Chlorosuccinimide → 4-(4-Bromo-2-chlorophenylamino)-5,6-dichloronicotinic acid

HRID 1161802Notes

Reaction equation

HRID 1161802 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[C:14]([C:15]([OH:17])=[O:16])=[CH:13][N:12]=[C:11]([Cl:18])[CH:10]=2)=[C:4]([Cl:19])[CH:3]=1.C1C(=O)N([Cl:27])C(=O)C1.S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>CN(C=O)C.O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[C:14]([C:15]([OH:17])=[O:16])=[CH:13][N:12]=[C:11]([Cl:18])[C:10]=2[Cl:27])=[C:4]([Cl:19])[CH:3]=1

Participants

6

Reactant 3

HCID 31398Chlorosuccinimide2×HCID 656671Sodium PyrosulfiteHCID 218669844-(4-Bromo-2-chlorophenylamino)-6-chloronicotinic acid

Product 1

HCID 116612174-(4-Bromo-2-chlorophenylamino)-5,6-dichloronicotinic acidYield 90%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a thick suspension of 4-(4-bromo-2-chlorophenylamino)-6-chloronicotinic acid (13.25 g, 36.8 mmol) in 350 ml DMF was added NCS (4.94 g, 37 mmol) and the suspension was stirred at room temperature for 3 days. Since the reaction did not go to completion (NMR control), an additional 1.987 g NCS was added and the mixture was stirred for 18 h, upon which the reaction went to completion. The mixture was poured into a solution of 20 g sodium metabisulfite in H2O (1 l) and the thick suspension was rest for 30 min. It was filtered, and the precipitate was washed with water, then with hexanes and it was dried in oil pump vacuo at 50° C. for 24 hours to obtain the desired compound as a white solid (13.11 g, 90%). 1H-NMR (500 MHz, DMSO-D6): δ=9.90 (s, br, 1H), 8.63 (s, 1H), 7.74 (s, 1H), 7.43-7.42 (dd, 1H), 6.99-6.97 (dd, 1H).

Workup

  1. stirringthe mixture was stirred for 18 h, upon which the reaction
  2. customfor 30 min
  3. filtrationIt was filtered
  4. washthe precipitate was washed with water
  5. dry with materialwith hexanes and it was dried in oil pump vacuo at 50° C. for 24 hours

Sources & evidence

ORD record
ord-fdac48a81cb946218a6e39de4202d8c5
Source dataset
uspto-grants-2010_10
Patent number
US07820664B2

Reaction notes

Loading…