Abstract
The mechanism of N-methylformamide metathesis with dimethyl carbonate, which leads to the formation of N,O-dimethyl carbamate, is studied using the quantum-chemical B3LYP/6-311++G(df,p) approach. The reaction consists of three stages: the conversion of formamide to iminol; the adding of dimethyl carbonate at the azomethine bond of iminol; and decomposition of the resulting product into carbamate and methyl formate. The second stage limits the rate of interaction. All stages proceed through concerted cyclic transition state, and all of them are catalyzed efficiently by a monomer and a dimer of methanol.
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REFERENCES
M. Selva, C. A. Marque, and P. Tundo, Cazz. Chim. Ital. 123, 515 (1993).
S. P. Gupte, A. B. Shivarkar, and R. V. Chaudhari, Chem. Commun., No. 24, 2620 (2001).
A. B. Shivarkar, S. P. Gupte, and R. V. Chaudhari, J. Mol. Catal. A 223, 85 (2004).
X. Guo, J. Shang, J. Li, et al., Synthet. Commun. 41, 1102 (2011).
T. Duong, R. H. Prager, A. D. Ward, and D. I. B. Kerr, Aust. J. Chem. 29, 2651 (1976).
R. W. Mason, US Patent No. 6781010.
U. Romano and R. Tesei, US Patent No. 4100351.
N. Kébir, M. Benoit, C. Legrand, and F. Burel, Eur. Polym. J. 96, 87 (2017).
N. Kebir, M. Benoit, and F. Burel, Eur. Polym. J. 107, 155 (2018).
D. Wu, X. Fu, F. Xiao, J. Li, N. Zhao, W. Sun, and Y. Wei, Catal. Commun. 9, 680 (2008).
J. J. Gao, H. Q. Li, and Y. Zhang, Chin. Chem. Lett. 18, 149 (2007).
E. Gattiglia, F. Turturro, F. P. Lamantia, and A. Valenza, J. Appl. Polym. Sci. 46, 1887 (1992).
Transreactions in Condensation Polymers, Ed. by S. Fakirov (Wiley-VCH, Weimheim, 1999).
D. A. Costa, C. Marize, and F. Oliveira, Int. J. Polym. Mater. 51, 393 (2002).
Reactive Extrusion. Principles and Applications, Ed. by G. Beyer and Ch. Hopmann (Wiley-VCH, Weimheim, 2018).
H. Sardon, A. Pascual, D. Mecerreyes, et al., Macromolecules 48, 3153 (2015).
L. Maisonneuve, O. Lamarzelle, E. Rix, et al., Chem. Rev. 115, 12407 (2015).
J. Y. Simon, The Toxicology and Biochemistry of Insecticides (CRC, Boca Raton, FL, 2015).
A. K. Ghosh and M. Brindisi, J. Med. Chem. 58, 2895 (2015).
J. E. Cheong, M. Zaffagni, I. Chung, et al., Eur. J. Med. Chem. 144, 372 (2018).
F. Aricò and P. Tundo, Russ. Chem. Rev. 79, 479 (2010).
P. Wang, Sh. Liu, and Y. Deng, Chin. J. Chem. 35, 821 (2017).
L. Z. Pillon and L. A. Utracki, Polym. Eng. Sci. 24, 1300 (1984).
J.-Ch. Ho and K.-H. Wei, J. Polym. Sci., Part B 38, 2124 (2000).
F.-Ch. Pai, S.-M. Lai, and H. H. Chu, J. Appl. Polym. Sci. 130, 2563 (2013).
J. Gug and M. J. Sobkowicz, J. Appl. Polym. Sci. 133, 43350 (2016).
S. Fakirov, Prog. Polym. Sci. (2018). https://doi.org/10.1016/j.progpolymsci.2018.09.003
J.-X. Guo and J.-J. Ho, J. Phys. Chem. A 103, 6433 (1999).
P. E. Allegrettia, C. B. Milazzoa, E. A. Castrob, et al., J. Mol. Struct.: THEOCHEM 589–590, 161 (2002).
M. K. Hazra and T. Chakraborty, J. Phys. Chem. A 109, 7621 (2005).
D. Guzmán-Angel, R. Inostroza-Rivera, S. Gutiérrez-Oliva, et al., Theor. Chem. Acc. 135, 37 (2016).
R. M. Vichietti, A. B. F. da Silva, and R. L. A. Haiduke, Mol. Astrophys. 10, 1 (2018).
S. T. Gadge, A. Mishra, A. L. Gajengi, et al., RSC Adv. 4, 50271 (2014).
K. H. Bouhadir, L. Abramian, A. Ezzeddine, et al., Molecules 17, 13290 (2012).
E. Marsault, H. R. Hoveyda, M. L. Peterson, et al., J. Med. Chem. 49, 7190 (2006).
W.-Ch. Shieh, S. Dell, A. Bach, et al., Org. Chem. 68, 1954 (2003).
A. James, J. A. Cella, and S. W. Bacon, Org. Chem. 49, 1122 (1984).
A. W. Burgstahler, J. Am. Chem. Soc. 73, 3021 (1951).
H. Bredereck, G. Simchen, and E. Goknel, Angew. Chem., Int. Ed. Engl. 3, 704 (1964).
H. Ulrich and A. A. R. Sayigh, Angew. Chem., Int. Ed. Engl. 6, 844 (1966).
G.-Y. Yeap, A.-T. Mohammad, and H. Osman, Mol. Cryst. Liq. Cryst. 552, 177 (2012).
A.-T. Mohammad, G.-Y. Yeap, and H. Osman, J. Mol. Struct. 1087, 88 (2015).
I. A. Mohammed, M. Ahmed, R. Ikram, et al., Lat. Am. J. Pharm. 37, 540 (2018).
T. Tsuneda, Density Functional Theory in Quantum Chemistry (Springer, Tokyo, Heidelberg, New York, Dordrecht, London, 2014).
V. Sahni, Quantal Density Functional Theory (Springer, Berlin, Heidelberg, 2016).
A. D. Becke, J. Chem. Phys. 96, 2155 (1992).
A. D. Becke, J. Chem. Phys. 97, 9173 (1992).
A. D. Becke, J. Chem. Phys 98, 5648 (1993).
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, et al., Gaussian 09, Revision A.1 (Gaussian Inc., Wallingford CT, 2009).
S. K. Reddy and S. Balasubramanian, J. Phys. Chem. B 116, 14892 (2012).
L. Gontrani, O. Russina, and F. C. Marincola, J. Chem. Phys. 131, 244503 (2009).
D. Guzmán-Angel, R. Inostroza-Rivera, S. Gutiérrez-Oliva, et al., Theor. Chem. Acc. 135, 37 (2006).
M. K. Hazra and T. Chakraborty, J. Phys. Chem. A 109, 7621 (2005).
A. Ya. Samuilov, F. B. Balabanova, Ya. D. Samuilov, and A. I. Konovalov, Russ. J. Gen. Chem. 85, 1808 (2015).
R. Waterman, Organometallics 32, 7249 (2013).
H. Bauer, M. Alonso, Ch. Farber, et al., Nat. Catal. 1, 40 (2018).
S. Yadav, R. Dixit, K. Vanka, et al., Chem. Eur. J. 26, 1269 (2018).
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Samuilov, A.Y., Alekbaev, D.R. & Samuilov, Y.D. Catalytic Metathesis of N-Methylformamide with Dimethyl Carbonate by Alcohol Associates. Russ. J. Phys. Chem. 93, 2365–2372 (2019). https://doi.org/10.1134/S0036024419120240
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DOI: https://doi.org/10.1134/S0036024419120240