Behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate
https://doi.org/10.32362/2410-6593-2022-17-5-377-383
Abstract
Objectives. To study the patterns of behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate.
Methods. The study employed infrared and nuclear magnetic resonance spectroscopy, as well as elemental analysis.
Results. The formation of mixtures of tautomeric forms of silicon-containing urea—N-(trimethylsilyl) morpholine-4-carboxamide and trimethylsilylmorpholine-4-carboximidoate—was established.
Conclusions. It is shown that the composition and structure of the resulting products are determined both by the presence of a morpholine substituent at the nitrogen atom and by the type of isocyanate used. Unlike the trimethylsilyl derivative of morpholine, morpholine itself reacts with trimethylsilyl isocyanate to form a mixture of tautomeric forms.
About the Authors
L. O. BelovaRussian Federation
Liya O. Belova, Dr. Sci. (Chem.), Professor, K.A. Andrianov Department of Chemistry and Technology of Organoelement Compounds, M.V. Lomonosov Institute of Fine Chemical Technologies
86, Vernadskogo pr., Moscow, 119571
Scopus Author ID 7102282244
RSCI SPIN-code 3499-7697
N. A. Golub
Russian Federation
Nataliya A. Golub, Cand. Sci. (Chem.) Associate Professor, K.A. Andrianov Department of Chemistry and Technology of Organoelement Compounds, M.V. Lomonosov Institute of Fine Chemical Technologies
86, Vernadskogo pr., Moscow, 119571
Scopus Author ID 56084643600
RSCI SPIN-code 4240-3509
M. V. Pletneva
Russian Federation
Mariya V. Pletneva, Cand. Sci. (Chem.) Associate Professor, K.A. Andrianov Department of Chemistry and Technology of Organoelement Compounds, M.V. Lomonosov Institute of Fine Chemical Technologies
86, Vernadskogo pr., Moscow, 119571
Scopus Author ID 37104888400
RSCI SPIN-code 9399-0150
N. I. Kirilina
Russian Federation
Nadezhda I. Kirilina, Cand. Sci. (Chem.), Leading Engineer
38, Entuziastov shosse, Moscow, 111123
Scopus Author ID 57193056863
RSCI SPIN-code 4549-8907
A. D. Kirilin
Russian Federation
Alexey D. Kirilin, Dr. Sci. (Chem.), Professor, Head of the K.A. Andrianov Department of Chemistry and Technology of Organoelement Compounds, M.V. Lomonosov Institute of Fine Chemical Technologies
86, Vernadskogo pr., Moscow, 119571
Scopus Author ID 6603604447
ResearcherID О-9744-215
RSCI SPIN-code 5500-5030
References
1. Rakhlin V.I., Tsyrendorzhieva I.P., Sysoev S.V., Rumyantsev Yu.M., Maslova O.V., Kosinova M.L. 4-(Trimethylsilyl)morpholine: synthesis, characterization, and prospects of use in film deposition processes. Izvestiya Akademii Nauk. Seriya Khimicheskaya. 2017;(12):2283–2289 (in Russ.).
2. Yoshida K., Liu Q., Yasue R., Wada S., Kimura R., Konishi T., Ogasawara M. Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis. ACS Catalysis. 2020;10(1):292–301. https://doi.org/10.1021/acscatal.9b04438
3. Zhong W., Xu W., Yang Q., Kato T., Liu Y., Maruoka K. A new approach for the copper-catalyzed functionalization of alkyl hydroperoxides with organosilicon compounds via in-situ-generated alkylsilyl peroxides. Tetrahedron. 2022;112:132627. https://doi.org/10.1016/j.tet.2021.132627
4. Zasukha S., Khairulin A., Shermolovich Y. The reactions of N-trimethylsilyl substituted ethers of α- and β-amino acids with sulfur tetrafluoride and morpholinosulfur trifluoride. J. Sulfur Chem. 2021;42(5):477–489. https://doi.org/10.1080/17415993.2021.1912045
5. Yang J., Shkrob I., Liu K., Connell J., Dietz-Rado N.L., Zhang Z., Liao C. 4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries. J. Electrochem. Soc. 2020;167(7):070533. https://doi.org/10.1149/1945-7111/ab7a9e
6. Herbig M., Kroke E. Low cost apparatus for rapid boiling point determination of small air sensitive samples under inert atmosphere. Thermochimica Acta. 2017;654:81–84. https://doi.org/10.1016/j.tca.2017.05.005
7. Herbig M., Böhme U., Kroke E. Insertion of CO2 and related heteroallenes into the Si-N-bond of methyl(N-morpholino)silanes. Inorg. Chim. Acta. 2018;73:20–28. https://doi.org/10.1016/j.ica.2017.12.020
8. Jahn U.A., Schroth W. Novel and simple method for the preparation of imivium salts. Tetrahedron Lett. 1993;34(37):5863–5866. https://doi.org/10.1016/S0040-4039(00)73799-3
9. Sinitsa A.D., Parkhomenko N.A., Stukalo E.A. Reactions of trimethylsilylamines with α-substituted alkyl isocyanates. Zhurnal Obshchei Khimii. 1977;47(9):2077–2081 (in Russ.).
10. Belova L.O., Golub N.A., Storozhenko P.A., Kirilin A.D. Unusual Behavior of Nitrogen-Containing Organosilicon Compounds in the Reactions with Isocyanates. Russ. J. Gen. Chem. 2021;91(5):820–827. https://doi.org/10.1134/S1070363221050108
11. Original Russian Text: Kozyukov V.P., Sheludyakov V.D., Mironov V.F. Silicon-containing isocyanates. Uspekhi Khimii. 1973;42(8):1451–1480 (in Russ.).
12. Klebe J.F., Bush J.B., Lyon, J.E. The Addition of Silylamines and Silazanes to Isocyanates J. Am. Chem. Soc. 1964;86(20):4400–4406. https://doi.org/10.1021/ja01074a035
Supplementary files
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1. IR spectrum of trimethylsilylmorpholine-4-carboxyimidoate 6 and N-(trimethylsilyl)morpholine-4-carboxamide 6ʹ. | |
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Indexing metadata ▾ |
- The patterns of behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate were studied.
- The formation of mixtures of tautomeric forms of silicon-containing urea—N-(trimethylsilyl) morpholine-4-carboxamide and trimethylsilylmorpholine-4-carboximidoate—was established.
- The composition and structure of the resulting products are determined both by the presence of a morpholine substituent at the nitrogen atom and by the type of isocyanate used. Unlike the trimethylsilyl derivative of morpholine, morpholine itself reacts with trimethylsilyl isocyanate to form a mixture of tautomeric forms.
Review
For citations:
Belova L.O., Golub N.A., Pletneva M.V., Kirilina N.I., Kirilin A.D. Behavior of morpholine and its trimethylsilyl derivative in reactions with trimethylsilyl isocyanate. Fine Chemical Technologies. 2022;17(5):377-383. https://doi.org/10.32362/2410-6593-2022-17-5-377-383