Acetic acid methylene chloride → Methyl 6-amino-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate

HRID 494701Notes

Reaction equation

HRID 494701 reaction equation
[CH3:1][O:2][C:3](=[O:23])[C:4]1[C:9]([NH:10][C:11]2[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][C:12]=2[Cl:18])=[C:8]([Cl:19])[C:7]([N:20]=[N+]=[N-])=[N:6][CH:5]=1.ClCCl.C(O)(=O)C>[Zn].C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:23])[C:4]1[C:9]([NH:10][C:11]2[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][C:12]=2[Cl:18])=[C:8]([Cl:19])[C:7]([NH2:20])=[N:6][CH:5]=1

Participants

5

Reactant 2

HCID 21922555Acetic acid methylene chlorideHCID 59519382Methyl 6-azido-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate

Product 1

HCID 59519500Methyl 6-amino-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinateYield 98%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Zinc powder (10 g, 155 mmol) was added portionwise to a suspension of 6-azido-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinic acid methyl ester (27) (12.94 g, 31 mmol) in 3:1 dichloromethane/acetic acid (300 mL). After fifteen minutes the reaction mixture was poured into 700 mL ethyl acetate, washed with water, saturated sodium bicarbonate and brine. The organic solution was dried over NaSO4, filtered, and concentrated in vacuo to provide the desired product (28) as an off-white solid (11.85 g, 98%). MS (APCI+) m/z 390, 392, 394 (M+; Cl, Br pattern) detected.

Workup

  1. washwashed with water, saturated sodium bicarbonate and brine
  2. dry with materialThe organic solution was dried over NaSO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-48793d9a77984ef486ed13941ca4b84f
Source dataset
uspto-grants-2009_05
Patent number
US07538120B2

Reaction notes

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