Methanol → 6-(Methylamino)nicotinaldehyde

HRID 534775Notes

Reaction equation

HRID 534775 reaction equation
[CH3:1][NH:2][C:3]1[N:8]=[CH:7][C:6]([C:9]#N)=[CH:5][CH:4]=1.CC(C[Al]CC(C)C)C.CO.[OH:22]S(O)(=O)=O>C1(C)C=CC=CC=1>[CH3:1][NH:2][C:3]1[N:8]=[CH:7][C:6]([CH:9]=[O:22])=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 1118Sulfuric AcidHCID 16682954DibahHCID 178608996-(Methylamino)pyridine-3-carbonitrile

Product 1

HCID 184162986-(Methylamino)nicotinaldehyde

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-78 °C

Procedure

To 6-(methylamino)-3-pyridinecarbonitrile (D94) (0.1 g, 0.752 mmol) in toluene (10 mL) cooled to −78 C under argon was added Dibal-H (1.88 mL, 1M solution in toluene, 11.2 mmol) dropwise. The reaction was stirred at −78° C. and then allowed to warm to room temperature overnight. MeOH (0.47 mL) and 2 M H2SO4 (1.42 mL) were added and mixture was stirred for 1.5 h then concentrated in vacuo. The residue was partitioned between water and EtOAc. The aqueous layer was extracted with EtOAc and the combined organic layers were dried and concentrated to give the title compound (0.067 g). δH (CDCl3, 400 MHz) 9.78 (1H, s), 8.52 (1H, d), 7.92 (1H, dd), 6.45 (1H, d), 5.38 (1H, br.s), 3.04 (3H, d). MS (ES): MH+ 137.1.

Workup

  1. temperatureto warm to room temperature overnight
  2. stirringmixture was stirred for 1.5 h
  3. concentrationthen concentrated in vacuo
  4. customThe residue was partitioned between water and EtOAc
  5. extractionThe aqueous layer was extracted with EtOAc
  6. customthe combined organic layers were dried
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-055b213759f34416bed1dfd49fc46710
Source dataset
uspto-grants-2014_10
Patent number
US08853218B2

Reaction notes

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