Ammonium Chloride → {4-[2-Amino-4-(5-bromo-pyridin-2-ylcarbamoyl)-phenylsulfanyl]-phenyl}-carbamic acid 2,2,2-trichloro-ethyl ester

HRID 605325Notes

Reaction equation

HRID 605325 reaction equation
[Cl:1][C:2]([Cl:35])([Cl:34])[CH2:3][O:4][C:5](=[O:33])[NH:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][C:14]2[CH:19]=[CH:18][C:17]([C:20](=[O:29])[NH:21][C:22]3[CH:27]=[CH:26][C:25]([Br:28])=[CH:24][N:23]=3)=[CH:16][C:15]=2[N+:30]([O-])=O)=[CH:9][CH:8]=1.[Cl-].[NH4+]>O1CCCC1.C(O)C.O.[Fe]>[Cl:35][C:2]([Cl:1])([Cl:34])[CH2:3][O:4][C:5](=[O:33])[NH:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][C:14]2[CH:19]=[CH:18][C:17]([C:20](=[O:29])[NH:21][C:22]3[CH:27]=[CH:26][C:25]([Br:28])=[CH:24][N:23]=3)=[CH:16][C:15]=2[NH2:30])=[CH:9][CH:8]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 67040335{4-[4-(5-Bromo-pyridin-2-ylcarbamoyl)-2-nitro-phenylsulfanyl]-phenyl}-carbamic acid 2,2,2-trichloro-ethyl ester

Product 1

HCID 67040870{4-[2-Amino-4-(5-bromo-pyridin-2-ylcarbamoyl)-phenylsulfanyl]-phenyl}-carbamic acid 2,2,2-trichloro-ethyl esterYield 95.3%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 18504229Ethanol tetrahydrofuran waterSolvent

Procedure

A mixture of the product of Example 364C (1.63 g, 2.63 mmol), iron powder (0.737 g, 13.1 mmol, 5 equiv., from Acros, electrolytically reduced, reagent, powder), and ammonium chloride (0.211 g, 3.94 mmol, 1.5 equiv.) in tetrahydrofuran/ethanol/water (30/30/10 mL) was heated under reflux for 2.5 hours. The reaction mixture was cooled to room temperature and filtered through Celite, rinsing the Celite pad with 50 mL of ethanol. The resulting filtrate was evaporated under reduced pressure and the residue was partitioned between ethyl acetate (100 mL) and water (100 mL). The aqueous phase was washed with ethyl acetate (2×100 mL). The combined organic phases were washed with brine (50 mL), dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure to give the title compound (1.48 g, 95%) as a faintly yellow solid.

Workup

  1. temperatureunder reflux for 2.5 hours
  2. filtrationfiltered through Celite
  3. washrinsing the Celite pad with 50 mL of ethanol
  4. customThe resulting filtrate was evaporated under reduced pressure
  5. customthe residue was partitioned between ethyl acetate (100 mL) and water (100 mL)
  6. washThe aqueous phase was washed with ethyl acetate (2×100 mL)
  7. washThe combined organic phases were washed with brine (50 mL)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-d5cfba0994494d7baaf682842242259a
Source dataset
uspto-grants-2011_03
Patent number
US07910595B2

Reaction notes

Loading…