Ethyl Acetate → Methyl 6-amino-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate

HRID 558210Notes

Reaction equation

HRID 558210 reaction equation
[N:1]([C:4]1[C:13]([Cl:14])=[C:12]([NH:15][C:16]2[CH:21]=[CH:20][C:19]([Br:22])=[CH:18][C:17]=2[Cl:23])[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][N:5]=1)=[N+]=[N-].CCOC(C)=O>C(Cl)Cl.CC(O)=O.[Zn]>[NH2:1][C:4]1[C:13]([Cl:14])=[C:12]([NH:15][C:16]2[CH:21]=[CH:20][C:19]([Br:22])=[CH:18][C:17]=2[Cl:23])[C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][N:5]=1

Participants

6

Reactant 2

HCID 8857Ethyl AcetateHCID 59519382Methyl 6-azido-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate

Product 1

HCID 59519500Methyl 6-amino-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

To a suspension of methyl 6-azido-4-(4-bromo-2-chlorophenylamino)-5-chloronicotinate (316 mg, 0.76 mmol) in a mixture of DCM (6 ml) and AcOH (2 ml) was added Zn dust (255 mg, 3.9 mmol) in small portions. After complete addition it was furthers stirred at room temperature for 30 min. Then, the mixture was poured into EtOAc (30 ml), washed with H2O, saturated sodium bicarbonate solution and brine. The organic fractions were dried with Na2SO4 and the solvents were removed and the product was dried in oil-pump vacuo (246 mg, 83%). Rf (CHCl3/MeOH 30:1)=0.3. 1H-NMR (500 MHz, DMSO-D6): δ=9.17 (s, 1H), 8.45 (s, 1H), 7.70-7.70 (d, 1H), 7.38-7.36 (dd, 1H), 7.1 (s, 1H, br), 6.68-6.67 (d, 1H), 3.76 (s, 3H).

Workup

  1. additionAfter complete addition it
  2. washwashed with H2O, saturated sodium bicarbonate solution and brine
  3. dry with materialThe organic fractions were dried with Na2SO4
  4. customthe solvents were removed
  5. customthe product was dried in oil-pump vacuo (246 mg, 83%)

Sources & evidence

ORD record
ord-244bc66615d440e7a49439f444af004f
Source dataset
uspto-grants-2011_11
Patent number
US08063049B2

Reaction notes

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