Ethylene Glycol → 2-Bromo-5-(1,3-dioxolan-2-YL)pyridine

HRID 1400912Notes

Reaction equation

HRID 1400912 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][N:3]=1.[CH2:10](O)[CH2:11][OH:12].C1(C)C=CC(S(O)(=O)=O)=CC=1.O>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]2[O:12][CH2:11][CH2:10][O:7]2)=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 174Ethylene GlycolHCID 962WaterHCID 6101p-Toluenesulfonic acidHCID 117692346-Bromo-3-pyridinecarboxaldehyde

Product 1

HCID 184696682-Bromo-5-(1,3-dioxolan-2-YL)pyridineYield 98.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 6-bromonicotinaldehyde (10.1 g, 51.6 mmol) in toluene (400 mL) was added ethylene glycol (11.4 mL, 206 mmol) and p-toluenesulfonic acid (0.98 g, 5.16 mmol), and the reaction mixture was heated to reflux with azeotropic removal of the water using a Dean-Stark trap, for 2.5 h. The mixture was cooled down and washed with saturated NaHCO3 solution and brine. The organic phase was dried over anhydrous MgSO4 and concentrated to afford title compound 300 (11.7 g, 98% yield) as a brown solid, which was used in the next step without further purification. 1H NMR (300 MHz, DMSO-d6) δ (ppm): 8.46 (d, J=2.7 Hz, 1H), 7.65 (dd, J=8.1, 2.7 Hz, 1H), 7.51 (d, J=8.1 Hz, 1H), 5.83 (s, 1H), 4.20-4.00 (m, 4H).

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureThe mixture was cooled down
  3. washwashed with saturated NaHCO3 solution and brine
  4. dry with materialThe organic phase was dried over anhydrous MgSO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-a9f0ffc72bc84e8f927d5146a1dd6783
Source dataset
uspto-grants-2014_12
Patent number
US08906852B2

Reaction notes

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