Ethyl Bromide → HCID 131717191, compound

HRID 1587115Notes

Reaction equation

HRID 1587115 reaction equation
C(Br)C.[Mg].[S:5]1[CH:9]=[CH:8][CH:7]=[C:6]1[C:10]#[CH:11].[Cl:12][CH2:13][C:14]([C:16]1([Cl:19])[CH2:18][CH2:17]1)=[O:15].[Cl-].[NH4+]>C(OCC)C>[Cl:12][CH2:13][C:14]([C:16]1([Cl:19])[CH2:18][CH2:17]1)([OH:15])[C:11]#[C:10][C:6]1[S:5][CH:9]=[CH:8][CH:7]=1

Participants

7

Reactant 5

HCID 6332Ethyl BromideHCID 25517Ammonium ChlorideHCID 52462582-EthynylthiopheneHCID 5462224MagnesiumHCID 11062580Ethanone, 2-chloro-1-(1-chlorocyclopropyl)-

Product 1

HCID 131717191HCID 131717191, compoundYield 97.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

22.2 g (0.203 mole) of ethyl bromide are slowly added to 4.9 g (0.203 mole) of magnesium turnings in 100 ml of diethyl ether. After completion of the addition, the reaction mixture is heated under reflux for 30 minutes and then cooled to room temperature, and a solution of 20 g (0.185 mole) of 2-thienylethine in 50 ml of diethyl ether is subsequently added dropwise with stirring. The mixture is heated under reflux for 1 hour and again cooled to room temperature. 28.3 g (0.185 mole) of 1-chloro-cyclopropyl chloromethyl ketone are added dropwise with stirring and the mixture is then heated under reflux for a further 2 hours. After cooling to room temperature, the reaction mixture is poured into a saturated aqueous ammonium chloride solution and the mixture is extracted three times with diethyl ether. The combined organic phases are washed once with water, dried over sodium sulphate and concentrated under reduced pressure. 47.0 g (97% of theory) of 1-chloro-2-(1-chlorocyclopropyl)-4-(thiophen-2-yl)-but-3-in-2-ol are obtained in this way in the form of an oil which is reacted further without additional purification.

Workup

  1. additionAfter completion of the addition
  2. temperaturethe reaction mixture is heated
  3. temperatureunder reflux for 30 minutes
  4. temperatureThe mixture is heated
  5. temperatureunder reflux for 1 hour
  6. temperatureagain cooled to room temperature
  7. stirringwith stirring
  8. temperaturethe mixture is then heated
  9. temperatureunder reflux for a further 2 hours
  10. temperatureAfter cooling to room temperature
  11. extractionthe mixture is extracted three times with diethyl ether
  12. washThe combined organic phases are washed once with water
  13. dry with materialdried over sodium sulphate
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3f75b36a555e4f9da2f9f62e3b79a002
Source dataset
uspto-grants-1993_06
Patent number
US05216180

Reaction notes

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