Dimethylformamide → 4-Ethoxy-2-methylbenzaldehyde

HRID 636358Notes

Reaction equation

HRID 636358 reaction equation
[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([CH3:10])[CH:7]=[CH:8][CH:9]=1)[CH3:2].P(Cl)(Cl)(Cl)=O.CN([CH:19]=[O:20])C.C([O-])(=O)C.[Na+]>C(OCC)(=O)C.CCCCCC>[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([CH:19]=[O:20])=[C:6]([CH3:10])[CH:5]=1)[CH3:2]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 693053-EthoxytolueneHCID 517045Sodium Acetate

Product 1

HCID 132097014-Ethoxy-2-methylbenzaldehydeYield 20.4%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

Using an analogous formylation procedure to that employed by Campaigne et al 3-ethoxytoluene (10.18 g, 75 mmol) was added dropwise to a mixture of phosphorous oxychloride (6.88 mL, 75 mmol) and DMF (21 mL, 0.272 mol) at 0° C. and the resultant mixture was heated to 80-90° C. for 4 hrs before being poured onto crushed ice. The solution was taken to pH 7 with saturated sodium acetate, extracted with dichloromethane and upon drying and solvent removal a clear colourless oil was obtained. Column chromatography (silica, ethyl acetate/hexane, 1:9, Rf 0.33) gave the title compound as a clear colourless oil (1.13 g, 20.40% based on reacted material). 1H n.m.r. [400 MHZ, CDCl3] δ 6 10.09, s, 1H, CHO; 7.73, d, J 8.6 Hz, 1H, H6; 6.81, dd, J 8.5, 1, 1H, H5, 6.72, d, J 1 Hz, 1H, H3; 4.09, q, J 7 Hz, 2H, OCH2CH3; 2.63, s, 3H, ArCH3; 1.43, t, J 6.95 Hz, 3H, CH2CH3. 13C n.m.r. [100 MHZ, CDCl3] d 190.95, CHO; 162.88, C4; 143.02, C2; 134.59, C6; 127.53, C1; 117.23, C3; 111.67, C5; 63.54, OCH2CH3; 19.70, ArCH3; 14.47, OCH2CH3. Mass spectrum (f.a.b.) calculated 164.083724, found 164.084.

Workup

  1. additionbefore being poured
  2. customonto crushed ice
  3. extractionextracted with dichloromethane
  4. customupon drying
  5. customsolvent removal a clear colourless oil
  6. customwas obtained

Sources & evidence

ORD record
ord-428a26a080cc4f7ab875bcba49335108
Source dataset
uspto-grants-2001_02
Patent number
US06194414B1

Reaction notes

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