Dichloromethane → 2,3-Diamino-4-(2-thienyl)-6-ethoxycarbonylaminopyridine

HRID 1434887Notes

Reaction equation

HRID 1434887 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([C:11]2[S:12][CH:13]=[CH:14][CH:15]=2)[CH:5]=[C:4]([NH:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[N:3]=1.[BH4-].[Na+].[Cl-].[NH4+].C(Cl)Cl>C(O)C.C(OCC)(=O)C.[C].[Pd]>[NH2:1][C:2]1[C:7]([NH2:8])=[C:6]([C:11]2[S:12][CH:13]=[CH:14][CH:15]=2)[CH:5]=[C:4]([NH:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[N:3]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 25517Ammonium ChlorideHCID 4311764Sodium borohydrideHCID 579367972-Amino-3-nitro-4-(2-thienyl)-6-ethoxycarbonylaminopyridine

Product 1

HCID 579368002,3-Diamino-4-(2-thienyl)-6-ethoxycarbonylaminopyridineYield 90.2%

Reagents, catalysts & solvents 3

HCID 178418390HCID 178418390, compoundCatalystHCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

2-Amino-3-nitro-4-(2-thienyl)-6-ethoxycarbonylaminopyridine (1.57 g, 5.1 mmol) and 10% palladium-carbon (255 mg) were dissolved in ethanol (77 ml)-ethyl acetate (38 ml). To this mixture, a 1 M aqueous sodium borohydride solution (15.3 ml) was added at 0° C. and stirred at 0° C. for 1 hour. This solution was mixed with a 5% aqueous ammonium chloride solution (23.4 ml) and filtered through celite. The celite was washed with water (204 ml). The filtrate and this washing solution were mixed and evaporated under reduced pressure to remove ethanol and ethyl acetate, followed by extraction three times with ethyl acetate (150 ml). This solution was dried over sodium sulfate and evaporated under reduced pressure to remove the solvent, followed by silica gel column chromatography (methylene chloride:ethyl acetate=7:3 to 1:1) to purify the desired product, 2,3-diamino-4-(2-thienyl)-6-ethoxycarbonylaminopyridine (Rf 0.39/methylene chloride:ethyl acetate=1:2) (1.28 g, yield 90%).

Workup

  1. filtrationfiltered through celite
  2. washThe celite was washed with water (204 ml)
  3. additionThe filtrate and this washing solution were mixed
  4. customevaporated under reduced pressure
  5. customto remove ethanol and ethyl acetate
  6. extractionfollowed by extraction three times with ethyl acetate (150 ml)
  7. dry with materialThis solution was dried over sodium sulfate
  8. customevaporated under reduced pressure
  9. customto remove the solvent

Sources & evidence

ORD record
ord-dbdc3f239afd4552bafce9e1c72ad08c
Source dataset
uspto-grants-2009_11
Patent number
US07615628B2

Reaction notes

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