Hydrochloric Acid → 2,6-Dichloro-4-hydroxybenzaldehyde

HRID 2427462Notes

Reaction equation

HRID 2427462 reaction equation
C([Si]([O:8][C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([Cl:16])[CH:10]=1)(C)C)(C)(C)C.C([Li])(CC)C.CN(C)[CH:24]=[O:25].Cl>O1CCCC1.O.CCOCC>[Cl:16][C:11]1[CH:10]=[C:9]([OH:8])[CH:14]=[C:13]([Cl:15])[C:12]=1[CH:24]=[O:25]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 18007485Tert-butyl(3,5-dichlorophenoxy)dimethylsilaneHCID 178418400CID 53628100

Product 1

HCID 5283822,6-Dichloro-4-hydroxybenzaldehyde

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-68 °C

Procedure

Dissolve tert-butyl-(3,5-dichloro-phenoxy)-dimethyl-silane (425 g, 1.5 mol) in 4 L dry tetrahydrofuran and cool to −68° C. Slowly add 1.1 equivalents of sec-butyl lithium (103.1 g, 1.61 mol) at −68° C. (˜1.75 hr). After addition is complete, stir the reaction at −70° C. for 30 min. Add dimethylformamide (168.5 g, 2.3 mol) and stir the reaction at −70° C. for 1 hr. Add 1 M hydrochloric acid in water (3.5 L) and allow the reaction to warm to room temperature. Pour the reaction mixture into ether (5 L), wash with water then brine. Dry over sodium sulfate and concentrate under vacuum to an orange solid. Triturate with cold dichloromethane and filter to recover 250 g (80%) pale yellow solid.

Workup

  1. customat −68° C.
  2. custom(˜1.75 hr)
  3. additionAfter addition
  4. customthe reaction at −70° C. for 30 min
  5. customthe reaction at −70° C. for 1 hr
  6. customthe reaction
  7. temperatureto warm to room temperature
  8. washwash with water
  9. dry with materialDry over sodium sulfate
  10. concentrationconcentrate under vacuum to an orange solid
  11. customTriturate with cold dichloromethane
  12. filtrationfilter
  13. customto recover 250 g (80%) pale yellow solid

Sources & evidence

ORD record
ord-b6d227f573024d048c5b2a323a5eef4d
Source dataset
uspto-grants-2011_06
Patent number
US07968585B2

Reaction notes

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