4-Fluorophenylboronic acid → HCID 59320849, compound

HRID 341183Notes

Reaction equation

HRID 341183 reaction equation
Br[C:2]1[CH:3]=[C:4]([N+:16]([O-:18])=[O:17])[C:5]([NH:8][C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([NH2:15])[CH:10]=2)=[N:6][CH:7]=1.[F:19][C:20]1[CH:25]=[CH:24][C:23](B(O)O)=[CH:22][CH:21]=1>COCCOC.C([O-])([O-])=O.[Na+].[Na+]>[F:19][C:20]1[CH:25]=[CH:24][C:23]([C:2]2[CH:3]=[C:4]([N+:16]([O-:18])=[O:17])[C:5]([NH:8][C:9]3[CH:14]=[CH:13][CH:12]=[C:11]([NH2:15])[CH:10]=3)=[N:6][CH:7]=2)=[CH:22][CH:21]=1

Participants

5

Reactant 2

HCID 2856454-Fluorophenylboronic acidHCID 59320866N1-(5-Bromo-3-nitro-2-pyridinyl)-1,3-benzenediamine

Product 1

HCID 59320849HCID 59320849, compoundYield 62.4%

Reagents, catalysts & solvents 2

HCID 80711,2-DimethoxyethaneSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of PdCl2dppf (300 mg, 0.4 mmol), N-(5-bromo-3-nitro-pyridin-2-yl)-benzene-1,3-diamine (Preparation P1, 2.5 g, 8.2 mmol) and 4-fluorophenylboronic acid (1.4 g, 10 mmol) in DME (16 ml) and 2N Na2CO3 (16 ml) was deoxygenated by evacuate/fill N2 (×3), then stirred and heated at 80° C. under N2 for 4 hours. After cooling to RT the mixture was partitioned between EtOAc/H2O and then filtered through Celite. The organic layer was washed with brine (×1) then dried (MgSO4), filtered and evaporated. The residue was purified by chromatography on silica (10→50% EtOAc/petrol) to give the title compound (1.66 g) as a dark red/brown solid. 1H NMR (400 MHz, DMSO-d6): 9.85 (1H, s), 8.87 (1H, d), 8.70 (1H, d), 7.82 (2H, dd), 7.33 (2H, t), 7.02 (1H, t), 6.92-6.81 (2H, m), 6.40 (1H, d), 5.15 (2H, s).

Workup

  1. customwas deoxygenated
  2. customby evacuate/fill N2 (×3)
  3. temperatureAfter cooling to RT the mixture
  4. customwas partitioned between EtOAc/H2O
  5. filtrationfiltered through Celite
  6. washThe organic layer was washed with brine (×1)
  7. dry with materialthen dried (MgSO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by chromatography on silica (10→50% EtOAc/petrol)

Sources & evidence

ORD record
ord-a6f5c4d9188b4c4a98bebddbfcc54b53
Source dataset
uspto-grants-2014_11
Patent number
US08895745B2

Reaction notes

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