Benzyl Bromide → 4-(Benzyloxy)-2,6-dichlorobenzaldehyde

HRID 1672711Notes

Reaction equation

HRID 1672711 reaction equation
[Cl:1][C:2]1[CH:9]=[C:8]([OH:10])[CH:7]=[C:6]([Cl:11])[C:3]=1[CH:4]=[O:5].C(=O)([O-])[O-].[K+].[K+].[CH2:18](Br)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>CN(C)C=O>[Cl:1][C:2]1[CH:9]=[C:8]([O:10][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH:7]=[C:6]([Cl:11])[C:3]=1[CH:4]=[O:5]

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 5283822,6-Dichloro-4-hydroxybenzaldehyde

Product 1

HCID 111502104-(Benzyloxy)-2,6-dichlorobenzaldehyde

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Treat a mixture of 2,6-dichloro-4-hydroxy-benzaldehyde (250 g, 1.3 mol) and potassium carbonate (361.8 g, 2.62 mol) in 2 L dimethylformamide with benzyl bromide (268.64 g, 1.57 mol). Stir the reaction at room temperature for 1 hour. Filter off solids and pour into 12 L of water. Filter off solid, wash several times with water, air dry and dissolve in ethyl acetate. Dry over magnesium sulfate, filter and concentrate under vacuum to ˜1.5 L. Allow to sit overnight then filter. Wash solid with minimal amount of hexane and vacuum dry. Concentrate the filtrate under vacuum and triturate with hexane to yield a second crop of product which when combined with the first crop equals 245 g white crystals. Repeat to obtain a 3rd crop of 80 g as a light-tan powder (88% overall yield): 1H NMR (400 MHz, DMSO-d6) δ 10.26 (s, 1H), 7.43 (m, 5H), 7.28 (s, 2H), 5.25 (s, 2H).

Workup

  1. additionTreat
  2. customthe reaction at room temperature for 1 hour
  3. filtrationFilter off solids
  4. additionpour into 12 L of water
  5. filtrationFilter off solid
  6. washwash several times with water, air
  7. customdry
  8. dissolutiondissolve in ethyl acetate
  9. dry with materialDry over magnesium sulfate
  10. filtrationfilter
  11. concentrationconcentrate under vacuum to ˜1.5 L
  12. filtrationthen filter
  13. washWash solid with minimal amount of hexane and vacuum
  14. customdry
  15. concentrationConcentrate the filtrate under vacuum
  16. customtriturate with hexane
  17. customto yield a second crop of product which when
  18. customRepeat to obtain a 3rd crop of 80 g
  19. customas a light-tan powder (88% overall yield)

Sources & evidence

ORD record
ord-b83049ffcee14ff9bd10a3fec32f3b1e
Source dataset
uspto-grants-2011_08
Patent number
US07998999B2

Reaction notes

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