Propargyl alcohol → HCID 14152343, compound

HRID 622860Notes

Reaction equation

HRID 622860 reaction equation
[Ar].N.[Li].[CH2:4]([OH:7])[C:5]#[CH:6].Br[CH2:9][CH2:10][CH2:11][CH2:12][CH:13]=[CH2:14].[Cl-].[NH4+]>O1CCCC1>[CH2:4]([OH:7])/[CH:5]=[CH:6]/[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]=[CH2:9]

Participants

7

Reactant 5

HCID 7859Propargyl alcoholHCID 25517Ammonium ChlorideHCID 759066-Bromo-1-hexeneHCID 3028194Lithium2×HCID 22052841HCID 22052841, compound

Product 1

HCID 14152343HCID 14152343, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

100 ml liquid ammonia and a catalytic amount of ferric nitrate (5 mg) are put into a 250 ml three-neck flask which is provided with an agitator, dry-ice condenser, dropping funnel with pressure compensation and with argon/ammonia flushing. 1.88 g (0.268M) lithium is added in portions to this mixture in such a manner that the blue color disappears between the additions. 7.21 g (7.49 ml, 0.129M) propargyl alcohol is added to the reaction mixture in 20 ml dry tetrahydrofuran during 25 minutes and the mixture is allowed to react for 1.5 hours during reflux after the addition. Subsequently, 14.0 g (10.86 ml, 85.8 mM) 1-bromo-5-hexene in 30 ml dry tetrahydrofuran is added over 30 minutes and the mixture is again allowed to react under reflux for 2.5 hours. Then, 2.05 g (0.298M) lithium is added in portions to the reaction mixture and the mixture is allowed to react one more hour. Subsequently, ammonium chloride is added in such an amount that the blue color of the reaction solution disappears and the main amount of the ammonia can evaporate. The reaction mixture is subsequently put in 20 g of ice and the mixture is allowed to warm up overnight to 25° C. The reaction mixture is extracted with ether and dried over magnesium sulfate. After the solvent has been drawn off, 9.3 g (66.4 mM) E-nona-2,8-diene-1-ol is obtained by bulb tube distillation of the residue at 105° C./0.5 mm pressure. This corresponds to a yield of 78%.

Workup

  1. customto react for 1.5 hours
  2. temperatureduring reflux
  3. additionafter the addition
  4. customto react
  5. temperatureunder reflux for 2.5 hours
  6. customto react one more hour
  7. customthe main amount of the ammonia can evaporate
  8. temperatureto warm up overnight to 25° C
  9. extractionThe reaction mixture is extracted with ether
  10. dry with materialdried over magnesium sulfate

Sources & evidence

ORD record
ord-7044dc4cb0234aa99cbba61916e39730
Source dataset
uspto-grants-1988_09
Patent number
US04772727

Reaction notes

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