Sulfuric Acid → HCID 22262058, compound

HRID 406351Notes

Reaction equation

HRID 406351 reaction equation
Cl[CH2:2][C:3]([CH3:5])=[CH2:4].[CH:6]1[C:11]([OH:12])=[CH:10][CH:9]=[C:8]([CH3:13])[CH:7]=1.S(=O)(=O)(O)O.[OH-].[Na+]>COC(C)(C)C>[CH3:4][C:3]1([CH3:5])[C:10]2[CH:9]=[C:8]([CH3:13])[CH:7]=[CH:6][C:11]=2[O:12][CH2:2]1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 2879P-CresolHCID 112413-Chloro-2-methyl-1-propeneHCID 14798Sodium Hydroxide2×

Product 1

HCID 22262058HCID 22262058, compound

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

3-Chloro-2-methylpropene (9.7 mL) was added dropwise to a mixed solution of p-cresol (CAS #106-44-5, 10.8 g) and concentrated sulfuric acid (2.5 g), and the mixture was stirred at room temperature for one hour and 20 minutes. The reaction solution was ice-cooled and a 5 N sodium hydroxide aqueous solution (20 mL) was added, followed by stirring at 90° C. for 45 minutes. A 5 N sodium hydroxide aqueous solution (10 mL) was added to the reaction solution, and the mixture was stirred at 90° C. for two hours and 45 minutes. The reaction solution was left to cool to room temperature. tert-Butyl methyl ether was added to the reaction solution, and the organic layer was separated. The resulting organic layer was sequentially washed with water (three times) and brine, dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (carrier: Merck silica gel 60 (230-400 mesh); elution solvent:heptane:ethyl acetate=1:0→49:1). The target fraction was concentrated and the resulting residue was purified again by silica gel column chromatography (carrier: Chromatorex™ NH; elution solvent: heptane). The target fraction was concentrated and the resulting residue was distilled under reduced pressure to obtain 1.87 g of the target compound (bp. 102° C./20 mmHg). The property values of the compound are as follows.

Workup

  1. temperaturecooled
  2. stirringby stirring at 90° C. for 45 minutes
  3. stirringthe mixture was stirred at 90° C. for two hours and 45 minutes
  4. waitThe reaction solution was left
  5. temperatureto cool to room temperature
  6. customthe organic layer was separated
  7. washThe resulting organic layer was sequentially washed with water (three times) and brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe resulting residue was purified by silica gel column chromatography (carrier: Merck silica gel 60 (230-400 mesh); elution solvent:heptane:ethyl acetate=1:0→49:1)
  11. concentrationThe target fraction was concentrated
  12. customthe resulting residue was purified again by silica gel column chromatography (carrier: Chromatorex™ NH; elution solvent: heptane)
  13. concentrationThe target fraction was concentrated
  14. distillationthe resulting residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-010e65e189344d8eb52fa8a59485c74c
Source dataset
uspto-grants-2014_06
Patent number
US08754100B2

Reaction notes

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