Hydrogen Sulfide → 4-(4'-Amino-4-phenyl-[2,5']bithiazolyl-2'-ylamino)-benzenesulfonamide

HRID 1167823Notes

Reaction equation

HRID 1167823 reaction equation
NS(C1C=CC(NC2SC(C#N)=C(N)N=2)=CC=1)(=O)=O.S.[NH2:21][S:22]([C:25]1[CH:30]=[CH:29][C:28]([NH:31][C:32]2[S:33][C:34]([C:38](=[S:40])[NH2:39])=[C:35]([NH2:37])[N:36]=2)=[CH:27][CH:26]=1)(=[O:24])=[O:23].Br[CH2:42][C:43]([C:45]1[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=1)=O>C(N(CC)CC)C.N1C=CC=CC=1.CO>[NH2:37][C:35]1[N:36]=[C:32]([NH:31][C:28]2[CH:29]=[CH:30][C:25]([S:22]([NH2:21])(=[O:24])=[O:23])=[CH:26][CH:27]=2)[S:33][C:34]=1[C:38]1[S:40][CH:42]=[C:43]([C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[N:39]=1

Participants

7

Reactant 4

HCID 402Hydrogen SulfideHCID 6259Phenacyl bromideHCID 229939182-(4-Aminosulfonylphenyl)amino-4-amino-thiazole-5-carbonitrileHCID 229939582-(4-Aminosulfonylphenyl)amino-4-amino-thiazole-5-carbothioamide

Product 1

HCID 99105144-(4'-Amino-4-phenyl-[2,5']bithiazolyl-2'-ylamino)-benzenesulfonamide

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 22561186Pyridine triethylamineSolvent

Procedure

To a solution of 2-(4-aminosulfonylphenyl)amino-4-amino-thiazole-5-carbonitrile (0.59 g, 2 mmol) in 20% triethylamine/pyridine (50 ml) was bubbled H2S gas at ice-water temperature for 30 minutes. Then the reaction solution was sealed and stirred at room temperature overnight. Argon gas was bubbled through the reaction solution for 60 minutes to replace the H2S, and then the solvents were removed at reduced pressure. The residue was dissolved in EtOAc, and the EtOAc solution was then washed with 5% citric acid (50 ml×3) followed by brine. The solvent was removed in vacuo and the residue was triturated in Et2O. The product 2-(4-aminosulfonylphenyl)amino-4-amino-thiazole-5-carbothioamide was collected by filtration (0.56 g, 95%). To prepare the title compound, a solution of 2-(4-aminosulfonylphenyl)amino-4-amino-thiazole-5-carbothioamide (164 mg, 0.5 mmol) and α-bromoacetophenone (110 mg, 0.55 mmol) in MeOH (20 ml) was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was dissolved in EtOAc (50 ml). The EtOAc solution was washed with saturated NaHCO3 (10 ml), followed by brine. Purification of the residue by silica gel chromatography provided 4-(4′-amino-4-phenyl-[2,5′]bithiazolyl-2′-ylamino)-benzenesulfonamide. Mp 233-235° C. (decomp.). 1H NMR (CD3OD): δ7.96 (s, 1H), 7.82 (s, 4H), 7.44-7.25 (m, 4H). ESIMS (MH+): 430; (M−H−): 428.

Workup

  1. customThen the reaction solution was sealed
  2. customArgon gas was bubbled through the reaction solution for 60 minutes
  3. customthe solvents were removed at reduced pressure
  4. dissolutionThe residue was dissolved in EtOAc
  5. washthe EtOAc solution was then washed with 5% citric acid (50 ml×3)
  6. customThe solvent was removed in vacuo
  7. customthe residue was triturated in Et2O
  8. filtrationThe product 2-(4-aminosulfonylphenyl)amino-4-amino-thiazole-5-carbothioamide was collected by filtration (0.56 g, 95%)
  9. customTo prepare the title compound
  10. customThe solvent was removed in vacuo
  11. dissolutionthe residue was dissolved in EtOAc (50 ml)
  12. washThe EtOAc solution was washed with saturated NaHCO3 (10 ml)
  13. customPurification of the residue by silica gel chromatography

Sources & evidence

ORD record
ord-6ed9253d67a34ab1a9d9e5a9b90fea21
Source dataset
uspto-grants-2003_09
Patent number
US06620828B2

Reaction notes

Loading…