Water → 3-(4-Chlorophenyl)-3-methylbutyraldehyde

HRID 1441005Notes

Reaction equation

HRID 1441005 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Br)=[CH:4][CH:3]=1.[CH3:10][C:11]([CH3:15])=[CH:12][CH:13]=[O:14].O>O1CCCC1.[Cu]Br>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:11]([CH3:15])([CH3:10])[CH2:12][CH:13]=[O:14])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 962WaterHCID 610203-Methyl-2-butenalHCID 178478191HCID 178478191, compound

Product 1

HCID 153325663-(4-Chlorophenyl)-3-methylbutyraldehydeYield 38.6%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Under a nitrogen atmosphere, a stirred solution of 21.6 grams (0.10 mole) of 4-chlorophenylmagnesium bromide (1M in diethyl ether) in 100 mL of tetrahydrofuran was cooled to -15° C., and 0.7 gram (catalyst) of copper(I) bromide was added in one portion. Upon completion of addition, 9.7 mL (0.10 mole) of 3-methyl-2-butenal was added dropwise during a 1.5 hour period, while maintaining the reaction mixture temperature below -10° C. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature, where it stirred for about 18 hours. The reaction mixture was then poured into 300 mL of water and extracted with two 200 mL portions of diethyl ether. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel, using 50% petroleum ether in methylene chloride. The appropriate product-containing fractions were combined and concentrated under reduced pressure, yielding 7.6 grams of 3-(4-chlorophenyl)-3-methylbutyraldehyde. The NMR spectrum was consistent with the proposed structure.

Workup

  1. additionwas added dropwise during a 1.5 hour period
  2. temperaturewhile maintaining the reaction mixture temperature below -10° C
  3. additionUpon completion of addition
  4. extractionextracted with two 200 mL portions of diethyl ether
  5. dry with materialThe combined extracts were dried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure to a residue
  8. additionThe appropriate product-containing fractions
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-d39ee35e2c8d46349e8140c7a3549779
Source dataset
uspto-grants-1996_03
Patent number
US05502054

Reaction notes

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