Calcium Chloride → Ethyl 5,6-diaminonicotinate

HRID 1644587Notes

Reaction equation

HRID 1644587 reaction equation
[NH2:1][C:2]1[C:12]([N+:13]([O-])=O)=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][N:3]=1.[Cl-].[Ca+2].[Cl-]>C(O)C.[Zn]>[NH2:13][C:12]1[C:2]([NH2:1])=[N:3][CH:4]=[C:5]([CH:11]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7]

Participants

5

Reactant 2

HCID 5284359Calcium ChlorideHCID 22387769Ethyl 6-amino-5-nitropyridine-3-carboxylate

Product 1

HCID 9877541Ethyl 5,6-diaminonicotinateYield 89.7%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Procedure

To a solution (150 ml) of ethyl 6-amino-5-nitronicotinate (5.0 g) and 6N aqueous calcium chloride solution (50 ml) in ethanol was added zinc powder (77 g) with heating under reflux. The reaction mixture was heated under reflux for 2 hr, and the zinc powder was removed by filtration. The filtrate was concentrated, diluted with water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated to give the title compound (3.85 g, yield 89%) as pale-brown crystals. 1H NMR (DMSO-d6) δ: 1.37 (3H, t, J=7.0 Hz), 4.38 (2H, q, J=7.1 Hz), 4.95 (2H, s), 6.28 (2H, s), 7.15 (1H, d, J=2.1 Hz), 7.94 (1H, d, J=2.1 Hz).

Workup

  1. temperaturewith heating
  2. temperatureunder reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureunder reflux for 2 hr
  5. customthe zinc powder was removed by filtration
  6. concentrationThe filtrate was concentrated
  7. additiondiluted with water
  8. extractionextracted with ethyl acetate
  9. washThe extract was washed with water
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-6cadfe73d968459189843b5bc4f06fdf
Source dataset
uspto-grants-2012_02
Patent number
US08124617B2

Reaction notes

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