Ethyl Bromide → HCID 178442804, compound

HRID 2352527Notes

Reaction equation

HRID 2352527 reaction equation
[Mg].[CH2:2](Br)[CH3:3].[CH:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]>O1CCCC1>[C-:2]#[C-:3].[CH:5]#[C:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]

Participants

5

Reactant 3

HCID 6332Ethyl BromideHCID 129971-DecyneHCID 5462224Magnesium2×

Product 1

HCID 178442804HCID 178442804, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

19.35 g of magnesium (0.79 gramme-atom) and then 750 cm3 of anhydrous tetrahydrofuran (THF) are placed in a 2-liter round-bottomed flask equipped with a stirrer and an argon inlet. 90.25 g of ethyl bromide (1.15 equivalent) are then introduced dropwise so as to maintain the THF refluxing. When the addition is complete, this refluxing is maintained until the magnesium has been completely converted. 100 g of 1-decyne (0.72 mol) are then added dropwise at this temperature in the course of approximately half an hour, and the mixture is maintained refluxing for a further hour and a half after the addition is complete. 5.20 g of cuprous cyanide are then introduced and boiling is maintained for a further hour. To the 1-decyne acetylide thereby formed, 250 g of 1,4-dichloro-2-butyne, or 2.8 equivalents with respect to the decyne, are added at a temperature maintained at between 40° and 50° C. Boiling is maintained for 5 hours. The solvent is removed in a rotary evaporator. The oily mass obtained is cooled and stirred in the presence of 350 cm3 of water saturated with ammonium chloride, and then extracted 3 times with ether. The ether phase is washed twice with water, dried over magnesium sulphate and then concentrated at normal pressure, and the remaining ether is then removed under a pressure of 26.6×102Pa. The crude 1-chloro-2,5-tetradecadiyne is distilled at a temperature of between 118° C. and 125° C. under 2.6 Pa. In the final fractions at between 125° C. and 130° C. under 4 Pa, the remainder of the expected product is distilled mixed with 1-bromo-2,5-tetradecadiyne, which forms during the reaction by exchange of chlorine with bromine.

Workup

  1. customequipped with a stirrer and an argon inlet
  2. additionWhen the addition
  3. temperaturethe mixture is maintained
  4. temperaturerefluxing for a further hour
  5. additiona half after the addition
  6. temperatureboiling is maintained for a further hour

Sources & evidence

ORD record
ord-63a60249e7844ae599937cde08357209
Source dataset
uspto-grants-1989_10
Patent number
US04877789

Reaction notes

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