Sulfuric Acid → HCID 90431845, compound

HRID 929425Notes

Reaction equation

HRID 929425 reaction equation
[CH3:1][Mg]Br.[CH3:4][C@:5]1([CH:16]=[O:17])[CH2:7][C@H:6]1[C@H:8]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH3:9].S(=O)(=O)(O)O>>[CH3:4][C@:5]1([C@H:16]([OH:17])[CH3:1])[CH2:7][C@H:6]1[C@H:8]([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[CH3:9]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 90431827HCID 90431827, compoundHCID 178418573HCID 178418573, compound

Product 1

HCID 90431845HCID 90431845, compoundYield 67%

Procedure

Under a nitrogen atmosphere, methyl magnesium bromide (0.97 mol/L, tetrahydrofuran solution, 8.5 ml, 8.25 mmol) was placed into a 100-ml flask equipped with a stirring apparatus, a dropping funnel, and a thermometer, and cooled to −10° C. (1S*,2S*)-1-Methyl-2-[(R*)-1-phenylethyl]cyclopropane carbaldehyde (1.03 g, 5.5 mmol) was placed into the dropping funnel, and added dropwise in 5 minutes with the temperature kept at −10° C. After stirring for 60 minutes, a 20% aqueous sulfuric acid solution (4.5 g) was added. After stirring for 10 minutes, the aqueous layer was separated, and the organic layer was washed twice with water (10 ml). The solvent was recovered under reduced pressure to obtain a condensed residue. This residue was purified by silica gel column chromatography (hexane:ethyl acetate=10:1). (R*)-1-[(1S*,2S*)-1-Methyl-2-((R*)-1-phenylethyl)cyclopropyl]ethanol (0.75 g, 3.68 mmol, 67% yield) was obtained as the main isomer, and (S*)-1-[(1S*,2S*)-1-methyl-2-((R*)-1-phenylethyl)cyclopropyl]ethanol (0.205 g, 1.0 mmol, 18% yield) was obtained as a minor isomer. The relative configurations of the main isomer and the minor isomer were determined by NOESY measurement.

Workup

  1. customequipped with a stirring apparatus, a dropping funnel
  2. additionadded dropwise in 5 minutes with the temperature
  3. customkept at −10° C
  4. stirringAfter stirring for 10 minutes
  5. customthe aqueous layer was separated
  6. washthe organic layer was washed twice with water (10 ml)
  7. customThe solvent was recovered under reduced pressure
  8. customto obtain a condensed residue
  9. customThis residue was purified by silica gel column chromatography (hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-bfb4972241dc4021a28539363d494f35
Source dataset
uspto-grants-2016_03
Patent number
US09296675B2

Reaction notes

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