Citric Acid → (+)-2-Cyano-2-methylhexanol

HRID 358934Notes

Reaction equation

HRID 358934 reaction equation
C([O:3][C:4](=O)[C:5]([C:11]#[N:12])([CH3:10])[CH2:6][CH2:7][CH2:8][CH3:9])C.[Cl-].[Li+].[BH4-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCCC1.C(O)C>[C:11]([C:5]([CH3:10])([CH2:6][CH2:7][CH2:8][CH3:9])[CH2:4][OH:3])#[N:12]

Participants

7

Reactant 4

HCID 311Citric AcidHCID 433294Lithium ChlorideHCID 4311764Sodium borohydrideHCID 14495732(+)-2-Cyano-2methylhexanoic acid-ethyl-ester

Product 1

HCID 14793448(+)-2-Cyano-2-methylhexanolYield 63.8%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 915 mg (5 mM) of (+)-2-cyano-2methylhexanoic acid-ethyl-ester ([α]D +2.2 degrees (c 2.782, methanol)) in 8 ml of dry tetrahydrofuran was added dropwise to a mixture of 423 mg (10 mM) of anhydrous lithium chloride and 379 mg (10 mM) of sodium borohydride under stirring at room temperature. Then, 17 ml of dry ethanol was added thereto, followed by reaction for 18 hours at room temperature. After the reaction, the reaction mixture was cooled on an ice bath and acidified to pH 4 by adding 10% citric acid. A precipitate formed at that time was removed by filtration, and the solvent in the filtrate was removed by reduced pressure distillation. Then, 5 ml of distilled water was added to the remaining product, and the mixture was subjected to extraction with dichlocomethane. The organic layer was dried on sodium sulfate, and the solvent was distilled off under reduced pressure, followed further by distillation to obtain (-)-2-cyano-2-methylhexanol. Yield:63.8%, [α]D -1.2 degree (c 2.393, methylene chloride).

Workup

  1. customfollowed by reaction for 18 hours at room temperature
  2. customAfter the reaction
  3. temperaturethe reaction mixture was cooled on an ice bath
  4. customA precipitate formed at that time
  5. customwas removed by filtration
  6. customthe solvent in the filtrate was removed by reduced pressure distillation
  7. additionThen, 5 ml of distilled water was added to the remaining product
  8. extractionthe mixture was subjected to extraction with dichlocomethane
  9. customThe organic layer was dried on sodium sulfate
  10. distillationthe solvent was distilled off under reduced pressure
  11. distillationfollowed further by distillation

Sources & evidence

ORD record
ord-83608d5799984897a4da2b33e26448c7
Source dataset
uspto-grants-1991_03
Patent number
US04999130

Reaction notes

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