N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide → N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-amino-dibenzo[b,d]furan-1-carboxamide

HRID 1788088Notes

Reaction equation

HRID 1788088 reaction equation
[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:31])[C:7]=1[NH:8][C:9]([C:11]1[C:19]2[C:18]3[CH:20]=[C:21]([N+:24]([O-])=O)[CH:22]=[CH:23][C:17]=3[O:16][C:15]=2[C:14]([O:27][CH:28]([F:30])[F:29])=[CH:13][CH:12]=1)=[O:10]>[Ni].CN(C=O)C>[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:31])[C:7]=1[NH:8][C:9]([C:11]1[C:19]2[C:18]3[CH:20]=[C:21]([NH2:24])[CH:22]=[CH:23][C:17]=3[O:16][C:15]=2[C:14]([O:27][CH:28]([F:29])[F:30])=[CH:13][CH:12]=1)=[O:10]

Participants

4

Reactant 1

HCID 10050271N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide

Product 1

HCID 10320896N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-amino-dibenzo[b,d]furan-1-carboxamide

Reagents, catalysts & solvents 2

HCID 935NickelCatalyst2×HCID 6228DimethylformamideSolvent

Procedure

Second, N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-aminodibenzo[b,d]furan-1-carboxamide was prepared by reacting N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide (prepared using the procedure of Example 4) with Raney Nickel. In particular, to a 500 mL pressure vessel was added N′-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide (2.00 g, 4.27 mmol), DMF (30.0 mL) and Raney Nickel (1.79 g). The reaction mixture was hydrogenated (50 psi) for 23 h (reaction monitored by HPLC). The reaction mixture was filtered, washed with DMF (20 mL) and the filtrate concentrated to a 5 mL volume (distilled below 70° C. under vacuum). Water (33.0 mL) was added, the precipitate filtered, washed with water (20 mL) and dried in a vacuum oven (65° C.) to yield the amine as a cream colored solid (1.67 g, 91.3%). Purity 98.67% by HPLC.

Workup

  1. customprepared
  2. customfor 23 h
  3. custom(reaction monitored by HPLC)
  4. filtrationThe reaction mixture was filtered
  5. washwashed with DMF (20 mL)
  6. concentrationthe filtrate concentrated to a 5 mL volume (distilled below 70° C. under vacuum)
  7. additionWater (33.0 mL) was added
  8. filtrationthe precipitate filtered
  9. washwashed with water (20 mL)
  10. customdried in a vacuum oven (65° C.)

Sources & evidence

ORD record
ord-6b0e8e1cb5944cfeb487d069970659bb
Source dataset
uspto-grants-2009_03
Patent number
US07511150B2

Reaction notes

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