Hydrochloric Acid → 4-amino-N-[3-[(E)-N-(diaminomethylideneamino)-C-methylcarbonimidoyl]phenyl]benzamide;dihydrochloride

HRID 547556Notes

Reaction equation

HRID 547556 reaction equation
[ClH:1].Cl.[NH2:3][C:4](=[N:6]/[N:7]=[C:8](/[C:10]1[CH:11]=[C:12]([NH:16][C:17](=[O:27])[C:18]2[CH:23]=[CH:22][C:21]([N+:24]([O-])=O)=[CH:20][CH:19]=2)[CH:13]=[CH:14][CH:15]=1)\[CH3:9])[NH2:5].CCO.Cl>[Fe].O>[ClH:1].[ClH:1].[NH2:24][C:21]1[CH:20]=[CH:19][C:18]([C:17]([NH:16][C:12]2[CH:13]=[CH:14][CH:15]=[C:10](/[C:8](=[N:7]/[N:6]=[C:4]([NH2:5])[NH2:3])/[CH3:9])[CH:11]=2)=[O:27])=[CH:23][CH:22]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 702EthanolHCID 87307446N-[3-[(E)-N-(diaminomethylideneamino)-C-methylcarbonimidoyl]phenyl]-4-nitrobenzamide;dihydrochloride

Product 1

HCID 873068154-amino-N-[3-[(E)-N-(diaminomethylideneamino)-C-methylcarbonimidoyl]phenyl]benzamide;dihydrochlorideYield 212.2%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Procedure

To a refluxing suspension of amide F4 (2.02 g, 5.36 mmol) in 2:1 EtOH:H2O (100 mL) were sequentially added Fe dust (1.20 g, 21.44 mmol) and c.HCl (2 mL), and the resulting suspension was refluxed for 14 h. After this time, the hot reaction mixture was filtered through a pad of Celite, and the solvent was removed under reduced pressure. The residue was re-dissolved in hot H2O, and the resulting suspension filtered through a pad of Celite. Solvent was removed under reduced pressure, and the residue dried via three MeOH-azeotrope cycles. The resulting residue was reprecipitated from acidified MeOH to afford triamine F5 (2.18 g, quantitative) as an amorphous cream solid; 1H NMR (400 MHz, DMSO): δ 11.30 (s, 1H, hydrazonyl-N+—H), 10.05 (s, 1H, ArC(O)NHAr), 8.21 (s, 1H, ArH), 8.20-7.55 (m, 8H, ArH & ═C(NH2)2), 7.36 (t, J=7.90 Hz, 1H, ArH), 6.91 (d, J=7.96 Hz, 1H, ArH), 5.30 (v br s, 3H, ArNH3+), 2.35 (s, 3H, Ar(CH3)═N—); LCMS (APCI+): 311 (100%).

Workup

  1. filtrationAfter this time, the hot reaction mixture was filtered through a pad of Celite
  2. customthe solvent was removed under reduced pressure
  3. dissolutionThe residue was re-dissolved in hot H2O
  4. filtrationthe resulting suspension filtered through a pad of Celite
  5. customSolvent was removed under reduced pressure
  6. dry with materialthe residue dried via three MeOH-azeotrope cycles
  7. customThe resulting residue was reprecipitated

Sources & evidence

ORD record
ord-b3bba3f84c3b48399cef1fffec8f06b8
Source dataset
uspto-grants-2011_05
Patent number
US07939546B2

Reaction notes

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