Dimethyl Sulfoxide → 4-Chloro-2-ethoxybenzaldehyde

HRID 1435146Notes

Reaction equation

HRID 1435146 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Cl:11][C:12]1[CH:19]=[CH:18][C:15]([CH2:16][OH:17])=[C:14]([O:20][CH2:21][CH3:22])[CH:13]=1.C(N(CC)CC)C>ClCCl>[Cl:11][C:12]1[CH:19]=[CH:18][C:15]([CH:16]=[O:17])=[C:14]([O:20][CH2:21][CH3:22])[CH:13]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 60051025HCID 60051025, compound

Product 1

HCID 600510294-Chloro-2-ethoxybenzaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Oxalyl chloride (4.87 g, 38.4 mmol) is added to dry dichloromethane (80 ml) cooled to below −60° C. under an atmosphere of nitrogen followed by dropwise addition of a solution of dry dimethyl sulphoxide (6.25 g, 80.10 mmol) in dry dichloromethane (25 ml) with stirring. After stirring for 15 min. at −78° C., a solution of 4-chloro-2-ethoxybenzyl alcohol (5.97 g, 32.0 mmol) in dry dichloromethane (35 ml) is added dropwise to give a white suspension. The suspension is stirred at −78° C. for 0.5 h then added triethylamine (16.18 g, 0.16 mol) rapidly. The mixture is stirred at room temperature for 1.5 h before quenching with aqueous saturated sodium bicarbonate (100 ml). The aqueous phase is separated and extracted with dichloromethane (2×). The combined organic phases is washed with aqueous HCl (1M) and then with brine, dried over magnesium sulphate, filtered and evaporated to a yellow solid. The solid is dissolved in diethyl ether and purified by eluting through a short plug of flash silica. Evaporate to give 4-chloro-2-ethoxybenzaldehyde as a pale yellow solid.

Workup

  1. temperaturecooled to below −60° C. under an atmosphere of nitrogen
  2. stirringAfter stirring for 15 min. at −78° C.
  3. customto give a white suspension
  4. stirringThe suspension is stirred at −78° C. for 0.5 h
  5. stirringThe mixture is stirred at room temperature for 1.5 h
  6. custombefore quenching with aqueous saturated sodium bicarbonate (100 ml)
  7. customThe aqueous phase is separated
  8. extractionextracted with dichloromethane (2×)
  9. washThe combined organic phases is washed with aqueous HCl (1M)
  10. dry with materialwith brine, dried over magnesium sulphate
  11. filtrationfiltered
  12. customevaporated to a yellow solid
  13. dissolutionThe solid is dissolved in diethyl ether
  14. custompurified
  15. washby eluting through a short plug of flash silica
  16. customEvaporate

Sources & evidence

ORD record
ord-59494c3e1d894686ab978baaa91a936e
Source dataset
uspto-grants-2009_11
Patent number
US07615648B2

Reaction notes

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