1,2-Dichloroethane → 4-(2-CHLOROETHOXY)-3-METHOXYBENZALDEHYDE

HRID 366815Notes

Reaction equation

HRID 366815 reaction equation
[O:1]=[CH:2][C:3]1[CH:11]=[CH:10][C:8]([OH:9])=[C:5]([O:6][CH3:7])[CH:4]=1.C([O-])([O-])=O.[K+].[K+].[Cl:18][CH2:19][CH2:20]Cl>CN(C=O)C>[Cl:18][CH2:19][CH2:20][O:9][C:8]1[CH:10]=[CH:11][C:3]([CH:2]=[O:1])=[CH:4][C:5]=1[O:6][CH3:7]

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 1183VanillinHCID 11430Potassium Carbonate

Product 1

HCID 107750234-(2-CHLOROETHOXY)-3-METHOXYBENZALDEHYDEYield 85.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
67.5 °C

Procedure

A mixture of vanillin (10.00 g, 65.7 mmol), K2CO3 (45.4 g, 329 mmol), 1,2-dichloroethane (104 mL, 1.31 mol), and DMF (300 mL) was stirred at 65-70° C. for 16 h. The dichloroethane was evaporated and the remaining slurry was poured onto ice. The oil that separated was extracted with Et2O (×4) and EtOAc (×3). The combined extracts were washed with water (×3), dried (Na2SO4 /MgSO4), and evaporated to give a clear oil that solidified upon trituration with hexanes. Crystallization from Et20 gave 4-(2-chloroethoxy)-3-methoxybenzaldehyde (12.04 g, 85%) as white needles, mp 60-61° C. 1H NMR (CDCl3) δ 9.87 (s, 1 H, CHO), 7.46 (dd, J=8.0, 2.0 Hz, 1 H, H-6), 7.43 (d, J=2.0 Hz, 1 H, H-5), 6.99 (d, J=8.0 Hz, 1 H, H-2), 4.36 (t, J=6.1 Hz, 2 H, OCH2), 3.94 (s, 3 H, OCH3), 3.89 (t, J=6.1 Hz, 2 H, CH2Cl); 13C NMR δ 190.8 (CHO), 153.9 (C-4), 150.0 (C-3), 130.8 (C-1), 126.3 (C-6), 112.3 (C-2), 109.8 (C-5), 68.9 (OCH2), 56.0 (OCH3), 41.2 (CH2Cl).

Workup

  1. customThe dichloroethane was evaporated
  2. additionthe remaining slurry was poured onto ice
  3. customThe oil that separated
  4. extractionwas extracted with Et2O (×4) and EtOAc (×3)
  5. washThe combined extracts were washed with water (×3)
  6. dry with materialdried (Na2SO4 /MgSO4)
  7. customevaporated
  8. customto give a clear oil that
  9. customCrystallization from Et20

Sources & evidence

ORD record
ord-cdcb81c40547461bbd61cafb72d733c6
Source dataset
uspto-grants-2000_10
Patent number
US06130237

Reaction notes

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