Hydrochloric Acid → Methyl 4-{[2-(chloromethyl)-2-propenyl]oxy}-3-formylbenzoate

HRID 1791043Notes

Reaction equation

HRID 1791043 reaction equation
CN(C)C=O.[Cl:6][CH2:7][C:8]([CH2:10]Cl)=[CH2:9].[CH:12]([C:14]1[CH:15]=[C:16]([CH:21]=[CH:22][C:23]=1[OH:24])[C:17]([O:19][CH3:20])=[O:18])=[O:13].Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[Cl:6][CH2:7][C:8](=[CH2:9])[CH2:10][O:24][C:23]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][C:14]=1[CH:12]=[O:13]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 158593-Chloro-2-chloromethyl-1-propeneHCID 212595Benzoic acid, 3-formyl-4-hydroxy-, methyl ester

Product 1

HCID 22042284Methyl 4-{[2-(chloromethyl)-2-propenyl]oxy}-3-formylbenzoateYield 52.4%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolvent

Procedure

45 ml of dimethylformamide and then 1.15 ml (9.95 mmol) of 2-chloromethyl-3-chloro-1-propene are added under argon to 717 mg (3.98 mmol) of methyl 3-formyl-4-hydroxybenzoate as a mixture with 1.055 g (9.95 mmol) and 440 mg (1.195 mmol) of tetrabutylammonium iodide. The solution is stirred for 26 hours and then water is added. In order to break the emulsion, the pH is brought to 7 using a 1N hydrochloric acid solution. The aqueous phase is extracted several times with ether and then the combined organic phases are washed several times with water and with brine. After drying over magnesium sulfate and concentrating under vacuum, the crude reaction product is purified by chromatography on silica gel (ethyl acetate/heptane 20/80) to give 560 mg (52%) of methyl 4-{[2-(chloromethyl)-2-propenyl]oxy}-3-formylbenzoate in the form of a white solid; 1H NMR (300 MHz, CDCl3): 10.44 (s, 1H), 8.45 (d, J=2.4 Hz, 1H), 8.18 (dd, J=2.4 Hz and 8.4 Hz, 1H), 7.04 (d, J=8.4 Hz, 1H), 5.44 and 5.39 (2s, 2H), 4.79 (s, 2H), 4.19 (s, 2H), 3.87 (s, 3H).

Workup

  1. extractionThe aqueous phase is extracted several times with ether
  2. washthe combined organic phases are washed several times with water
  3. dry with materialAfter drying over magnesium sulfate
  4. concentrationconcentrating under vacuum
  5. customthe crude reaction product
  6. customis purified by chromatography on silica gel (ethyl acetate/heptane 20/80)

Sources & evidence

ORD record
ord-0276606162d6416e9332d1d0a1662348
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

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