Tetrafluoro-m-phenylenediamine dihydrochloride → HCID 135409376, compound

HRID 1061729Notes

Reaction equation

HRID 1061729 reaction equation
[N:1]([CH:4]([CH3:26])[CH2:5][N:6]1[C:14]2[CH:13]=[C:12]([O:15]CC3C=CC=CC=3)[CH:11]=[C:10]3[CH2:23][CH2:24][CH2:25][C:8]([C:9]=23)=[N:7]1)=[N+]=[N-].C([O-])=O.[NH4+].C1(N)C(F)=C(F)C(F)=C(N)C=1F.Cl.Cl>C(O)C.[Pd]>[NH2:1][CH:4]([CH3:26])[CH2:5][N:6]1[C:14]2[CH:13]=[C:12]([OH:15])[CH:11]=[C:10]3[C:9]=2[C:8]([CH2:25][CH2:24][CH2:23]3)=[N:7]1

Participants

6

Reactant 3

HCID 149026Tetrafluoro-m-phenylenediamine dihydrochlorideHCID 2723923Ammonium formateHCID 22285722HCID 22285722, compound

Product 1

HCID 135409376HCID 135409376, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a solution of the product from Step G (0.74 g, 2.2 mmol) in ethanol under a nitrogen atmosphere at room temperature was added Pd/C (10%, 0.10 g) followed by ammonium formate (0.54 g, 8.5 mmol). This suspension was stirred for 24 h at room temperature followed by filtration through a filter-aide. The filtrate was evaporated to a residue that was purified by column chromatography (silica, 5% to 20% gradient of methanol in dichloromethane) to give a solid that was converted to the dihydrochloride salt, which was crystallized from methanol/ether (0.38 g, 58%): m.p 286-288° C.; MS (ES) m/z 232 (M+); 1H NMR (DMSO-d6) δ 8.28 (3H, brs), 6.59 (1H, s), 6.43 (1H, s), 4.40-4.22 (2H, m), 3.61 (11H, m), 2.79 (4H, m), 2.27 (2H, m), 1.18 (3H, d, J=8.0 Hz).

Workup

  1. filtrationfollowed by filtration through a filter-aide
  2. customThe filtrate was evaporated to a residue that
  3. customwas purified by column chromatography (silica, 5% to 20% gradient of methanol in dichloromethane)
  4. customto give a solid
  5. customwas crystallized from methanol/ether (0.38 g, 58%)
  6. custom286-288° C.

Sources & evidence

ORD record
ord-7d3c4b52fe604ed18b72aed7e175e07f
Source dataset
uspto-grants-2005_11
Patent number
US06960608B2

Reaction notes

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