Hydrochloric Acid → 5-Acetyl-2-{[2-(chloromethyl)-2-propenyl]oxy}benzaldehyde

HRID 1791059Notes

Reaction equation

HRID 1791059 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[Cl:7][CH2:8][C:9]([CH2:11]Cl)=[CH2:10].[C:13]([C:16]1[CH:17]=[CH:18][C:19]([OH:24])=[C:20]([CH:23]=1)[CH:21]=[O:22])(=[O:15])[CH3:14].Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.O>[C:13]([C:16]1[CH:17]=[CH:18][C:19]([O:24][CH2:11][C:9]([CH2:8][Cl:7])=[CH2:10])=[C:20]([CH:23]=1)[CH:21]=[O:22])(=[O:15])[CH3:14]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 158593-Chloro-2-chloromethyl-1-propeneHCID 30853915-Acetylsalicylaldehyde

Product 1

HCID 220422715-Acetyl-2-{[2-(chloromethyl)-2-propenyl]oxy}benzaldehydeYield 52.7%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

6.02 g (16.31 mmol) of tetrabutylammonium iodide, 6.17 g (2.5 equivalents) of sodium carbonate and, finally, 6.7 ml (58.2 mmol) of 2-chloromethyl-3-chloro-1-propene are successively added to 3.82 g (23 mmol) of 5-acetyl-2-hydroxybenzaldehyde, prepared according to Tromelin, A. et al., Synthesis, (1985), 1074–1076, and then Laali, K. et al., Journal of Organic Chemistry, 58, (1993), 1385–1392, in solution in 250 ml of N,N-dimethylformamide. The medium is stirred for 21 hours. After addition of water and 1N hydrochloric acid, the solution is extracted with dichloromethane. The organic phase is subsequently washed, then dried and, finally, concentrated under vacuum. The crude reaction product is purified by chromatography on silica gel (ethyl acetate/heptane 20/80) to give 3.06 g (52%) of 5-acetyl-2-{[2-(chloromethyl)-2-propenyl]oxy}benzaldehyde in the form of a yellow-white solid; 1H NMR (300 MHz, CDCl3): 10.49 (s, 1H), 8.38 (d, J=2.1 Hz, 1H), 8.18 (dd, J=2.1 Hz and 8.7 Hz, 1H), 7.08 (d, J=8.7 Hz, 1H), 5.46 and 5.41 (2s, 2H), 4.83 (s, 2H), 4.21 (s, 2H), 2.58 (s, 3H).

Workup

  1. customprepared
  2. customet al., Synthesis, (1985), 1074–1076
  3. extractionthe solution is extracted with dichloromethane
  4. washThe organic phase is subsequently washed
  5. customdried
  6. concentrationfinally, concentrated under vacuum
  7. customThe crude reaction product
  8. customis purified by chromatography on silica gel (ethyl acetate/heptane 20/80)

Sources & evidence

ORD record
ord-d42fe0218dfb4682b7e7b0388106e575
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

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