Ethyl bromoacetate → Ethyl 2-(2-amino-6-chloropyridin-3-ylamino)acetate

HRID 509648Notes

Reaction equation

HRID 509648 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([NH2:9])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]>CN(C=O)C>[NH2:8][C:6]1[C:5]([NH:9][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:4][CH:3]=[C:2]([Cl:1])[N:7]=1

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 106306156-Chloropyridine-2,3-diamine

Product 1

HCID 86697560Ethyl 2-(2-amino-6-chloropyridin-3-ylamino)acetateYield 50.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A stirred mixture of 6-chloropyridine-2,3-diamine (E-24) (7.2 g, 50 mol, 1.0 eq) and potassium carbonate (6.9 g, 50 mmol, 1 eq) in DMF (100 mL) was stirred for 30 min and then ethyl bromoacetate (9.2 g, 55 mmol, 1.1 eq) was added, the resulting mixture was stirred at 60-70° C. for 3 h. The reaction was complete based on TLC analysis. The reaction mixture was poured into ice-water (200 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with brine, dried over Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford the desired product ethyl 2-(2-amino-6-chloropyridin-3-ylamino)acetate (E-25) (5.8 g, 50.5% yield) as a white solid. 1H NMR (300 MHz, DMSO-d6) δ: 6.39 (m, 2H), 5.93 (bs, 2H), 5.32 (m, 1H), 4.08 (m, 2H), 3.88 (d, J=6.0 Hz, 2H), 1.15 (m, 3H); ESI-MS m/z: 230.05 [M+H]+.

Workup

  1. stirringthe resulting mixture was stirred at 60-70° C. for 3 h
  2. extractionextracted with ethyl acetate (3×100 mL)
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-1e631473876f445bbb2ce5703af7d4f8
Source dataset
uspto-grants-2015_08
Patent number
US09096590B2

Reaction notes

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