Ammonium Chloride → 1-Chloro-14-methyl-nonadeca-7,10-diyn-13-ene

HRID 1606676Notes

Reaction equation

HRID 1606676 reaction equation
C[Mg]Br.[Cl:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]#[CH:12].Br[CH2:14][C:15]#[C:16][CH2:17][CH:18]=[C:19]([CH3:25])[CH2:20][CH2:21][CH2:22][CH2:23][CH3:24].[Cl-].[NH4+]>CCOCC.O1CCCC1>[Cl:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]#[C:12][CH2:14][C:15]#[C:16][CH2:17][CH:18]=[C:19]([CH3:25])[CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 903601-Octyne, 8-chloro-HCID 540103301-Bromo-6-methylundec-2-yn-5-eneHCID 178418573HCID 178418573, compound

Product 1

HCID 536494751-Chloro-14-methyl-nonadeca-7,10-diyn-13-ene

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To 21 ml. of 3M ethereal methyl magnesium bromide in 47.5 ml. of dry tetrahydrofuran under nitrogen was added 9.2 g. of 1-chloro-7-octyne in 15 ml. of tetrahydrofuran. The mixture was heated under reflux for 30 min., then was allowed to cool to room temperature during another 30 minutes after which 365 mg. of cuprous chloride was added. The mixture was heated under reflux for 20 min., then a solution of 14 g. of 1-bromo-6-methyl-undec-2-yn-5-ene in 12.9 ml. of tetrahydrofuran was added. The mixture was heated under reflux for 10 hrs. then cooled in an ice bath and 250 ml. saturated aqueous ammonium chloride was added. Ether was added and the mixture was filtered through Celite (diatomaceous earth filter ald) and separated. The thus obtained ether layer was washed with saturated aqueous sodium chloride, dried with magnesium sulfate, and evaporated. The thus obtained residue was distilled through a rocking short-path distillation apparatus, collecting 11.5 g. of a mixture comprising 1-chloro-14-methylnonadeca-7,10-dlyn-13-ene at a bath temperature of 180°-190°/0.005 mm.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 30 min.
  3. temperatureThe mixture was heated
  4. temperatureunder reflux for 20 min.
  5. temperatureThe mixture was heated
  6. temperatureunder reflux for 10 hrs
  7. temperaturethen cooled in an ice bath
  8. filtrationthe mixture was filtered through Celite (diatomaceous earth filter ald)
  9. customseparated
  10. washThe thus obtained ether layer was washed with saturated aqueous sodium chloride
  11. dry with materialdried with magnesium sulfate
  12. customevaporated
  13. distillationThe thus obtained residue was distilled through a rocking short-path distillation apparatus
  14. customcollecting 11.5 g
  15. customtemperature of 180°-190°/0.005 mm

Sources & evidence

ORD record
ord-3f0e9d7706ed464cad9b18604a06fab2
Source dataset
uspto-grants-1976_04
Patent number
US03953499

Reaction notes

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