Methyl Isobutyl Ketone → HCID 11073868, compound

HRID 912409Notes

Reaction equation

HRID 912409 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH:4]([CH3:11])[CH2:5][CH2:6][CH2:7][C:8](=[O:10])[CH3:9].CC(OC)(C)C.[OH-].[Na+].C(C(C)=O)C(C)C>P(=O)(O)(O)O>[CH3:1][O:2][C:3](=[O:12])[C@@H:4]([CH3:11])[CH2:5][CH2:6][CH2:7][C:8](=[O:10])[CH3:9]

Participants

6

Reactant 4

HCID 7909Methyl Isobutyl KetoneHCID 14798Sodium HydroxideHCID 15413tert-Butyl methyl etherHCID 539109Heptanoic acid, 2-methyl-6-oxo-, methyl ester

Product 1

HCID 11073868HCID 11073868, compoundYield 41.5%

Reagents, catalysts & solvents 1

HCID 1004Phosphoric AcidSolvent

Conditions

Temperature
10 °C

Procedure

10.6 g (content 94.3%, 5.75 mmol) of a racemate of 2-methyl-6-oxoheptanoic acid methyl ester and 20.0 g of MTBE were suspended in 50.0 g of 0.1 M phosphoric acid buffered solution (pH 7.0). The suspension was cooled to 10° C., then, 2.0 g (moisture percentage 56%, enzymatic activity 4028 KU/Kg, reduced by dry product) of immobilized Aspergillus flavus ATCC11492 strain-derived esterase (prepared by a method described in JP-A No. 2003-70471) was added, and the mixture was stirred at 10° C. for 51 hours while maintaining pH at 7.0 to 7.5 by appropriately adding 4% NaOH aqueous solution. Thereafter, the reaction solution was filtrated using Radiolite (filtration aid, trade name: manufactured by Showa Chemical Industry Co., Ltd.), to remove the esterase. The resultant filtrate was extracted twice with 25 g and 12.5 g of methyl isobutyl ketone (MIBK), then, the resultant organic layers were combined and washed with 15% saline, to obtain a MIBK solution of optically active (S)-2-methyl-6-oxoheptanoic acid methyl ester (optical purity 98.9% ee, yield 41.5%). The optical purity was analyzed by HPLC [Chiralpak AS-H, 4.6 mm×25 cm (manufactured by Daicel Chemical Industries, Ltd.)] like in Example 1.

Workup

  1. custom2.0 g (moisture percentage 56%, enzymatic activity 4028 KU/Kg, reduced by dry product) of immobilized Aspergillus flavus ATCC11492 strain-derived esterase (prepared by a method
  2. addition2003-70471) was added
  3. temperaturewhile maintaining pH at 7.0 to 7.5
  4. filtrationThereafter, the reaction solution was filtrated
  5. filtrationRadiolite (filtration aid, trade name: manufactured by Showa Chemical Industry Co., Ltd.)
  6. customto remove the esterase
  7. extractionThe resultant filtrate was extracted twice with 25 g and 12.5 g of methyl isobutyl ketone (MIBK)
  8. washwashed with 15% saline

Sources & evidence

ORD record
ord-dc8ec84e6ce34eeaa41515db2fb4f275
Source dataset
uspto-grants-2011_09
Patent number
US08026081B2

Reaction notes

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