Ethylene Glycol → 4-((1,3-Dioxolan-2-yl)methyl)benzonitrile

HRID 332695Notes

Reaction equation

HRID 332695 reaction equation
[OH:1][CH2:2][CH2:3][C:4]1[CH:11]=[CH:10][C:7]([C:8]#[N:9])=[CH:6][CH:5]=1.[CH3:12][C:13](OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=[O:14].C(=O)([O-])O.[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+].C(O)CO.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(Cl)Cl>[O:1]1[CH2:12][CH2:13][O:14][CH:2]1[CH2:3][C:4]1[CH:11]=[CH:10][C:7]([C:8]#[N:9])=[CH:6][CH:5]=1

Participants

8

Reactant 6

HCID 174Ethylene GlycolHCID 6101p-Toluenesulfonic acidHCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 28008154-(2-Hydroxyethyl)benzonitrile

Product 1

HCID 38007934-((1,3-Dioxolan-2-yl)methyl)benzonitrileYield 99.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-(2-hydroxyethyl)benzonitrile (1.09 g, 7.41 mmol) in DCM (20 mL), was added Dess-Martin Periodinane (3.77 g, 8.84 mmol), and the reaction mixture stirred at room temperature for 1 hour. A 1:1 mixture of saturated aqueous sodium hydrogen carbonate and saturated sodium thiosulfate was added, and the bi-phasic mixture stirred for 1 hour. The organic phase was separated, and the aqueous phase extracted with further DCM (×3). The combined organic extracts were dried with anhydrous magnesium sulphate, and the solvent evaporated at reduced pressure. The crude material was dissolved in toluene (40 mL) and ethylene glycol (2.29 g, 37.05 mmol), and p-toluenesulfonic acid (0.14 g, 0.74 mmol) added. The mixture was heated under Dean and Stark conditions for 2 hours. The solvent was evaporated under reduced pressure, and the residue partitioned between saturated aqueous sodium hydrogen carbonate and ethyl acetate. The organic phase was removed, and the aqueous phase was extracted with further ethyl acetate (×3). The combined organic phases were dried with anhydrous magnesium sulphate, and the solvent evaporated at reduced pressure to afford the title compound (1.40 g, 99%).

Workup

  1. additionwas added
  2. stirringthe bi-phasic mixture stirred for 1 hour
  3. customThe organic phase was separated
  4. extractionthe aqueous phase extracted with further DCM (×3)
  5. dry with materialThe combined organic extracts were dried with anhydrous magnesium sulphate
  6. customthe solvent evaporated at reduced pressure
  7. dissolutionThe crude material was dissolved in toluene (40 mL)
  8. temperatureThe mixture was heated under Dean and Stark conditions for 2 hours
  9. customThe solvent was evaporated under reduced pressure
  10. customthe residue partitioned between saturated aqueous sodium hydrogen carbonate and ethyl acetate
  11. customThe organic phase was removed
  12. extractionthe aqueous phase was extracted with further ethyl acetate (×3)
  13. dry with materialThe combined organic phases were dried with anhydrous magnesium sulphate
  14. customthe solvent evaporated at reduced pressure

Sources & evidence

ORD record
ord-35152a74d6e94271b9ac74eb28735322
Source dataset
uspto-grants-2014_11
Patent number
US08877774B2

Reaction notes

Loading…