First author et al.
Report
Fig. 7. The process of hydro-esterification of MF and ethylene.
the reacted liquid are tested by GC chromatogram (in Fig. S8).
Acknowledgements
Conclusions
This work was supported by the National Key R&D Program
of China (2017YFA0206802, 2017YFA0700103), the National
Natural Science Foundation of China (91545201, 91645116),
the Programs of the Chinese Academy of Sciences
(ZDRW-CN-2016-1, QYZDJ-SSW-SLH028), and the Natural
Science Foundation of Fujian Province (2018J06005), Youth
Innovation Promotion Association CAS, China Postdoctoral
Science Foundation (2016LH0018).
In this work, a high-performance RuCl3-[PPN]Cl-Et4NI catalyst
system is first reported for this reaction. The conversion of MF
and the selectivity to MP reach to 93.9% and 90.9%, respectively,
at a mild reaction condition (165 °C, 2.5 MPa) by adopting DMF as
solvent. However, promoters ([PPN]Cl and Et4NI) are complex
organic compounds, which increase the difficulty of studying
reaction mechanism and further industrialization. Therefore, we
further develop a high-performance inorganic catalyst system
(RuCl3-NaI). It is worth highlighting that the conversion of MF and
selectivity to MP is 88.8% and 97.6%, respectively. And the yield
of MP (86.7%) is comparable with that of RuCl3-[PPN]Cl-Et4NI
catalyst system (85.4%). NaI, as a promoter, may inhibit the
decomposition of MF and be conducive to the formation of MP.
Compared with promoters containing organic group, using
inorganic promoter (NaI) is beneficial to the purification and
separation of products. We hope that this work will re-arouse the
attention to the reaction of MF and ethylene to MP.
References
[1] An, J.; Wang, Y.; Lu, J.; Zhang, J.; Zhang, Z.; Xu, S.; Liu, X.; Zhang, T.;
Gocyla, M.; Heggen, M.; Dunin-Borkowski, R. E.; Fornasiero, P.;
Wang, F. Acid-Promoter-Free Ethylene Methoxycarbonylation
over Ru Clusters/Ceria: the Catalysis of Interfacial Lewis Acid-Base
Pair. J. Am. Chem. Soc., 2018, 140, 4172–4181.
Experimental
Materials
[2] Mahboub, M. J. D.; Dubois, J. L.; Cavani, F.; Rostamizadeh, M.;
Patience, G. S. Catalysis for the synthesis of methacrylic acid and
methyl methacrylate. Chem. Soc. Rev., 2018, 47, 7703–7738.
[3] Isnard, P.; Denise, B.; Sneeden, R. P. A. Transition Metal Catalyzed
Interaction of Ethylene with Alkyl Formate. J. Organomet. Chem.,
1983, 256, 135–139.
Ruthenium trichloride (RuCl3, 99.5%), Tetraethylammonium
iodide (Et4NI, 99%), Bis(triphenylphosphine)iminium chloride
([PPN]Cl, 98%), Sodium chloride (NaCl, 99%), Sodium iodide (NaI,
99%), N,N-Dimethylformamide (DMF, 99.9%), n-Butanol (99.5%),
Methylbenzene (99%), N,N-Diethylformamide (DEF, 99%),
Formamide (99%), N-Methylformamide (NMF, 99%), Morpholine
(99%), N,N-Dimethylacetamide (DMA, 99%). All above chemicals
are purchased from Adamas-beta Co. Ltd.. MF (99%;
Sigma-Aldrich Co. Ltd.), Ethylene (99.9%; Dalian Special Gases Co.
Ltd), CO (99.99%; Dalian Special Gases Co. Ltd). All the chemicals
were used as received without further purification.
[4] Clegg, W.; Eastham, G. R.; Elsegood, M. R. J.; Tooze, R. P.; Wang, X.
L.; Whiston, K. Highly active and selective catalysts for the
production of methyl propanoate via the methoxycarbonylation of
ethene. Chem. Commun. 1999, 18, 1877–1878.
Synthesis of MP from MF and ethylene
The reaction equation is shown below:
HCOOCH3 + CH2 = CH2 → C2H5COOCH3
[5] Sugiyama, S.; Bando, T.; Tanaka, H.; Nakagawa, K.; Sotowa, K. I.;
Katou, Y.; Mori, T.; Yasukawa, T.; Ninomiya, W. Direct Oxidative
Esterification of Propionaldehyde to Methyl Propionate Using
Heavy-metal-free Palladium Catalysts under Pressurized Oxygen. J.
Jpn. Petrol. Inst., 2011, 54, 380–384.
All reactions were carried out in stainless steel autoclaves (25
mL inner volume). Evaluation process of catalyst is as follows.
Firstly, the corresponding DMF, MF, RuCl3 and promoters were
added in the reactor and then sealed it. Secondly, ethylene was
blown into the reactor several times to replace air. Then, 2.5 MPa
ethylene was introduced into the reactor, and heated the
autoclave under magnetic stirring. After reaction, the magnetic
stirring was stopped and it was cooled to room temperature. The
pure MP is obtained by vacuum distillation of products. The 1H
NMR spectra of MP is shown in Fig. S11.
The composition of liquid products was analyzed by a
GC-2014 gas chromatograph (Shimadzu) equipped with a flame
ionization detector (FID). The capillary column connected to the
FID is composed with AE.FFAP fixation solution (50 m × 0.15 mm ×
0.5 μm). Standard working curve method was adopted to achieve
quantification in this work. The quantitative details were in part 7
of SI. In RuCl3-NaI catalyst system, the contained substances in
[6] Williams, B. R. J.; Gabriel, A.; Andrews, R. C. the Relation Between
the Hydrolysis Equilibrium Constant of Esters and the strengths of
the Corresponding Acids. J. Am. Chem. Soc., 1928, 50, 1267–1271.
[7] Diao, Y.; Yan, R.; Zhang, S.; Yang, P.; Li, Z.; Wang, L.; Dong, H. Effects
of Pb and Mg doping in Al2O3-supported Pd catalyst on direct
oxidative esterification of aldehydes with alcohols to esters. J.
Mol. Catal., 2009, 303, 35–42.
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Chin. J. Chem. 2019, 37, XXX-XXX
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