Acetic Acid → HCID 86740796, compound

HRID 280396Notes

Reaction equation

HRID 280396 reaction equation
S(Cl)(C)(=O)=O.[C:6]([OH:9])(=O)[CH3:7].[O:10]1[CH2:14][CH2:13][CH2:12][CH2:11]1>C#C.C#C.[Zn]>[CH:12]([C@@H:11]1[O:10][C@H:7]1[CH2:6][OH:9])=[C:13]=[CH:14][C:11]#[C:12][C:13]#[CH:14]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 8028TetrahydrofuranHCID 31297Methanesulfonyl chloride

Product 1

HCID 86740796HCID 86740796, compound

Reagents, catalysts & solvents 1

HCID 86740797HCID 86740797, compoundCatalyst

Conditions

Temperature
-78 °C

Procedure

In a separate flask, the mesylate of 6-[(tetrahydro-2H-pyran-2-yl)oxy]-4-hexen-1-yn-3-ol was prepared via the following procedure. To a stirred solution of 6-(tetrahydro-2H-pyran-2-yl)oxy]-4-hexen-1-yn-3-ol (98 mg, 0.5 mmole), anhydrous lithium bromide (43 mg, 0.5 mmole) and a few milligrams of 1,10-phenanthroline in 5 ml of tetrahydrofuran at -78° C. was added n-butyllithium dropwise until a brown color was obtained (ca. 0.5 mmole of n-butyllithium). The mixture was stirred for one-half hour whereupon mesyl chloride (38 μl, 0.5 mmole) was added dropwise. The brown color discharged to yellow. The solution was stirred for 10 minutes at -78° C. and was then added all at once (via short teflon cannula and argon pressure) to the above stirred -20° C. solution of zinc diacetylene. The resultant mixture was stirred at -20° C. for 15 minutes and was then acidified by the addition of a solution of acetic acid in tetrahydrofuran. The mixture was then concentrated to ca. 1/4 volume and 30 ml of a mixture of ether-hexane 1:1 was added with stirring whereupon a gum separated. The supernatant was then filtered through a pad of silica gel. The filtrate was concentrated to dryness and immediately redissolved in a few ml of ether-hexane 1:5 (some solid did not dissolve). This solution of crude product was then purified via flash chromatography (LPS-1 silica gel, ether-hexane 1:10) to afford pure title compound (30 mg). This allene was stored in solution in ether-hexane in the freezer.

Workup

  1. additionwas added dropwise
  2. concentrationThe mixture was then concentrated to ca. 1/4 volume and 30 ml of a mixture of ether-hexane 1:1
  3. additionwas added
  4. stirringwith stirring whereupon a gum
  5. customseparated
  6. filtrationThe supernatant was then filtered through a pad of silica gel
  7. concentrationThe filtrate was concentrated to dryness
  8. dissolutionimmediately redissolved in a few ml of ether-hexane 1:5 (some solid
  9. dissolutiondid not dissolve)
  10. customThis solution of crude product was then purified via flash chromatography (LPS-1 silica gel, ether-hexane 1:10)

Sources & evidence

ORD record
ord-14f61e24d52045b0980153e41488c184
Source dataset
uspto-grants-1986_05
Patent number
US04588828

Reaction notes

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