Hydrazine hydrate (1:1) → HCID 59144118, compound

HRID 424548Notes

Reaction equation

HRID 424548 reaction equation
[CH3:1][N:2]([CH2:10][CH2:11][CH2:12][N:13]1[CH2:18][CH2:17][S:16][C:15]2[CH:19]=[C:20]([N+:23]([O-])=O)[CH:21]=[CH:22][C:14]1=2)[C:3](=[O:9])[O:4][C:5]([CH3:8])([CH3:7])[CH3:6].O.NN>CO.[Ni]>[NH2:23][C:20]1[CH:21]=[CH:22][C:14]2[N:13]([CH2:12][CH2:11][CH2:10][N:2]([CH3:1])[C:3](=[O:9])[O:4][C:5]([CH3:6])([CH3:7])[CH3:8])[CH2:18][CH2:17][S:16][C:15]=2[CH:19]=1

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 59144140HCID 59144140, compound

Product 1

HCID 59144118HCID 59144118, compoundYield 99.8%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

A suspension of tert-butyl methyl(3-(7-nitro-2H-benzo[b][1,4]thiazin-4(3H)-yl)propyl)carbamate (0.6 g, 1.633 mmol) in dry methanol (10 mL) was treated with Raney-Nickel (0.1 g, 1.633 mmol) followed by hydrazine hydrate (0.595 mL, 16.33 mmol) at room temperature. The resulting mixture was refluxed for 10 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 (2M NH3 in MeOH):CH2Cl2) on silica gel to obtain title product (0.55 g, quantitative) as a brown syrup. 1H NMR (DMSO-d6) δ 6.46 (d, 1H, J=9.6 Hz), 6.25-6.21 (m, 2H), 4.44 (s, 2H), 3.32-3.28 (m, 2H), 3.19 (t, 2H, J=6.9 Hz), 3.04 (t, 2H, J=7.2 Hz), 3.00-2.97 (m, 2H), 2.77 (s, 3H), 1.74-1.62 (m, 2H), 1.38 (s, 9H); ESI-MS (m/z, %): 338 (MH+, 100), 337 (96), 282 (54).

Workup

  1. temperatureThe resulting mixture was refluxed for 10 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 (2M NH3 in MeOH):CH2Cl2) on silica gel

Sources & evidence

ORD record
ord-2670a74d17a8417289ad1faaa8594524
Source dataset
uspto-grants-2012_01
Patent number
US08106043B2

Reaction notes

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