Benzyl Alcohol → 1-(Benzyloxycarbonyl)cyclopropanecarboxylic acid

HRID 388494Notes

Reaction equation

HRID 388494 reaction equation
[C:1]1([C:7]([OH:9])=[O:8])([C:4]([OH:6])=[O:5])[CH2:3][CH2:2]1.S(Cl)(Cl)=O.[CH2:14](O)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[OH-].[Na+]>O1CCCC1.C(N(CC)CC)C>[CH2:14]([O:5][C:4]([C:1]1([C:7]([OH:9])=[O:8])[CH2:3][CH2:2]1)=[O:6])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 14798Sodium HydroxideHCID 24386Thionyl ChlorideHCID 690171,1-Cyclopropanedicarboxylic acid

Product 1

HCID 574708601-(Benzyloxycarbonyl)cyclopropanecarboxylic acidYield 74%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8471TriethylamineSolvent

Procedure

1,1-Cyclopropanedicarboxylic acid (5.02 g) was dissolved in tetrahydrofuran (50 ml) under a nitrogen atmosphere, and triethylamine (5.38 ml) was added dropwise with stirring and cooling in an ice water bath. After stirring at the same temperature for 30 minutes, thionyl chloride (2.82 ml) was added dropwise with cooling in ice water bath. After stirring at the same temperature for 30 minutes, a solution of benzyl alcohol (4.39 ml) in tetrahydrofuran (25 ml) was added with cooling in an ice water bath, and the reaction mixture was gradually brought to room temperature and stirred overnight. A 2N aqueous solution of sodium hydroxide (100 ml) was added to the reaction mixture, and tetrahydrofuran was distilled off under reduced pressure. tert-Butyl methyl ether (25 ml) was added to the resultant aqueous solution, followed by stirring. The organic layer and the aqueous layer were separated. The aqueous layer was cooled in an ice water bath, and 2N hydrochloric acid (50 ml) was added to adjust pH 4. Ethyl acetate (150 ml) was added, and the reaction mixture was stirred for a while. The organic layer was separated, washed with brine, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was dried under reduced pressure to give the title compound (6.29 g, 74%) as a pale yellow oil.

Workup

  1. temperaturecooling in an ice water bath
  2. stirringAfter stirring at the same temperature for 30 minutes
  3. stirringAfter stirring at the same temperature for 30 minutes
  4. temperaturewith cooling in an ice water bath
  5. customwas gradually brought to room temperature
  6. stirringstirred overnight
  7. distillationwas distilled off under reduced pressure
  8. additiontert-Butyl methyl ether (25 ml) was added to the resultant aqueous solution
  9. stirringby stirring
  10. customThe organic layer and the aqueous layer were separated
  11. temperatureThe aqueous layer was cooled in an ice water bath
  12. addition2N hydrochloric acid (50 ml) was added
  13. additionEthyl acetate (150 ml) was added
  14. stirringthe reaction mixture was stirred for a while
  15. customThe organic layer was separated
  16. washwashed with brine
  17. dry with materialdried over anhydrous sodium sulfate
  18. customThe residue obtained
  19. distillationby distilling off the solvent
  20. customwas dried under reduced pressure

Sources & evidence

ORD record
ord-6a8ed7bed3b543d6a8b2cf15786d1b76
Source dataset
uspto-grants-2013_02
Patent number
US08377938B2

Reaction notes

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