Acetic Acid → HCID 90408825, compound

HRID 2177608Notes

Reaction equation

HRID 2177608 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=2)[CH:5]=[C:4]([CH3:18])[N:3]=1.C(O)(=O)C.Cl>CO.O1CCOCC1.[Zn]>[CH3:18][C:4]1[N:3]=[CH:2][C:7]([NH2:8])=[C:6]([NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=2)[CH:5]=1

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 90408903HCID 90408903, compound

Product 1

HCID 90408825HCID 90408825, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of N-(2-chloro-6-methyl-3-nitropyridin-4-yl)pyridin-2-amine (860 mg, 3.25 mmol) in methanol (30 mL) was added zinc powder (2.12 g, 32.49 mmol) and acetic acid (0.93 mL, 16.25 mmol). The reaction was heated to reflux and stirred for 2 h after which time 4M HCl in dioxane was added (4.0 mL, 16.0 mmol). After stirring at reflux overnight, the zinc was filtered off and the filtrate was concentrated. The residue was dissolved in CH2Cl2 (100 mL) and IPA (10 mL) and 5% Na2CO3 (aq) was added until pH 11 was obtained. The organic layer was separated. Solid NaCl was added to the water layer to saturate it and then it was extracted with 20% IPA/CH2Cl2 three times. The organic layers were combined, dried over anhydrous MgSO4, filtered and concentrated to an oil (550 mg, 85%). MS (ESI) mass calcd. C11H12N4, 200.11. m/z found, 201.1 [M+H]+.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux
  3. additionwas added (4.0 mL, 16.0 mmol)
  4. temperatureat reflux overnight
  5. filtrationthe zinc was filtered off
  6. concentrationthe filtrate was concentrated
  7. dissolutionThe residue was dissolved in CH2Cl2 (100 mL)
  8. additionIPA (10 mL) and 5% Na2CO3 (aq) was added until pH 11
  9. customwas obtained
  10. customThe organic layer was separated
  11. additionSolid NaCl was added to the water layer
  12. concentrationto saturate it
  13. extractionit was extracted with 20% IPA/CH2Cl2 three times
  14. dry with materialdried over anhydrous MgSO4
  15. filtrationfiltered
  16. concentrationconcentrated to an oil (550 mg, 85%)

Sources & evidence

ORD record
ord-d5b7d35f9c3a49419e31ab56d4f3bd20
Source dataset
uspto-grants-2015_06
Patent number
US09066946B2

Reaction notes

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