Ammonium Chloride → (E)-4-methyl-3,5-dioxa-7-octadecen-9,12-diyne

HRID 1106006Notes

Reaction equation

HRID 1106006 reaction equation
C([Mg]Br)C.[CH3:5][CH:6]([O:10][CH2:11]/[CH:12]=[CH:13]/[C:14]#[CH:15])[O:7][CH2:8][CH3:9].Br[CH2:17][C:18]#[C:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24].[Cl-].[NH4+]>O1CCCC1>[CH3:5][CH:6]([O:10][CH2:11]/[CH:12]=[CH:13]/[C:14]#[C:15][CH2:17][C:18]#[C:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[O:7][CH2:8][CH3:9]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 27570871-Bromo-2-octyneHCID 12821656(E)-4-methyl-3,5-dioxa-7-decen-9-yneHCID 178418443HCID 178418443, compound

Product 1

HCID 12821657(E)-4-methyl-3,5-dioxa-7-octadecen-9,12-diyne

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of ethyl magnesium bromide in tetrahydrofuran (47 mL, 1.17 M) was treated dropwise with a solution of (E)-4-methyl-3,5-dioxa-7-decen-9-yne (7.7 g) in tetrahydrofuran (10 mL). After complete addition, the mixture was heated at 60° for 45 min, cooled to room temperature, treated with anhydrous cuprous chloride (0.35 g, dried at 145° at 0.05 mmHg for 16 hours) and stirred for 10 min. The 1-bromo-2-octyne (7.23 g) in tetrahydrofuran (10 mL) was added dropwise to the above mixture (mild exothermic reaction) and after complete addition the resulting mixture was heated for 45 min at 60° C. After this time, the contents were cooled to room temperature, poured onto saturated aqueous ammonium chloride solution and extracted with ether. The combined ether extracts were washed with brine, dried (MgSO4) and concentrated. The residue was purified by liquid chromatography (two columns, 3% by volume ethyl acetate in 97% by volume hexane) to yield the product (E)-4-methyl-3,5-dioxa-7-octadecen-9,12-diyne

Workup

  1. additionAfter complete addition
  2. temperaturethe mixture was heated at 60° for 45 min
  3. additionafter complete addition the resulting mixture
  4. temperaturewas heated for 45 min at 60° C
  5. temperatureAfter this time, the contents were cooled to room temperature
  6. extractionextracted with ether
  7. washThe combined ether extracts were washed with brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customThe residue was purified by liquid chromatography (two columns, 3% by volume ethyl acetate in 97% by volume hexane)

Sources & evidence

ORD record
ord-e8692df58ebf42428deb26e771aab419
Source dataset
uspto-grants-1982_01
Patent number
US04311645

Reaction notes

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