Formic Acid → 6-Amino-4-methylnicotinaldehyde

HRID 644748Notes

Reaction equation

HRID 644748 reaction equation
[C:1]([C:3]1[C:4]([CH3:16])=[CH:5][C:6]([NH:9]C(=O)C(F)(F)F)=[N:7][CH:8]=1)#N.C(O)=[O:18]>O.[Ni].[Al]>[NH2:9][C:6]1[N:7]=[CH:8][C:3]([CH:1]=[O:18])=[C:4]([CH3:16])[CH:5]=1

Participants

5

Reactant 2

HCID 284Formic AcidHCID 86618113N-(5-Cyano-4-methyl-2-pyridinyl)-2,2,2-trifluoroacetamide

Product 1

HCID 552846706-Amino-4-methylnicotinaldehyde

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6336846Nickel aluminideSolvent

Procedure

A solution of N-(5-cyano-4-methyl-2-pyridinyl)-2,2,2-trifluoroacetamide (D98) (0.050 g, 0.22 mmol) in formic acid (1.35 mL) was diluted with water (0.48 mL) and nickel/aluminium alloy (0.122 g) was added. The reaction mixture was heated at reflux under argon for 2 h then filtered while still hot, washing with further formic acid (3×5 mL). The filtrate and washings were concentrated, diluted with toluene (5 mL) and re-concentrated to give the crude title compound as a pale yellow solid (0.053 g) which was used in the next step without further purification. δH (CDCl3, 400 MHz) 9.91 (1H, s), 8.34 (1H, s), 6.31 (1H, s), 5.49 (2H, br.s), 2.57 (3H, s). MS (ES): MH+ 137.2.

Workup

  1. additionwas added
  2. temperatureThe reaction mixture was heated
  3. temperatureat reflux under argon for 2 h
  4. filtrationthen filtered while still hot,
  5. washwashing with further formic acid (3×5 mL)
  6. concentrationThe filtrate and washings were concentrated
  7. additiondiluted with toluene (5 mL)
  8. concentrationre-concentrated

Sources & evidence

ORD record
ord-5423e2aaa79a47d5993dd10a4c2e0c23
Source dataset
uspto-grants-2010_04
Patent number
US07700599B2

Reaction notes

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