C([Mg]Br)C.[CH:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14].[Cl:15][CH2:16][C:17]#[C:18][CH2:19]Cl.[NH4+].[Cl-]>C1COCC1.[Cu]Cl>[Cl:15][CH2:16][C:17]#[C:18][CH2:19][C:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]38 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-decyne 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 286 mg of copper(I) chloride were added and the mixture was again heated under reflux for 1 hour. It was then cooled to between 40° C. and 50° C. and 12.5 g of 1,4-dichloro-2-butyne dissolved in 25 ml of anhydrous THF were added. The mixture was refluxed for 1 hour and then maintained under stirring for 15 h at room temperature before heating again under reflux for 2 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-tetradecadiyne (b.p.=111-114° C., 0.36 mbar) in the form of an orange-colored oil (yield 52.4%).
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