Hydrochloric Acid → 2-phenethylbenzaldehyde

HRID 1006040Notes

Reaction equation

HRID 1006040 reaction equation
C(Cl)(=O)C(Cl)=O.[C:7]1([CH2:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:8]([C:13](O)=[O:14])=[CH:9][CH:10]=[CH:11][CH:12]=1.CN(C=O)C.Cl>ClCCl>[CH2:16]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH:13]=[O:14])[CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 78603o-Phenethylbenzoic acid

Product 1

HCID 107271692-phenethylbenzaldehydeYield 26%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-70 °C

Procedure

Oxalyl chloride (9.1 ml) was added to a suspension of 2-bibenzylcarboxylic acid (20 g) in dichloromethane (200 ml) followed by 0.1 ml of DMF. The mixture was stirred for 15 hours and evaporated to dryness. The residue was dissolved in diglyme (150 ml) and cooled to −70° C. under argon. Lithium tri-t-butoxyaluminohydride (177 ml of a 0.5M solution in diglyme) was added dropwise such that the temperature of the reaction mixture did not exceed −65° C. The reaction mixture was stirred for a further 2 hours at −70° C. and then poured onto ice. The slurry obtained was acidified (HCl) and extracted with diethyl ether (3×75 ml). The combined ether extracts were washed with brine and dried (MgSO4). The solvent was removed and the residue dissolved in petroleum ether (BP 60-80° C.) and washed once with aqueous saturated sodium bicarbonate, five times with water and twice with brine then dried. Removal of the solvent gave an oil which was purified by chromatography on silica, eluting with dichloromethane-hexane (1:1 v/v), to give 2-(phenethyl)benzaldehyde, (4.83 g).

Workup

  1. customevaporated to dryness
  2. dissolutionThe residue was dissolved in diglyme (150 ml)
  3. additionLithium tri-t-butoxyaluminohydride (177 ml of a 0.5M solution in diglyme) was added dropwise such that the temperature of the reaction mixture
  4. customdid not exceed −65° C
  5. stirringThe reaction mixture was stirred for a further 2 hours at −70° C.
  6. additionpoured onto ice
  7. customThe slurry obtained
  8. extractionextracted with diethyl ether (3×75 ml)
  9. washThe combined ether extracts were washed with brine
  10. dry with materialdried (MgSO4)
  11. customThe solvent was removed
  12. dissolutionthe residue dissolved in petroleum ether (BP 60-80° C.)
  13. washwashed once with aqueous saturated sodium bicarbonate, five times with water and twice with brine
  14. customthen dried
  15. customRemoval of the solvent
  16. customgave an oil which
  17. customwas purified by chromatography on silica
  18. washeluting with dichloromethane-hexane (1:1 v/v)

Sources & evidence

ORD record
ord-7a80bcbc82394085b260fb0ee45e3844
Source dataset
uspto-grants-2004_09
Patent number
US06787562B2

Reaction notes

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