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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. Belova
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian 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
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
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
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
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
State Research Institute of Chemistry and Technology of Organoelement Compounds
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
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
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

1. IR spectrum of trimethylsilylmorpholine-4-carboxyimidoate 6 and N-(trimethylsilyl)morpholine-4-carboxamide 6ʹ.
Subject
Type Исследовательские инструменты
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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

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ISSN 2410-6593 (Print)
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