Epichlorohydrin → HCID 20315120, compound

HRID 2419211Notes

Reaction equation

HRID 2419211 reaction equation
B(F)(F)F.CCOCC.C(C1OC1)Cl.[CH:15]([NH:18][C:19](=O)[C:20]([C:22]1[S:23][C:24]([O:27][CH3:28])=[CH:25][CH:26]=1)=[O:21])([CH3:17])[CH3:16]>CCOCC>[CH:15]([NH:18][CH2:19][CH:20]([C:22]1[S:23][C:24]([O:27][CH3:28])=[CH:25][CH:26]=1)[OH:21])([CH3:17])[CH3:16]

Participants

5

Reactant 3

HCID 7835EpichlorohydrinHCID 8000Boron trifluoride etherateHCID 20315122HCID 20315122, compound

Product 1

HCID 20315120HCID 20315120, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To freshly distilled boron trifluoride etherate (61.0 mmoles) dissolved in 30 ml anhydrous ether, distilled epichlorohydrin (4.19 g, 46.0 mmoles) is added at such a rate to cause the solution to reflux. After addition, the solution is heated at reflux for 1.5 hr with vigorous stirring. The reaction mixture is cooled and most of the ether is removed with a pipette and the solid residue is dried with a stream of dry nitrogen. Anhydrous methylene chloride (50 ml) and the N-isopropyl-5-methoxy-2-thiopheneglyoxylamide (8.0 g, 39.0 mmole), described above, is added and the solution is stirred at room temperature for 56 hr. The methylene chloride is evaporated and replaced with 50 ml anhydrous methanol. The solution is cooled to 0° C. and sodium borohydride (4.0 g) is added portionwise over a period of 4 hr. The mixture is brought to room temperature, stirred for 24 hr then quenched with ice-water. The aqueous solution is extracted several times with ether. The combined ether extract are washed with water and brine, dried (MgSO4) and concentrated. The product is purified by chromatography on silica gel (400 g, chloroformmethanol, 8:2). Evaporation of the eluate and recrystallization of the residue from hexane gives the title compound; mp 81° C, γmaxCHCl3 3300, 3100, 1650, 1505, 1220 cm-1.

Workup

  1. additionis added at such a rate
  2. temperatureto reflux
  3. additionAfter addition
  4. temperaturethe solution is heated
  5. temperatureat reflux for 1.5 hr with vigorous stirring
  6. customis removed with a pipette
  7. customthe solid residue is dried with a stream of dry nitrogen
  8. additionis added
  9. customThe methylene chloride is evaporated
  10. temperatureThe solution is cooled to 0° C.
  11. additionsodium borohydride (4.0 g) is added portionwise over a period of 4 hr
  12. customis brought to room temperature
  13. stirringstirred for 24 hr
  14. customthen quenched with ice-water
  15. extractionThe aqueous solution is extracted several times with ether
  16. extractionThe combined ether extract
  17. washare washed with water and brine
  18. dry with materialdried (MgSO4)
  19. concentrationconcentrated
  20. customThe product is purified by chromatography on silica gel (400 g, chloroformmethanol, 8:2)
  21. customEvaporation of the eluate and
  22. customrecrystallization of the residue from hexane

Sources & evidence

ORD record
ord-e1504b7f889c48fd98e2a6337f7aaf06
Source dataset
uspto-grants-1978_08
Patent number
US04105663

Reaction notes

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