HCID 15735544, compound → HCID 15735587, compound

HRID 704605Notes

Reaction equation

HRID 704605 reaction equation
[CH:1]1(/[CH:7]=[C:8](/[CH2:14][P:15]([O:21]CC)([CH2:17][CH:18]([CH3:20])[CH3:19])=[O:16])\[C:9]([O:11]CC)=[O:10])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C1(/C=C(\CP(O)(CC(C)C)=O)/C(OCC)=O)CCCCC1.C1(/C=C(/CP(O)(CC(C)C)=O)\C(OCC)=O)CCCCC1.OP(C/C(=C\C(C)CCC(O)=O)/C(O)=O)(CC(C)C)=O>Cl.C(OCCCC)(=O)C.C(O)C.[OH-].[Na+]>[CH:1]1(/[CH:7]=[C:8](\[CH2:14][P:15]([OH:21])([CH2:17][CH:18]([CH3:19])[CH3:20])=[O:16])/[C:9]([OH:11])=[O:10])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]1

Participants

8

Reactant 4

HCID 15735544HCID 15735544, compoundHCID 15735657HCID 15735657, compoundHCID 18643487HCID 18643487, compoundHCID 86744540HCID 86744540, compound

Product 1

HCID 15735587HCID 15735587, compoundYield 49.5%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 14798Sodium HydroxideSolventHCID 20072624HCID 20072624, compoundSolvent

Procedure

A solution of 11.1 g (32.2 millimoles) of ethyl (E)-3-cyclohexyl-2-(ethoxyisobutylphosphinoyl)methylpropenoate in 100 ml of 4.3 N hydrogen chloride-butyl acetate was heated in a sealed tube for 48 hours. After cooling, the solvent was evaporated under reduced pressure to give a mixture of ethyl (Z)-3-cyclohexyl-2-(hydroxyisobutylphosphinoyl)methylpropenoate and ethyl (E)-3-cyclohexyl-2-(hydroxyisobutylphosphinoyl)methylpropenoate as a pale yellow oil. The (Z):(E) ratio determined by 1H-NMR was 90:10. The mixture was dissolved in a mixture of 32 ml of ethanol and 16 ml of 6 N sodium hydroxide, and heated under reflux for 3 hours. After cooling, the solvent was evaporated under reduced pressure. The residue was dissolved in 100 ml of water and made strongly acidic with hydrochloric acid, whereupon crystals precipitated. The crystals were collected by filtration and recrystallized from methanol-water (2:1) to give 4.6 g (yield 49%) of (Z)-3-cyclohexyl-2-(hydroxyisobutylphosphinoyl)methylpropenoic acid. Its melting point and IR and 1H-NMR were identical with those of the product obtained in Example 5 (b).

Workup

  1. temperatureAfter cooling
  2. customthe solvent was evaporated under reduced pressure
  3. customto give
  4. temperatureheated
  5. temperatureunder reflux for 3 hours
  6. temperatureAfter cooling
  7. customthe solvent was evaporated under reduced pressure
  8. dissolutionThe residue was dissolved in 100 ml of water
  9. customprecipitated
  10. filtrationThe crystals were collected by filtration
  11. customrecrystallized from methanol-water (2:1)

Sources & evidence

ORD record
ord-581971c643fe4c2091847840fec91167
Source dataset
uspto-grants-1991_01
Patent number
US04988681

Reaction notes

Loading…