Sulfuric Acid → 6-Chloropyridine-3-carbaldehyde

HRID 228352Notes

Reaction equation

HRID 228352 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#N)=[CH:4][N:3]=1.C1(C)C=CC=CC=1.CC(C[AlH]CC(C)C)C.[OH:26]S(O)(=O)=O>CO>[Cl:1][C:2]1[N:3]=[CH:4][C:5]([CH:6]=[O:26])=[CH:8][CH:9]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 1140TolueneHCID 14487Diisobutylaluminum hydrideHCID 51520946-Chloro-3-pyridinecarbonitrile

Product 1

HCID 27640536-Chloropyridine-3-carbaldehydeYield 62%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

Combine 6-chloro-nicotino-nitrile ((1.00 g, 7.21 mmol) and toluene (24 mL). Cool the resulting solution at 0° C. and add DIBAL-H (1.0 M in toluene, 7.58 mL, 7.58 mmol) dropwise. Stir the resulting red solution at 0° C. for 1 h. Then, add methanol (2 mL) followed by H2SO4 (aq. 2.0 M, 6 mL). Stir for 1 h at rt. Add CHCl3:isopropanol (3/1, 15 mL) and wash with Rochelle's salt solution (20 mL), followed by NaHCO3 (20 mL) and brine. Dry the combined organic layers over magnesium sulfate, filter and concentrate. Purify by flash chromatography (EtOAc/hexanes 10%) to give the title compound (530 mg, 62%).

Workup

  1. stirringStir for 1 h at rt
  2. washAdd CHCl3:isopropanol (3/1, 15 mL) and wash with Rochelle's salt solution (20 mL)
  3. dry with materialDry the combined organic layers over magnesium sulfate
  4. filtrationfilter
  5. concentrationconcentrate
  6. customPurify by flash chromatography (EtOAc/hexanes 10%)

Sources & evidence

ORD record
ord-20e47bc0c9c04ffc94353cf71d4ac51f
Source dataset
uspto-grants-2009_07
Patent number
US07560463B2

Reaction notes

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