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

HRID 558207Notes

Reaction equation

HRID 558207 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-465b1f20b5e746e790af590eb7aec95d
Source dataset
uspto-grants-2011_11
Patent number
US08063049B2

Reaction notes

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