Dimethylformamide → 2-Benzyloxy-3-(dimethylamino)acrolein

HRID 367004Notes

Reaction equation

HRID 367004 reaction equation
P(Cl)(Cl)(Cl)(Cl)Cl.C([O:9][CH:10](OCC)[CH2:11][O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)C.[CH3:23][N:24]([CH:26]=O)[CH3:25].[OH-].[Na+]>Cl.CCOCC>[CH2:13]([O:12][C:11](=[CH:23][N:24]([CH3:26])[CH3:25])[CH:10]=[O:9])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 14798Sodium HydroxideHCID 24819Phosphorus pentachlorideHCID 4321487Benzyloxyacetaldehyde diethyl acetal

Product 1

HCID 545210022-Benzyloxy-3-(dimethylamino)acroleinYield 46.2%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
60 °C

Procedure

Prepared by a modification of the literature procedure reported in Croat. Chim. Acta, 1966, 235. Phosphorus pentachloride (0.13 mol) was added to benzyloxyacetaldehyde diethyl acetal (0.13 mol) at 20-30° C. The reaction mixture was heated at 60° C. for 75 min and then cooled to 0° C. The reaction mixture was treated with DMF (0.39 mol) and stirred at room temperature for four days. The reaction mixture was diluted with 1.0N HCl(aq) (200 ml) and ether (200 ml). The ether layer was discarded and the aqueous layer was basified with 8N NaOH(aq). The aqueous layer was extracted with ethyl acetate and ether and the combined organic extracts were dried (MgSO4), filtered and evaporated in vacuo. The resulting black oil was purified by column chromatography to give the product as a brown solid (0.06 mol, 43%). δH (250 MHz; CDCl3) 8.62 (1H, s), 7.44-7.26 (5H, m), 6.18 (1H, s), 4.96 (2H, s), 3.04 (6H, s).

Workup

  1. customPrepared by a modification of the literature procedure
  2. temperaturecooled to 0° C
  3. extractionThe aqueous layer was extracted with ethyl acetate and ether
  4. dry with materialthe combined organic extracts were dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customThe resulting black oil was purified by column chromatography

Sources & evidence

ORD record
ord-ed877cb23e834ebe854cfc56067d845a
Source dataset
uspto-grants-2000_10
Patent number
US06133255

Reaction notes

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