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

HRID 1788090Notes

Reaction equation

HRID 1788090 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].[BH4-].[Na+].Cl>CO.[Pd]>[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

6

Reactant 3

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydride2×HCID 10050271N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide2×

Product 1

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

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 887MethanolSolvent2×

Conditions

Temperature
7.5 °C

Procedure

Fourth, 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 sodium borohydride in methanol and palladium on carbon (50% wet with water) catalyst. In particular, to a 100 mL 3-neck round bottom flask were added N-(3,5-dichloropyrid-4-yl)-4-difluoromethoxy-8-nitro-dibenzo[b,d]furan-1-carboxamide (0.468 g, 1 mmol), methanol (15.0 mL), and 10% Pd—C (50% wet, 0.012 g). The reaction mixture was cooled to 5-10° C. and treated with sodium borohydride (0.127 g, 4 mmol) in four portions. The reaction mixture was acidified with conc. HCl to pH˜6, filtered and the Pd-C catalyst was washed with MeOH (˜10 ml). The combined filtrate was concentrated to a residue and slurried in excess water. The solid was filtered, washed with water (75 mL) and dried in a vacuum oven (65° C.) overnight. The dried product appeared as a yellow solid (0.310 g, 70.7%). Purity 79.57% by HPLC.

Workup

  1. customprepared
  2. filtrationfiltered
  3. washthe Pd-C catalyst was washed with MeOH (˜10 ml)
  4. concentrationThe combined filtrate was concentrated to a residue
  5. filtrationThe solid was filtered
  6. washwashed with water (75 mL)
  7. customdried in a vacuum oven (65° C.) overnight

Sources & evidence

ORD record
ord-e144463b449443ad8ea96c41bd4203b8
Source dataset
uspto-grants-2009_03
Patent number
US07511150B2

Reaction notes

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