Potassium Hydroxide → 3-Amino-6-chloro-4-ethylamino-pyridine-2-carbonitrile

HRID 2246459Notes

Reaction equation

HRID 2246459 reaction equation
O.O.[Sn](Cl)(Cl)(Cl)Cl.[Cl:8][C:9]1[N:14]=[C:13]([C:15]#[N:16])[C:12]([N+:17]([O-])=O)=[C:11]([NH:20][CH2:21][CH3:22])[CH:10]=1.[OH-].[K+]>Cl.CN(C=O)C>[NH2:17][C:12]1[C:13]([C:15]#[N:16])=[N:14][C:9]([Cl:8])=[CH:10][C:11]=1[NH:20][CH2:21][CH3:22]

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 85782573Tin tetrachloride dihydrateHCID 866138696-Chloro-4-ethylamino-3-nitro-pyridine-2-carbonitrile

Product 1

HCID 867610713-Amino-6-chloro-4-ethylamino-pyridine-2-carbonitrileYield 79.5%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 6228DimethylformamideSolvent

Procedure

At 0° C., a solution of tin chloride dihydrate (25.9 g) in concentrate aqueous HCl (76 mL) was added dropwise over 40 minutes to a solution of 6-chloro-4-ethylamino-3-nitro-pyridine-2-carbonitrile (2.9 g) in DMF (70 mL). The mixture was stirred for 2.5 hours, then poured to a mixture of ice (400 g) and 50% potassium hydroxide (400 mL), extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with 2N sodium hydroxide (700 mL), then brine (3×100 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was chromatographed over silica gel (eluent: dichloromethane/ethyl acetate 9/1) to afford the title compound (2.0 g) as white crystals (mp=150° C.). 1H NMR (DMSO-d6) δ: 6.46 (s, 1H); 6.42 (br.s, 1H); 6.02 (br.s, 2H); 3.20 (q, J=8 Hz, 2H); 1.26 (t, J=8 Hz, 3H). MS m/z: 197/199 (M+1).

Workup

  1. extractionextracted with ethyl acetate (3×100 ml)
  2. washThe combined organic layers were washed with 2N sodium hydroxide (700 mL)
  3. dry with materialbrine (3×100 mL), dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was chromatographed over silica gel (eluent: dichloromethane/ethyl acetate 9/1)

Sources & evidence

ORD record
ord-0493cb3e289e477e821a51ecc6356d7b
Source dataset
uspto-grants-2010_03
Patent number
US07687515B2

Reaction notes

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