Citric Acid → 1268842-81-4

HRID 1026580Notes

Reaction equation

HRID 1026580 reaction equation
[C:1]([O:5][C:6]([C:8]1([C:11](O)=[O:12])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(Cl)(=O)OCC(C)C.[BH4-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCCC1.O.C(N(CC)CC)C>[OH:12][CH2:11][C:8]1([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]1

Participants

8

Reactant 4

HCID 311Citric AcidHCID 62365Isobutyl chloroformateHCID 4311764Sodium borohydrideHCID 199732091-(tert-butoxycarbonyl)cyclopropanecarboxylic acid

Product 1

HCID 680062131268842-81-4Yield 77.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent

Procedure

Under ice cooling, to a tetrahydrofuran solution (20 ml) of 1-(tert-butoxycarbonyl)cyclopropanecarboxylic acid (1.79 g) and triethylamine (1.48 ml) was added dropwise isobutyl chlorocarbonate (1.37 ml), followed by stirring for 1 hour. Under ice cooling, the supernatant was added dropwise to a mixed solvent solution of sodium borohydride (1.09 g) in tetrahydrofuran (20 ml) and water (5 ml), and stirred for 30 minutes. A 10% aqueous citric acid solution was added, and extracted with ethyl acetate. The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford tert-butyl 1-(hydroxymethyl)cyclopropanecarboxylate (1.28 g).

Workup

  1. stirringstirred for 30 minutes
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated sodium chloride solution
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-c86f584b9aff47708aa54ecb2965e3ce
Source dataset
uspto-grants-2014_05
Patent number
US08729095B2

Reaction notes

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