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Green Chemistry
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(30-80 °C) for a certain reaction time. Upon completion, the reactor was
flushed with tap water until cooling down to ambient temperature.
Finally, HCOOH could be liberated by following two post-treatment
methods, including: (1) after release of CO2, 2 mL hydrochloric acid
aqueous solution (0.3 M) or 3% acetic acid aqueous solution was added,
followed by heating at 30 °C for 0.5 h; (2) without release of CO2, in situ
injection of 1 mL H2O, followed by heating at 100 °C for 15 min. Along
with liquid HCOOH, phenylsilanetriol was obtained as white precipitate.
Notes and references
DOI: 10.1039/D0GC02142C
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Synthesis of N-containing benzoheterocyclic compounds
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For the synthesis of benzimidazoles, benzothiazole or benzoxazole,
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Product analysis
For determining the concentration of HCOOH after reaction, the
resulting mixture was transferred to a volumetric flask (25 mL) with
addition of water to gain a constant volume, which was then analyzed
quantitatively by HPLC (Agilent 1260) based on the standard curve
[HCOOH yield = (mole of HCOOH) / (mole of used total H-) × 100%].
Representative HPLC chromatogram of standard HCOOH aqueous
solution (Figure S5) and HCOOH standard curve (Figure S6) are supplied.
Regarding the commercially available N-containing benzoheterocyclics,
their concentrations were determined by GC (Agilent 7890B) and GC-
MS (Agilent 6890N GC/5973 MS) after dilution with 5 mL methanol
using 10 mg naphthalene as the internal standard (the product yield
was calculated relative to the used total H-).
For both cases, 1H NMR (diluted with DMSO-d6) was used to
quantitatively analyze unpurified products in the reaction mixtures
using 1,3,5-trimethoxybenzene as the internal standard. For the
structural identification of products, HRMS (ESI) analysis was measured
on a Q Exactive LC-MS/MS (Thermo Scientific) instrument. 1H and 13C
NMR analysis were recorded in DMSO-d6 on Bruker NMR spectrometers
at 400 MHz and 101 MHz respectively, JOEL ECX-500M spectrometers
at 500 MHz and 125 MHz using tetramethylsilane (TMS) as the internal
standard. All the experiments were repeated thrice, and the average
results are presented.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
We wish to thank the financial support from the National Natural
Science Foundation of China (21666008, 21908033, 21576059), Fok
Ying-Tong Education Foundation (161030), Guizhou Science
&
Technology Foundation ([2018]1037), Key Technologies R&D Program
of China (2014BAD23B01), and Program of Introducing Talents of
Discipline to Universities of China (111 Program, D20023). S.S. thanks
Department of Biotechnology (Government of India), New Delhi, India.
We also acknowledge the Computer Network Information Center of the
Chinese Academy of Sciences for performing theoretical calculations.
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