1,4-Dichloro-2-butyne → HCID 18673378, compound

HRID 1635779Notes

Reaction equation

HRID 1635779 reaction equation
C([Mg]Br)C.[CH:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].[Cl:16][CH2:17][C:18]#[C:19][CH2:20]Cl.[NH4+].[Cl-]>C1COCC1.[Cu]Cl>[Cl:16][CH2:17][C:18]#[C:19][CH2:20][C:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

7

Reactant 4

HCID 131821,4-Dichloro-2-butyneHCID 25517Ammonium ChlorideHCID 752491-UndecyneHCID 178418443HCID 178418443, compound

Product 1

HCID 18673378HCID 18673378, compoundYield 37.8%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

34.5 ml of a 1M solution of ethyl magnesium bromide in THF were added dropwise, at room temperature, to a solution of 5 grams of 1-undecyne in 15 ml of anhydrous THF, under an inert atmosphere with the addition complete, the mixture was maintained under stirring for 30 min at room temperature and then heated under reflux for 1 h 30 min. The mixture was cooled to room temperature and then 260 mg of copper(I) chloride were added and the mixture was again heated under reflux for 1 hour. The mixture was then cooled to room temperature and 11.3 g of 1,4-dichloro-2-butyne were added fairly rapidly. The mixture was refluxed for 1 h 30 min and then maintained under stirring for 15 h at room temperature before heating again under reflux for 3 h. The reaction medium was then cooled to 4° C. and hydrolyzed with care with a saturated aqueous solution of NH4Cl. The medium was then extracted 3 times with diethyl ether and the combined organic phases were washed 3 times with water and then with a saturated aqueous solution of NaCl before being dried over Na2SO4, filtered and concentrated under vacuum in a rotary evaporator. The oily residue containing 1,4-dichloro-2-butyne in excess was purified by distillation under reduced pressure to give 1-chloro-2,5-pentadecadiyne in the form of a colorless oil with a yield of 37.8%.

Workup

  1. temperaturewas maintained
  2. temperatureheated
  3. temperatureunder reflux for 1 h 30 min
  4. temperatureThe mixture was cooled to room temperature
  5. temperaturethe mixture was again heated
  6. temperatureunder reflux for 1 hour
  7. temperatureThe mixture was then cooled to room temperature
  8. temperatureThe mixture was refluxed for 1 h 30 min
  9. temperaturemaintained
  10. stirringunder stirring for 15 h at room temperature
  11. temperaturebefore heating again
  12. temperatureunder reflux for 3 h
  13. extractionThe medium was then extracted 3 times with diethyl ether
  14. washthe combined organic phases were washed 3 times with water
  15. dry with materialwith a saturated aqueous solution of NaCl before being dried over Na2SO4
  16. filtrationfiltered
  17. concentrationconcentrated under vacuum in a rotary evaporator
  18. additionThe oily residue containing 1,4-dichloro-2-butyne
  19. distillationin excess was purified by distillation under reduced pressure

Sources & evidence

ORD record
ord-a6d3dabcf8394ee89298ace712ead8c8
Source dataset
uspto-grants-2003_01
Patent number
US06511670B1

Reaction notes

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