Chloromethyl ethyl ether → HCID 53744314, compound

HRID 1584754Notes

Reaction equation

HRID 1584754 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:19]=[CH:18][C:7]([CH2:8][CH:9]([NH:13][C:14](=[O:17])[O:15][CH3:16])[CH2:10][CH:11]=[CH2:12])=[CH:6][CH:5]=1.[CH2:20]([O:22][CH2:23]Cl)[CH3:21]>O1CCCC1>[Cl:3][C:4]1[CH:19]=[CH:18][C:7]([CH2:8][CH:9]([N:13]([CH2:23][O:22][CH2:20][CH3:21])[C:14](=[O:17])[O:15][CH3:16])[CH2:10][CH:11]=[CH2:12])=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 18523Chloromethyl ethyl etherHCID 24758Sodium hydrideHCID 67597686HCID 67597686, compound

Product 1

HCID 53744314HCID 53744314, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A suspension of 10.0 g of sodium hydride (80% in mineral oil, 333 mmol) in dry THF (tetrahydrofuran) is heated to reflux under argon. A solution of 60.5 g (238 mmol) of methyl [1-(4-chlorobenzyl)but-3-enyl]carbamate in 50 ml of dry THF is added dropwise in the course of 1 hour. The mixture is then boiled under reflux for a further 2 hours until the evolution of gas subsides. The mixture is cooled to 0° C. and chloromethyl ethyl ether is added dropwise so that the reaction temperature does not rise above 5° C. After this, the mixture is slowly heated to 25° C. and stirred for 12 hours. Excess sodium hydride is cautiously destroyed with 1 ml of water before more water is added. The phases are separated and the aqueous phase is extracted again with tert-butyl methyl ether. The combined organic phases are washed with brine, dried over sodium sulfate and evaporated. The crude product is distilled at 0.1 mbar and has a boiling range of 120-125° C. TLC: ethyl acetate/hexane (1:6) Rf =0.34, FD-MS: M+ =311(313).

Workup

  1. temperatureis heated
  2. temperatureto reflux under argon
  3. temperatureunder reflux for a further 2 hours until the evolution of gas subsides
  4. customdoes not rise above 5° C
  5. temperatureAfter this, the mixture is slowly heated to 25° C.
  6. customExcess sodium hydride is cautiously destroyed with 1 ml of water before more water
  7. additionis added
  8. customThe phases are separated
  9. extractionthe aqueous phase is extracted again with tert-butyl methyl ether
  10. washThe combined organic phases are washed with brine
  11. dry with materialdried over sodium sulfate
  12. customevaporated
  13. distillationThe crude product is distilled at 0.1 mbar

Sources & evidence

ORD record
ord-c8774ffbd538427badf46dda3bf8057b
Source dataset
uspto-grants-1999_08
Patent number
US05935951

Reaction notes

Loading…