Ion ic Liqu id a s a n Efficien t P r om otin g Med iu m for F ixa tion of
CO2: Clea n Syn th esis of r-Meth ylen e Cyclic Ca r bon a tes fr om CO2
a n d P r op a r gyl Alcoh ols Ca ta lyzed by Meta l Sa lts u n d er Mild
Con d ition s
Yanlong Gu, Feng Shi, and Youquan Deng*
Center for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou 730000, China
ydeng@ns.lzb.ac.cn
Received August 1, 2003
Reactions of propargylic alcohols with CO2 in a [BMIm][PhSO3]/CuCl catalytic system to produce
the corresponding R-methylene cyclic carbonates were conducted with high yields. Mild reaction
conditions, enhanced rates, improved yields, and recyclable ionic liquid catalyst systems are the
remarkable features exhibited in this process. Furthermore, the use of large amounts of tertiary
amines as well as nitrogen-containing organic solvent as employed in previously studies was avoided.
In tr od u ction
5.0 MPa) was unavoidable in order to achieve good
results. Additionally, this reaction usually proceeded in
volatile organic solvents, such as DMF or THF. Therefore,
it is necessary to develop a mild, clean, and efficient
method for the synthesis of alkylidene carbonates from
carbon dioxide.
Development of green processes based on chemical
fixation of carbon dioxide (CO2) has received a great deal
of interest in recent years because carbon dioxide could
be used as a safe and cheap C1 building block to produce
useful organic compounds.1 A large number of studies
have been devoted to the fixation of CO2 for synthesis of
alkylidene carbonates, which are usually obtained from
reactions between CO2 and propargylic alcohols catalyzed
over various metal complexes2 including Cu, Co, Ru, and
Pd or in the presence of large amounts of tertiary
phosphines,3 because the five-membered ring alkylidene
carbonates are important intermediates for many organic
syntheses.4 However, the use of tertiary amines, large
amounts of organic solvents, and high CO2 pressure (ca.
Room temperature ionic liquids, especially those based
on the 1-alkyl-3-methylimidazolium cations, have shown
great promise as an attractive alternative to conventional
organic solvents, and much attention has been currently
focused on organic reactions promoted by ionic liquids.5
They are nonvolatile, recyclable, nonexplosive, easily
operable, and thermally robust.6 Recently, it was shown
that these novel materials had good dissolvability for
many gaseous substrates, such as CO2,7 which suggests
that they should be an effective medium for fixation of
carbon dioxide. In our previous work, it was found that
an ionic liquid could be an effective catalyst system for
cycloaddition of CO2 with propylene oxide8 and direct
synthesis of symmetrical dialkylurea from CO2 and
aliphatic amines.9 With our continuous research in the
fixation of CO2 using ionic liquid catalyst system, here,
* Corresponding author. Fax: +86-931-8277088.
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10.1021/jo0351365 CCC: $27.50 © 2004 American Chemical Society
Published on Web 12/25/2003
J . Org. Chem. 2004, 69, 391-394
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