Ammonium Chloride → n-[4-(4,7-Diamino-2-methylthieno[3,2-c]pyridin-3-yl)phenyl]-n'-(3-methylphenyl)urea

HRID 17128Notes

Reaction equation

HRID 17128 reaction equation
[NH2:1][C:2]1[C:7]2[C:8]([C:12]3[CH:17]=[CH:16][C:15]([NH:18][C:19]([NH:21][C:22]4[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[CH:23]=4)=[O:20])=[CH:14][CH:13]=3)=[C:9]([CH3:11])[S:10][C:6]=2[C:5]([N+:29]([O-])=O)=[CH:4][N:3]=1.[NH4+].[Cl-]>C(O)C.O.[Fe]>[NH2:1][C:2]1[C:7]2[C:8]([C:12]3[CH:17]=[CH:16][C:15]([NH:18][C:19]([NH:21][C:22]4[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[CH:23]=4)=[O:20])=[CH:14][CH:13]=3)=[C:9]([CH3:11])[S:10][C:6]=2[C:5]([NH2:29])=[CH:4][N:3]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 18450935n-[4-(4-Amino-2-methyl-7-nitrothieno[3,2-c]pyridin-3-yl)phenyl]-n'-(3-methylphenyl)urea

Product 1

HCID 18450933n-[4-(4,7-Diamino-2-methylthieno[3,2-c]pyridin-3-yl)phenyl]-n'-(3-methylphenyl)ureaYield 36.8%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A suspension of Example 66E (0.44 g, 1.01 mmol), NH4Cl (0.054 g, 1.01 mmol), and iron powder (0.45 g, 8.1 mmol) in ethanol (16 mL) and water (4 mL) was heated at 80° C. for 3 hours, cooled to room temperature, and filtered through diatomaceous earth (Celite®). The pad was washed with ethyl acetate and ethanol and the filtrate was extracted three times with ethyl acetate. The combined extracts were washed with brine, dried (Na2SO4), filtered, and concentrated. The residue was purified by flash column chromatography on silica gel with 5% methanol/dichloromethane to provide 0.15 g of the desired product. 1H NMR (300 MHz, DMSO-d6) δ 2.27 (s, 3H), 2.29 (s, 3H), 4.48 (s, 2H), 4.59 (s, 2H), 6.80 (d, J=7.46 Hz, 1H), 7.17 (t, J=7.80 Hz, 1H), 7.25-7.29 (m, 3H), 7.30 (s, 1H), 7.31 (s, 1H), 7.60 (d, J=8.81 Hz, 2H), 8.67 (s, 1H), 8.86 (s, 1H); MS (ESI(+)) m/e 404 (M+H)+.

Workup

  1. filtrationfiltered through diatomaceous earth (Celite®)
  2. washThe pad was washed with ethyl acetate and ethanol
  3. extractionthe filtrate was extracted three times with ethyl acetate
  4. washThe combined extracts were washed with brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by flash column chromatography on silica gel with 5% methanol/dichloromethane

Sources & evidence

ORD record
ord-59eb91be7fc548d38601a3465f5fa4e5
Source dataset
uspto-grants-2010_06
Patent number
US07737160B2

Reaction notes

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