4-Pyridinecarboxaldehyde → 4-(Diethoxymethyl)pyridine

HRID 2401796Notes

Reaction equation

HRID 2401796 reaction equation
O.[C:2]1(C)C=CC(S(O)(=O)=O)=C[CH:3]=1.[N:13]1[CH:18]=[CH:17][C:16]([CH:19]=[O:20])=[CH:15][CH:14]=1.C([O-])([O-])[O:22][CH2:23][CH3:24]>C(O)C>[CH2:2]([O:20][CH:19]([O:22][CH2:23][CH3:24])[C:16]1[CH:17]=[CH:18][N:13]=[CH:14][CH:15]=1)[CH3:3]

Participants

5

Reactant 3

HCID 133894-PyridinecarboxaldehydeHCID 521998p-Toluenesulfonic acid monohydrateHCID 53630039Ethylorthoformate

Product 1

HCID 153891924-(Diethoxymethyl)pyridineYield 97.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

p-Toluenesulfonic acid monohydrate (11.8 g, 62.0 mmol) was dissolved in dry ethanol (80 mL) at rt. 4-Pyridinecarboxaldehyde (4.71 mL, 50.0 mmol) was added, followed by ethyl orthoformate (20.79 mL, 125.0 mmol). The mixture was stirred at rt for 17 hours. The mixture was concentrated and the residue was basified with aqueous saturated NaHCO3 solution to ˜pH 8, extracted with EtOAc (150 mL), washed with brine, dried over Na2SO4, filtered, evaporated, and dried under high vacuum to give a liquid product. (9.06 g, yield 97.2%). LCMS: (FA) ES+ 182. 1H NMR (400 MHz, CDCl3) δ: 8.60-8.62 (m, 2H), 7.38-7.40 (m, 2H), 5.50 (s, 1H), 3.53-3.62 (m, 4H), 1.23-1.27 (m, 6H).

Workup

  1. concentrationThe mixture was concentrated
  2. extractionextracted with EtOAc (150 mL)
  3. washwashed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. customdried under high vacuum
  8. customto give a liquid product

Sources & evidence

ORD record
ord-2d86ab05d0dc4af09400c8d212aecdf6
Source dataset
uspto-grants-2014_08
Patent number
US08796268B2

Reaction notes

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