/z, %): 252 (MH+, 100).

Workup

  1. temperatureThe resulting mixture was refluxed for 5 minutes in a pre-heated oil bath
  2. customwas then brought to room temperature
  3. filtrationfiltered through a pad of Celite
  4. washwashed with methanol (3×10 mL)
  5. customThe combined methanol layers were evaporated
  6. customthe crude material was purified by flash column chromatography (5:95 (2 M NH3 in MeOH):CH2Cl2) on silica gel

Sources & evidence

ORD record
ord-20b67661b2354e2cb0db257569b0e256
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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