Benzyl Alcohol → 1-(Benzyloxycarbonyl)cyclopropanecarboxylic acid

HRID 2265613Notes

Reaction equation

HRID 2265613 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 thereto while stirring in an ice water bath. After stirring at the same temperature for 30 min, thionyl chloride (2.82 ml) was added dropwise while stirring in an ice water bath. After stirring at the same temperature for 30 min, a solution of benzyl alcohol (4.39 ml) in tetrahydrofuran (25 ml) was added while stirring in an ice water bath, and the reaction mixture was allowed to gradually warm up to room temperature, followed by stirring overnight. To the reaction mixture was added a 2N aqueous solution of sodium hydroxide (100 ml), and tetrahydrofuran was removed under reduced pressure. To the resultant aqueous solution was added tert-butyl methyl ether (25 ml) and stirred. The organic layer and the aqueous layer were separated. The aqueous layer was cooled in an ice water bath, and adjusted to pH 4 with 2N hydrochloric acid (50 ml). Ethyl acetate (150 ml) was added thereto and stirred for a while. The organic layer was separated, washed with brine, and dried over anhydrous sodium sulfate. The solvent was removed to give residue, which was dried under reduced pressure to provide the titled compound as a pale yellow oil (6.29 g, 74%).

Workup

  1. stirringAfter stirring at the same temperature for 30 min
  2. stirringwhile stirring in an ice water bath
  3. stirringAfter stirring at the same temperature for 30 min
  4. stirringwhile stirring in an ice water bath
  5. stirringby stirring overnight
  6. customwas removed under reduced pressure
  7. additionTo the resultant aqueous solution was added tert-butyl methyl ether (25 ml)
  8. stirringstirred
  9. customThe organic layer and the aqueous layer were separated
  10. temperatureThe aqueous layer was cooled in an ice water bath
  11. additionEthyl acetate (150 ml) was added
  12. stirringstirred for a while
  13. customThe organic layer was separated
  14. washwashed with brine
  15. dry with materialdried over anhydrous sodium sulfate
  16. customThe solvent was removed
  17. customto give residue, which
  18. customwas dried under reduced pressure

Sources & evidence

ORD record
ord-3e1b329cee604710a701038f82ba9753
Source dataset
uspto-grants-2010_12
Patent number
US07855290B2

Reaction notes

Loading…