Dimethyl acetylenedicarboxylate → HCID 19101927, compound

HRID 1974660Notes

Reaction equation

HRID 1974660 reaction equation
C([C:5]#[C:6][CH2:7][O:8][CH2:9][C:10]#[C:11][C:12]#CCC)#CCC.[CH3:16][O:17][C:18]([C:20]#[C:21][C:22]([O:24][CH3:25])=[O:23])=[O:19]>C1(C)C=CC=CC=1>[CH2:7]1[C:6]2[CH:5]=[C:21]([C:22]([O:24][CH3:25])=[O:23])[C:20]([C:18]([O:17][CH3:16])=[O:19])=[CH:12][C:11]=2[CH2:10][CH2:9][O:8]1

Participants

4

Reactant 2

HCID 12980Dimethyl acetylenedicarboxylateHCID 86747550HCID 86747550, compound

Product 1

HCID 19101927HCID 19101927, compoundYield 19.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
105 °C

Procedure

A mixture of 3-butynyl-2-propynyl ether (37.2 g, 0.344 mol), dimethylacetylenedicarboxylate (48.9 g, 0.344 mol) and toluene is divided into 2 portions and transferred to 2 addition funnels connected to the reaction vessel. The apparatus is fitted with a condenser and evacuated 4 times with a Firestone valve and nitrogen. The cobalt catalyst is added in equal amounts to each addition funnel. The reaction vessel which contains approximately 2L toluene is heated to 105° C. under a nitrogen atmosphere with stirring. The contents of the addition funnels are added dropwise at equivalent rates, at 105° C., over a 4 hour period. The reaction mixture is stirred overnight at 100° C. under a heat lamp (Visible light), cooled to room temperature and filtered through diatomaceous earth. The filtrate is concentrated in vacuo to a brown oil, which is flash chromatographed (silica gel, 95% hexane:ether acetate eluent) to afford the title product as a pale orange solid (16.5 g, 19.2%) identified by NMR analysis.

Workup

  1. additiontransferred to 2 addition funnels
  2. customThe apparatus is fitted with a condenser
  3. customevacuated 4 times with a Firestone valve and nitrogen
  4. additionThe cobalt catalyst is added in equal amounts to each addition funnel
  5. additionThe contents of the addition funnels are added dropwise at equivalent rates, at 105° C., over a 4 hour period
  6. stirringThe reaction mixture is stirred overnight at 100° C. under a heat lamp (Visible light)
  7. temperaturecooled to room temperature
  8. filtrationfiltered through diatomaceous earth
  9. concentrationThe filtrate is concentrated in vacuo to a brown oil, which
  10. customchromatographed (silica gel, 95% hexane:ether acetate eluent)

Sources & evidence

ORD record
ord-a9263c43078d41dfaa22af0820cc82de
Source dataset
uspto-grants-1994_02
Patent number
US05283335

Reaction notes

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