Structure and intramolecular mobility of some derivatives of bis(thio)phosphorylated amides in CCL4, CD2CL2, and CD3CN solutions

F.Kh. Karataeva^*, I.Z. Rakhmatullin^**, N.F. Galiullina^***, V.V. Klochkov^****

Kazan Federal University, Kazan, 420008 Russia

E-mail: ^*Farida.Karataeva@kpfu.ru, ^**IZRahmatullin@kpfu.ru,

^***nur608@mail.ru, ^****Vladimir.klochkov@kpfu.ru

Received January 12, 2023; Accepted January 25, 2023

ORIGINAL ARTICLE

Full text PDF

DOI: 10.26907/2542-064X.2023.1.149-157

For citation: Karataeva F.Kh., Rakhmatullin I.Z., Galiullina N.F., Klochkov V.V. Structure and intramolecular mobility of some derivatives of bis(thio)phosphorylated amides in CCL₄, CD₂CL₂, and CD₃CN solutions. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2023, vol. 165, no. 1, pp. 149–157. doi: 10.26907/2542-064X.2023.1.149-157. (In Russian)

Abstract

The structure and intramolecular mobility of some derivatives of bis(thio)phosphorylated amides in CCl₄, CD₂Cl₂, and CD₃CN solutions were examined by ¹H and ³¹P NMR spectroscopy. A comparative analysis of the temperature-dependent ¹H and ³¹P NMR spectra of the studied compounds with symmetric and asymmetric substitution at phosphorus atoms was carried out. Various intramolecular processes were identified – rotation around C-N bonds, conformational transformations of molecules, tautomerism, and phosphorylotropic rearrangement with the formation of various conformational forms. It was shown that a dynamic equilibrium of several forms is reached, with the amide (phosphazo-) form having a clear advantage.

Keywords: NMR spectroscopy, chemical shift, bis(thio)phosphorylated amides, phosphorylotropy, prototropy, tautomeric form, integral intensity, amide proton, concentration dependence of NH proton signals, temperature NMR spectra

Acknowledgements. This study was supported by the Kazan Federal University Strategic Academic Leadership Program (PRIORITY-2030).

Figure Captions

Fig. 1. Concentration dependence of the ¹Н NMR spectrum of compound 1 in CCL₄.

Fig. 2. ¹Н NMR temperature spectra in the resonance region of NH protons for compound 1 in a 5% solution in CD₂Cl₂.

Fig. 3. Concentration dependence of compound 2 in CCL₄.

Fig. 4. ³¹Р NMR spectrum for compound 1 in CD₃CN at 298 K.

Fig. 5. ¹Н NMR temperature spectra in the resonance region of NH and SH protons for compound 3 in CD₂CL₂, CD₃CN, and (CD₃)C=O.

References

1. Karataeva F.Kh., Efimov S.V., Klochkov V.V. NMR ¹H, ¹³C, ³¹P interpretation of phosphorylotropic rearrangement in N,N'-(bis)(diizopropoxyphosphorylamidocarbonyl)-1,10-diaza-18-сrown-6-ester in DMSO solution. BioNanoScience, 2019, vol. 9, no. 4, pp. 859–861. doi: 10.1007/s12668-019-00674-4.
2. Karatayeva F.Kh., Aganov A.V., Klochkov V.V. Dynamic ¹H, ¹³C, ³¹P NMR spectroscopy of the crown containing N-(thio)phosphoryl(thio)ureas. Appl. Magn. Reson., 1998, vol. 14, no. 4, pp. 545–558.
3. Karataeva F.Kh. Structure and intramolecular mobility of N-(thio)phosphoryl(thio)amides: ХVI.  ¹H, ¹³C and ³¹P NMR study of intramolecular dynamics of N,N′-bis(thio)phosphoryl(thio)urea containing an open-chain fragment in CD₂Cl₂ and CD₃CN solutions. Rus. J. Gen. Chem., 2011, vol. 81, no. 3, pp. 488–492. doi: 10.1134/S1070363211030078.
4. Thomas B., John A., Pfützner A., Grossmann G., Herrmann E. NMR-spektroskopische Untersuchungen an ¹⁵N-markierten N-Methyl-imidodiphosphorsäure-Derivaten. Z. Anorg. Allg. Chem., 1985, Bd. 525, H. 6, S. 7–13. doi: 10.1002/zaac.19855250602. (In German)
5. Riesel L., Sturm D. Untersuchungen zur Oxydation von N-Alkyl-bis-(difluoropho­sphor(III))-amiden. Z. Anorg. Allg. Chem., 1986, Bd. 539, H. 8, S. 183–186. doi: 10.1002/zaac.19865390817.
6. Tupchienko S.P., Dudchenko T.N., Gololobov Yu.G. Imide-amide rearrangement of imidothiopyrophosphates. Zh. Obshch. Khim., 1981, vol. 51, no. 5, pp. 1015–1020. (In Russian)
7. Karataeva F.Kh. Structure and intramolecular mobility of N-(phosporyl)-or (thiophosphoryl)amides and -thioamides: VII. Structure and dynamics of N-(diisopropoxythiophosphoryl)acetamide and –thioaceta­mide. Rus. J. Gen. Chem., 2000, vol. 70, no. 3, pp. 403–408.
8. Kabachnik M.I., Gilyarov V.A., Popov E.M. On imides of the phosphorus acids. Communication 7. Amide-imide tautomerism of the amides of pentavalent phosphorus acids. Bull. Acad. Sci. USSR, Div. Chem. Sci., 1961, vol. 10, no. 6, pp. 945–951. doi: 10.1007/BF00909162.

The content is available under the license Creative Commons Attribution 4.0 License.