Water → 2(5H)-Furanone

HRID 1699464Notes

Reaction equation

HRID 1699464 reaction equation
C(N([CH2:6][CH3:7])CC)C.[OH2:8].[CH:9]#[CH:10].[C]=[O:12]>O1CCOCC1.C/C(/O)=C\C(C)=O.[C-]#[O+].[C-]#[O+].[Rh]>[O:8]1[CH2:7][CH:6]=[CH:10][C:9]1=[O:12].[C:9]1(=[O:12])[O:8][CH2:7][CH2:6][CH2:10]1

Participants

8

Reactant 4

HCID 962WaterHCID 6326Acetylene2×HCID 8471TriethylamineHCID 178418416HCID 178418416, compound

Product 2

HCID 7302Gamma-ButyrolactoneYield 24%HCID 103412(5H)-FuranoneYield 59%

Reagents, catalysts & solvents 2

HCID 10879749HCID 10879749, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

The initial charge was 672 mg (2.6 mmol) of Rh(CO)2acac, 2.25 g (22.3 mmol) of triethylamine and 32.8 g (1.8 mol) of water in 400 ml of dioxane. 8.2 l (0.31 mol) of acetylene were injected at room temperature with stirring to a pressure of 3.6 bar. The pressure was then raised to 200 bar with carbon monoxide. The reaction batch was heated to 120° C., raising the pressure to 248 bar, and subsequently stirred for 2 h. After cooling and reactor decompression, a sample was taken and analyzed by gas chromatography using the technique of the internal standard. Based on the amount of acetylene used, 59% of 2(5H)-furanone and 24% of butyrolactone had formed. 50 bar of hydrogen were then injected at room temperature and the reaction batch heated to 200° C. in the autoclave, raising the pressure to 89 bar. The pressure was then raised to 200 bar with hydrogen, which was followed by 1 h of stirring. After cooling and autoclave decompression the autoclave's effluent was filtered. The filtrate was found to contain only 1% of the rhodium used. The solid filter residue was reusable as catalyst. Following a distillative workup, butyrolactone was isolated in a yield of 81%, based on the amount of acetylene used.

Workup

  1. additionThe initial charge
  2. customwere injected at room temperature
  3. temperatureraising the pressure to 248 bar
  4. stirringsubsequently stirred for 2 h
  5. temperatureAfter cooling
  6. customreactor decompression, a sample was taken

Sources & evidence

ORD record
ord-9c4ed46e53114b4bac24e2289f35c2a7
Source dataset
uspto-grants-2002_02
Patent number
US06346629B1

Reaction notes

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