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product after washing by Et2O. The obtained crude product was
dissolved in CH2Cl2 (10 mL), and crystallized by the addition of Et2O
(20 mL), yielding the complex of RuIII(TPP)Cl [332.8 mg, 90%,
412 nm (Soret band)] as a dark solid. By following the similar
procedures, when DBU was applied instead of K2CO3, the same
RuIII(TPP)Cl complex was obtained (The UV-vis spectra of the
obtained RuIII(TPP)Cl was provided in Figure S2 of ESI).
carbamate salt (Entry 17), which was convinced by the in situ
high-pressure FT-IR spectroscopic analysis (See Figure S3 in ESI).
Herein, even the substitution reaction of 1,2-dichloroethane
with aniline was not ensued.
Conclusion
The three-component reaction of primary aliphatic amine, CO2
and 1,2-dichloroethane (or its derivative) was accomplished Acknowledgements
over RuCl3 ·3H2OÀ H2TPP catalytic system for the synthesis of N-
substituded-2-oxazolidinones in the yields of 71~91% ([Ru]=
This work was financially supported by the National Natural
Science Foundation of China (No. 21972045).
°
1 mol%, 2 equiv. K2CO3 as base, 100 C, 9~15 h). In this
synthesis protocol, the combination of stoichiometric activation
of CO2 by the involved aliphatic amine with the Ru(III)-porphyrin
catalysis towards 1,2-dichloroethane (or its analogue) coopera- Conflict of Interest
tively contributes to this successful three-component reaction,
which proves to be a novel strategy for CO2-utilization. The UV-
vis spectroscopic analysis convinced that the Ru(III)-porphyrin
catalyst was able to efficiently activate 1,2-dichloroethane into
an active electrophilic intermediate (A) via utilizing 1,2-dichloro-
ethane as the axial ligand of Ru(III)-porphyrin.
The authors declare no conflict of interest.
Keywords: Carbamate salt Cooperative catalysis
·
·
Oxazolidinones · Ru(III)-porphyrin catalyst · Transformation of
CO2
Experimental Section
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Reagents and analysis: The chemical reagents were purchased
from Shanghai Aladdin Chemical Reagent Co. Ltd. and Alfa Aesar
1
China, and used as received. The H and 13C NMR were recorded on
a Bruker Avance 500 spectrometer. Gas chromatography (GC) was
performed on a SHIMADZU-2014 equipped with a DM-Wax capillary
column (30 m×0.25 mm×0.25 μm). GC-mass spectrometry (GC-MS)
which equipped with a DB-Wax capillary column (30 m×0.25 mm×
0.25 μm) was recorded on an Agilent 6890 instrument equipped
with an Agilent 5973 mass selective detector. The UV-vis spectra
were recorded by the Shimadzu UV-2700 spectrometer. The FT-IR
spectra were recorded on using a Nicolet NEXUS 670 spectrometer.
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[10] Y. Hu, J.-L. Song, C. Xie, H.-R. Wu, T. Jiang, G.-Y. Yang, B.-X. Han, ACS
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2017, 7, 243–249.
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General procedures for three-component reaction of CO2,
aliphatic amine and 1,2-dihaloethane: In a typical experiment,
RuCl3 ·3H2O (0.02 mmol), ligands (0.02 mmol) and K2CO3 (2.0 mmol)
were added into 1,2-dichloroethane (3.0 mL) and the amine
(2.0 mmol). The obtained mixture in a 50 mL Teflon-lined stainless-
steel autoclave was sealed and pressured by CO2 (1.0 MPa). Then
°
the reaction mixture was stirred vigorously at 100 C for 9 h. Upon
completion, the autoclave was cooled down to room temperature
and slowly depressurized. The solution was analyzed by GC to
determine the conversion (n-dodecane as internal standard) and
the selectivity (normalization method), and the products were
further identified by GC-MS and 1H/13C NMR spectrometers.
Pseudo in situ UV-vis absorption spectroscopic characterization:
The UV-vis spectra were recorded by the Shimadzu UV-2700
spectrometer. The same samples used in 1H NMR spectroscopic
characterization were also applied herein. The reaction mixture
°
upon treating at 100 C for different time (3 h, 6 h, or 9 h)
respectively in the autoclave were diluted by 1,2-dichloroethane
required for the UV-vis detection (MeOH as reference).
Preparation of RuIII(TPP)Cl complex: H2TPP [307.5 mg, 0.5 mmol,
421 nm (Soret band)] dissolved in CH3OH (30 mL) was added with
RuCl3 ·3H2O (103.7 mg, 0.5 mmol) and K2CO3 (69.1 mg, 0.5 mmol).
°
The obtained mixture was stirred at 100 C for 30 min. Then the
cooled solution was concentrated under vacuum to give the crude
Chem Asian J. 2021, 16, 1–8
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