Ethylene Glycol → 4-(1,3-dioxolan-2-yl)pyridine

HRID 1852348Notes

Reaction equation

HRID 1852348 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH:7]=[O:8])=[CH:3][CH:2]=1.[CH2:9](O)[CH2:10][OH:11].C1(C)C=CC(S(O)(=O)=O)=CC=1.[OH-].[Na+]>C1C=CC=CC=1>[O:8]1[CH2:9][CH2:10][O:11][CH:7]1[C:4]1[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=1

Participants

6

Reactant 4

HCID 174Ethylene GlycolHCID 6101p-Toluenesulfonic acidHCID 133894-PyridinecarboxaldehydeHCID 14798Sodium Hydroxide

Product 1

HCID 2833314-(1,3-dioxolan-2-yl)pyridine

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

A stirred solution of pyridine-4-carboxaldehyde (8.7 ml, 90 mmol), ethylene glycol (10 ml, 180 mmol) and p-toluene sulfonic acid (18.8 g, 99 mmol) in benzene (70 ml) was refluxed overnight. A Dean-Stark apparatus was used to remove water azeotropically from the reaction. After ˜15 h the mixture was cooled, then made basic with aq. NaOH (20% w/v, ˜30 ml). The benzene layer was isolated and the aqueous layer was washed with dichloromethane until no more product came out (˜5×60 ml). The combined organic phases were dried (Na2SO4) and solvent removed in vacuo to give the pure 4-(1,3 dioxolan-2-yl) pyridine [Registry No. 61379-59-7] as a pale yellow liquid that solidified under vacuum (12.57 g, 92%). 1H NMR (300 MHz, CDCl3): δ 4.06 (4H, m, O—(CH2)2—O), 5.82 (1H, s, O—CH—O), 7.39 (2H, d, J=6-Hz, H-3, H-5), 8.63 (2H, d, J=6 Hz, H-2, H-6) ppm.

Workup

  1. customto remove water
  2. customazeotropically from the reaction
  3. temperatureAfter ˜15 h the mixture was cooled
  4. washthe aqueous layer was washed with dichloromethane until no more product
  5. dry with materialThe combined organic phases were dried (Na2SO4) and solvent
  6. customremoved in vacuo

Sources & evidence

ORD record
ord-6f85a846b70b480299678bebbdc65d9f
Source dataset
uspto-grants-2015_02
Patent number
US08962003B2

Reaction notes

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