Hydrochloric Acid → HCID 69590731, compound

HRID 1744775Notes

Reaction equation

HRID 1744775 reaction equation
[CH:1]12[CH2:7][C:6](=[CH:8][C:9]([O:11]CC)=[O:10])[CH:5]1[CH2:4][CH2:3][CH2:2]2.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[OH-].[Na+].Cl>CC(C)=O>[C@@H:1]12[CH2:7][C:6](=[CH:8][C:9]([OH:11])=[O:10])[C@@H:5]1[CH2:4][CH2:3][CH2:2]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 62657Potassium Phosphate, TribasicHCID 57357985Ethyl (bicyclo[3.2.0]heptan-6-ylidene)acetate

Product 1

HCID 69590731HCID 69590731, compoundYield 33.5%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

The racemic ester of Example 4 (200 g; 1.11 mol) was added to a stirred solution of acetone (0.80 L) and potassium phosphate buffer (pH=7.2; 1.2 L). The hazy solution was stirred at 20–25° C. and Novozyme 435 (50 g), immobilized Candida Antarctica lipase B, was added to the reaction mixture. The suspension was then stirred at 20–25° C. for 120 hours. During this time a 1M aqueous solution of sodium hydroxide was added so as to maintain a pH of 8.1. Concentrated hydrochloric acid (45 ml) was added to pH 2–3 and the heterogeneous reaction mixture was filtered. The filter cake was washed with n-heptane (1.0 L). The two phase filtrate was separated and the aqueous phase re-extracted with tert-butylmethyl ether (0.50 L). The combined organic phases were extracted with a 1M aqueous solution of sodium hydroxide (0.4 L). The aqueous solution was then adjusted to pH 1–2 by the addtion of concentrated hydrochloric acid (40 ml) and extracted twice with tert-butylmethyl ether (0.40 L, then 0.20 L). The combined organic phases were washed with demineralised water (0.40 L) and concentrated in vacuo to give the title compound (56.5 g) in 33.5% yield as a pale yellow oil which crystallised on standing.

Workup

  1. stirringThe suspension was then stirred at 20–25° C. for 120 hours
  2. temperatureto maintain a pH of 8.1
  3. filtrationthe heterogeneous reaction mixture was filtered
  4. washThe filter cake was washed with n-heptane (1.0 L)
  5. customThe two phase filtrate was separated
  6. extractionthe aqueous phase re-extracted with tert-butylmethyl ether (0.50 L)
  7. extractionThe combined organic phases were extracted with a 1M aqueous solution of sodium hydroxide (0.4 L)
  8. extractionextracted twice with tert-butylmethyl ether (0.40 L
  9. washThe combined organic phases were washed with demineralised water (0.40 L)
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1dee4b549bc2483eaf8a3b336685f572
Source dataset
uspto-grants-2006_03
Patent number
US07018818B2

Reaction notes

Loading…