Phosphorus oxychloride → 4-Benzyloxy-2,3-methylenedioxybenzaldehyde

HRID 1904958Notes

Reaction equation

HRID 1904958 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]2[O:15][CH2:16][O:17][C:10]=12)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CN([CH:26]=[O:27])C1C=CC=CC=1.P(Cl)(Cl)(Cl)=O.ClCCl.CCCCCC>ClC1C=CC=CC=1>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH:26]=[O:27])=[C:11]2[O:15][CH2:16][O:17][C:10]=12)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 66737N-MethylformanilideHCID 141805661-Benzyloxy-2,3-methylenedioxybenzeneHCID 21226440Methylenechloride Hexane

Product 1

HCID 141805674-Benzyloxy-2,3-methylenedioxybenzaldehydeYield 13%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent2×

Conditions

Temperature
-5 °C

Procedure

1-Benzyloxy-2,3-methylenedioxybenzene (47.8 g) in chlorobenzene (50 ml) was added dropwise to a mixture of N-methylformanilide (34 g) and phosphorus oxychloride (38.5 g) in chlorobenzene (50 ml) maintained at -5° C. When the addition was complete the reaction mixture was allowed to warm to room temperature. It was then poured onto ice, and stirred overnight. The resulting mixture was extracted with ethyl acetate, washed with water and brine, and then dried and evaporated to yield 47.9 g of crude product as an isomeric mixture of aldehydes. Silica gel chromatography using 1:1 dichloromethane-hexane afforded 7 g of 4-benzyloxy-2,3-methylenedioxybenzaldehyde, mp 81°-82° C.

Workup

  1. additionWhen the addition
  2. temperatureto warm to room temperature
  3. additionIt was then poured onto ice
  4. extractionThe resulting mixture was extracted with ethyl acetate
  5. washwashed with water and brine
  6. customdried
  7. customevaporated
  8. customto yield 47.9 g of crude product

Sources & evidence

ORD record
ord-ad1dfd67f5084333920a600338427a12
Source dataset
uspto-grants-1989_06
Patent number
US04840965

Reaction notes

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