Sulfuric Acid → 6-Chloropyridine-3-carbaldehyde

HRID 492508Notes

Reaction equation

HRID 492508 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-61d13f6f5ee94ff6be1a31e68d0f611a
Source dataset
uspto-grants-2009_05
Patent number
US07531557B2

Reaction notes

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