1-Butanol → dibutyl but-2-ynedioate

HRID 2373104Notes

Reaction equation

HRID 2373104 reaction equation
[C:1]([OH:8])(=[O:7])[C:2]#[C:3][C:4]([OH:6])=[O:5].[CH2:9](O)[CH2:10][CH2:11][CH3:12].S(=O)(=O)(O)O>>[C:2]([C:1]([O:8][CH2:1][CH2:2][CH2:3][CH3:4])=[O:7])#[C:3][C:4]([O:6][CH2:9][CH2:10][CH2:11][CH3:12])=[O:5]

Participants

4

Reactant 3

HCID 2631-ButanolHCID 3712-Butynedioic acidHCID 1118Sulfuric Acid

Product 1

HCID 305768dibutyl but-2-ynedioate

Procedure

First, dibutyl acetylenedicarboxylate was prepared. A mixture of 2-butynedioic acid (5.0 g, 44 mmol), n-butyl alcohol (162 g, 2.19 mol), and sulfuric acid (0.86 g, 9 mmol) was heated at reflux for 6 hours. The mixture was cooled to ambient, washed with 10% aqueous NaHCO3 then with brine, dried (Na2SO4), concentrated, and the resulting crude product distilled under reduced pressure (bp 65-70° C./0.08 mm). Dibutyl acetylenedicarboxylate was obtained as a colorless oil (8.5 g, 86% of theory). 1H NMR (CDCl3): δ 1.90 (t, 6H), 1.38 (m, 4H), 1.65 (m, 4H), 4.20 (t, 4H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 6 hours
  3. temperatureThe mixture was cooled to ambient,
  4. washwashed with 10% aqueous NaHCO3
  5. dry with materialwith brine, dried (Na2SO4)
  6. concentrationconcentrated
  7. distillationthe resulting crude product distilled under reduced pressure (bp 65-70° C./0.08 mm)
  8. customDibutyl acetylenedicarboxylate was obtained as a colorless oil (8.5 g, 86% of theory)

Sources & evidence

ORD record
ord-d5676a8bd38f49cfac9f350a49e7b110
Source dataset
uspto-grants-2008_12
Patent number
US07459263B2

Reaction notes

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