Ivanovo, Ivanovo, Russian Federation
Ivanovo, Ivanovo, Russian Federation
UDK 547.712.2 Соединения, в молекулах которых циклы непосредственно соединены друг с другом
UDK 544.32 Термодинамические функции химических процессов
UDK 544.582.6 Изотопные эффекты
This review is based on the analysis of data on the structural and thermodynamic properties of tetra-N-alkyl-substituted bicyclic bis-urea of the octane series (glycolurils), singly and dissolved in H2O and D2O, obtained by other authors. The paper discusses issues of the influence of the stereochemical nature of these bioactive compounds on their hydration processes. The researched substances are the low-toxic glycolurils with pharmacologically pronounced psychotropic effects, known under the commercial names Mebicar (tetra-N-methylanalog), Bicaret (tetra-N-ethylanalog), and the cis- and trans-N-diethyl-dimethyl-analogs, Mebicaret and Albicar. The last listed glycoluril, which is chiral in stereochemical nature, was investigated as racemate. The study also included the analysis of the available results of calorimetric, densitometric, and spectroscopic (for Mebicar) studies of glycolurils solutions in H/D isotopologues of water as well as quantum-chemical calculations of molecular parameters of these heterocyclic compounds in the ideal gas phase. It has been shown that the hydration of each of the studied tetra-N-alkyl-substituted glycolurils can be generally regarded as a superposition of two mechanisms – hydrophobic and hydrophilic. In the case of Bicaret, the former is dominant, while for Mebicar the latter obviously predominates. Regarding to the structural state and solvation in aqueous medium of glycolurils with mixed N-alkyl-substitution such as Albicar and Mebicaret, the stereochemical nature of their molecules predetermines a kind of "thermodynamic balance (dualism)" between the mentioned mechanisms. The paper outlines the distinctive features of the hydration process of racemic Albicar against the effects of intermolecular interaction in aqueous solution of achiral Mebicaret.
tetra-N-alkyl-substituted glycoluriles; H/D water isotopologues; standard molar volumes and dissolution enthalpies; solvent isotope effects; molecular parameters; hydrophilic and hydrophobic hydration
1. Pletnev V.Z., Mihaylova I.Yu., Sobolev A.N., Galickiy N.M., Verenich A.I., Hmel'nickiy L.I., Lebedev O.V., Kravchenko A.N., Suvorova L.I. Prostranstvennaya struktura psihotropno-aktivnyh soedineniy ryada N-polialkilproizvodnyh 2,4,6,8-tetraazabiciklo[3.3.0]oktandiona-3,7 v kristalle po dannym rentgenostrukturnogo analiza. Bioorg. himiya. 1993. T. 19. № 6. S. 671-681.
2. Kravchenko A.N., Sigachev A.S., Maksareva E.Yu., Gazieva G.A., Trunova N.S., Lozhkin B.V., Pivina T.S., Il'in M.M., Nelyubina Yu.V., Davankov V.A., Lebedev O.V., Mahova N.N., Tartakovskiy V.A.. Sintez novyh hiral'nyh mono-, di-, tri- i tetraglikol'urilov. Izv. Akad. nauk. Ser. him. 2005. № 3. S. 1680-1692.
3. Viharev Yu.B., Anikina L.V., Chikunov I.E., Sigachev A.S., Kravchenko A.N., Shklyaev Yu.V., Mahova N.N. Neyroprotektornye svoystva N-funkcional'no-zameschennyh glikol'urilov. Voprosy biol. med. farm. himii. 2006. № 2. S. 12-16.
4. Ivanov E.V., Abrosimov V.K. Izotopnye effekty rastvoritelya v termodinamike gidratacii ciklicheskih proizvodnyh mocheviny. Himiya rastvorov biologicheski aktivnyh veschestv. Ser. «Problemy himii rastvorov». Ivanovo: IID, 2016. S. 17-92.
5. Kravchenko A.N., Baranov V.V., Gazieva G.A. Sintez glikol'urilov i ih analogov. Uspehi himii. 2018. T. 87. № 1. S. 89-108.
6. Panshina S.Yu., Ponomarenko O.V., Bakibaev A.A., Malkov V.S., Kotelnikov O.A., Tashenov A.K. Study of glycoluril and its derivatives by 1H and 13C NMR spectroscopy. Bull. Karaganda Univ. Chem. Ser. 2020. V. 99. N 3. P. 21-37. DOI:https://doi.org/10.31489/2020Ch3/21-37.
7. Val'dman A.V., Zaikonnikova I.V., Kozlovskaya M.M., Zimakova I.E. Izuchenie osobennostey spektra psihotropnoy aktivnosti mebikara. Byulleten' eksperim. biol. med. 1980. T. 89. № 5. S. 568-570.
8. Ryzhkina I.S., Kiseleva, Yu.V., Mishina O.A. Timosheva A.P., Sergeeva S.Yu., Kravchenko A.N., Konovalov A.I. Correlations between the self-organization, physicochemical properties, and biological activity of Mebicar in dilute aqueous solutions. Mendeleev Commun. 2013. V. 23. N 5. R. 262-264, DOI: 10.1016/ j.mencom.2013.09.008.
9. Ivanov E.V., Batov D.V. Enthalpy-related parameters of interaction of simplest α-amino acids with the pharmaceutical mebicar (N-tetramethylglycoluril) in water at 298.15 K. J. Chem. Thermodyn. 2019. V. 128. P. 159-163. DOI:https://doi.org/10.1016/j.jct.2018.08.022.
10. Ivanov E.V., Lebedeva E.Yu. Effect of temperature on volumetric behavior of glycine in aqueous mebicar (N-tetramethylglycoluril) at p ~ 0.1 MPa. J. Mol. Liq. 2017. V. 242. P. 235-243. DOI:https://doi.org/10.1016/j.molliq.2017.07.015.
11. Mashkovskiy M.D. Lekarstvennye sredstva. 16-e izd. M.: Novaya volna, 2020. 1216 s.
12. Ivanov E.V., Lebedeva E.Yu. Interaction-related volumetric and some other properties of urea solutions in aqueous N-tetramethylglycoluril (the mebicar drug) at different temperatures and under the ambient pressure. J. Mol. Liq. 2021. V. 331. P. 11512/1-115812/9. DOI:https://doi.org/10.1016/j.molliq.2021.115812.
13. Kostyanovsky R.G., Kadorkina G.K., Lyssenko K.A., Torbeev V.Yu., Kravchenko A.N., Lebedev O.V., Grintselev-Knyazev G.V., Kostyanovsky V.R. Chiral drugs via the spontaneous resolution. Mendeleev Commun. 2002. V. 12. N 1. P. 6-8. DOI:https://doi.org/10.1070/MC2002v012n01ABEH001521
14. Prokopov A.A., Kostebelov N.V., Berlyand A.A. Eksperimental'naya farmakokinetika al'bikara. Him.-farm. zhurn. 2002. № 3. S. 13-16.
15. Lenev D.A., Lyssenko K.A., Kostyanovsky R.G. The chiral drug Albicar: resolution of its racemate via complexation with BINOL. New J. Chem. 2010. V. 34. N 3. P. 403-404. DOI:https://doi.org/10.1039/b9nj00701f.
16. Berlyand A.S, Lebedev O.V., Prokopov A.A. Himiko-farmacevticheskiy analiz biologicheski aktivnogo veschestva al'bikar. Him.-farm. zhurn. 2013. T. 47. № 3. S. 52-54.
17. Anikina L.V., Vikharev Yu.B., Baranov V.V., Malyshev O.R., Kravchenko A.N. Preparative synthesis and pharmacological activity of Albicar racemate and enantiomers. Mendeleev Commun. 2018. V. 28. N 3. P. 317-319. DOI: 10.1016/ j.mencom.2018.05.030.
18. Ivanov E.V., Batov D.V., Baranov V.V., Kravchenko A.N. Temperature-dependent thermochemical properties of the Mebicaret (2,4-dimethyl-6,8-diethylglycoluril) solutions in H2O and D2O at the ambient pressure. Thermochim. Acta. 2016. V. 627. P. 48-54. DOI:https://doi.org/10.1016/j.tca.2016.01.010.
19. Ivanov E.V., Lebedeva E.Yu., Petrovskaya S.G., Baranov V.V., Kravchenko A.N., Ivanova N.G. Volume-related interaction parameters for dilute solutions of Mebicaret (2,4-dimethyl-6,8-diethylglycoluril) in normal and heavy water between 278.15 K and 318.15 K. J. Mol. Liq. 2017. V. 242. P. 160-167. DOI:https://doi.org/10.1016/j.molliq.2017.07.003.
20. Prokopov A.A., Berlyand A.S., Kazanceva O.N. Izuchenie metabolizma bikareta. Him.-farm. zhurn. 2002. T. 36. № 10. S. 5-6.
21. Prokopov A.A., Berlyand A.S., Kazanceva O.N. Izuchenie eksperimental'noy farmakokinetiki bikareta. Him.-farm. zhurn. 2003. T. 37. № 3. S. 25-28.
22. Chegaev K.Yu., Kravchenko A.N., Lebedev O.V., Strelenko Yu.A. New functional glycoluril derivatives. Mendeleev Commun. 2001. V. 11. N 1. P. 32-33. DOI: 10.1070/ MC2001v011n01ABEH00135.
23. Sanders M.P.A., Barbosa A.J.M., Zarzycka B., Nicolaes G.A.F., Klomp J.P.G., de Vlieg J., Del Rio A. Comparative analysis of pharmacophore screening tools. J. Chem. Inf. Model. 2012. V. 52. N 6. P. 1607-1620. DOI:https://doi.org/10.1021/ci2005274.
24. Katzung B.G., Vanderah T.W. Basic & Clinical Pharmacology. 15th ed. New York: McGraw Hill Professional, 2018. 1310 p.
25. Hurgin Yu.I., Lebedev O.V., Maksareva E.Yu., Zavizion V.A., Kudryashova V.A., Vorob'ev M.M., Orehova G.A., Danilenko A.N. Mezhmolekulyarnye vzaimodeystviya v vodnyh rastvorah mebikara. Izv. Akad. nauk. Ser. him. 1995. № 6. S. 1178-1179.
26. Ewing M.B, Lilley T.H., Olofsson G.M., Ratzsch M.T., Somsen G. Standard quantities in chemical thermodynamics. Fugacities, activities and equilibrium constants for pure and mixed phases (IUPAC Recommendations 1994). Pure Appl. Chem. 1994. V. 66. N 3. P. 533-552. DOI:https://doi.org/10.1351/pac199466030533.
27. Ivanov E.V. Thermodynamic interrelation between excess limiting partial molar characteristics of a liquid nonelectrolyte. J. Chem. Thermodyn. 2012. V. 47. P. 437-440. DOI:https://doi.org/10.1016/j.jct.2011.11.018.
28. Kustov A.V. Gidrofobnye effekty: Strukturnye, termodinamicheskie, prikladnye aspekty. Dostizheniya poslednih let. M.: Krasand, 2013. 224 s.
29. Wilhelm E. Chemical thermodynamics: A journey of many vistas. J. Solution Chem. 2014. V. 43. N 3. P. 525-576. DOI:https://doi.org/10.1007/s10953-014-0140-0.
30. Ben-Naim A. Solvation Thermodynamics. New York: Springer, 1987. 246 p. DOI:https://doi.org/10.1007/978-1-4757-6550-2.
31. Rabinovich I.B. Vliyanie izotopii na fiziko-himicheskie svoystva zhidkostey. M.: Nauka, 1968. 308 s.
32. Lobyshev V.I., Kalinichenko L.P. Izotopnye effekty D2O v biologicheskih sistemah. M.: Nauka, 1978. 216 s.
33. Engdahl A., Nelander B. On the relative stabilities of H- and D-bonded water dimmers. J. Chem. Phys. 1987. V. 86. N 4. P. 1819-1823. DOI:https://doi.org/10.1063/1.452182.
34. Abrosimov V.K., Ivanov E.V. Voda v nevodnyh rastvoritelyah: sostoyanie i sol'vataciya. Voda: Struktura, sostoyanie, sol'vataciya. Dostizheniya poslednih let. Ser. «Problemy himii rastvorov». M.: Nauka, 2003. S. 277-346.
35. Soper A.K., Benmore C.J. Quantum differences between heavy and light water. Phys. Rev. Lett. 2008. V. 101. N 6. N 065502/1-065502/4. DOI: 10.1103/ PhysRevLett.101.065502.
36. Ivanov E.V., Ivanova N.G. Sostoyanie i sol'vataciya H/D-izotopologov vody v aprotonnyh dipolyarnyh organicheskih sredah po rezul'tatam termohimicheskih issledovaniy. Ot himii k tehnologii. Shag za shagom. 2021. T. 2. № 1. S. 42-62. URL: https://drive.google.com/file/d/17wkupCzIUSz5SoxK58Ux7OgZY7sfhj-I/view
37. Grillon E., Gallo R., Pierrot M., Boileau J., Wimmer E. Isolation and X-ray structure of the intermediate dihydroxyimidazolidine (DHI) in the synthesis of glycoluril from glyoxal and urea. Tetrahedron Lett. 1988. V. 29. N 9. P. 1015-1016. DOI: 10.1016/ 0040–4039(88)85322-X.
38. Atavin E.G., Golubinskiy A.V., Kravchenko A.N., Lebedev O.V., Vilkov L.V. Elektronograficheskoe issledovanie struktury molekuly mebikara. Zhurn. strukturnoy. himii. 2005. T. 46. № 3. S. 430-434.
39. Abrosimov V.K., Krasnov A.V., Zhabanov Yu.A., Ivanov E.V. Molekulyarnaya struktura i ental'piya sublimacii 2,4,6,8-tetrametilglikol'urila – lekarstvennogo preparata «Mebikar». Izv. vuzov. Himiya him. tehnologiya. 2015. T. 58. № 1. S. 3-5.
40. Rezaei-Seresht E., Tayebee R. Synthesis of glycoluril derivatives catalyzed by some heteropolyoxometalates. J. Chem. Pharm. Res. 2011. V. 3. N 1. P. 103-107.
41. Dunning T.H., Jr. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J. Chem. Phys. 1989. V. 90. N 2. P. 1007-1023. DOI:https://doi.org/10.1063/1.456153.
42. Abrosimov V.K., Zhabanov Yu.A., Krasnov A.V., Ivanov E.V. Molekulyarnaya struktura metil-N-zameschennyh hiral'nyh glikol'urilov po rezul'tatam kvantovo-himicheskih DFT-raschetov. Izv. vuzov. Himiya him. tehnologiya. 2015. T. 58. № 8. S. 29-32.
43. Muller P. Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994). Pure Appl. Chem. 1994. V. 66. N 5. P. 1077-1184. DOI:https://doi.org/10.1351/pac199466051077.
44. Zacepina G.N. Fizicheskie svoystva i struktura vody. M.: Izd-vo MGU, 1987. 171 s.
45. Machida M., Kato K., Shiga M. Nuclear quantum effects of light and heavy water studied by all-electron first principles path integral simulations. J. Chem. Phys. 2018. V. 148. N 10. P. 102324/1-102324/11. DOI:https://doi.org/10.1063/1.5000091.
46. Berger A., Ciardi G., Sidler D., Hamm P., Shalit A. Impact of nuclear quantum effects on the structural inhomogeneity of liquid water. PNAS USA. 2019. V. 116. N 7. DOI:https://doi.org/10.1073/pnas.1818182116.
47. Belousov V.P., Panov M.Yu. Termodinamika vodnyh rastvorov neelektrolitov. L.: Himiya, 1983. 265 s.
48. Krestov G.A., Korolev V.P., Batov D.V. Differenciruyuschee zameschenie protiya deyteriem na svoystva rastvoriteley. Dokl. Akad. nauk SSSR. 1987. T. 293. № 4. S. 882-884.
49. Swain C.G., Bader R.F.W. The nature of the structure difference between light and heavy water and the origin of the solvent isotope effect−I. Tetrahedron. 1960. V. 10. N 3-4. P. 182-199. DOI:https://doi.org/10.1016/S0040-4020(01)97806-8.
50. Ivanov E.V., Lebedeva E.Yu., Abrosimov V.K., Ivanova N.G. Strukturnyy vklad effekta gidrofobnoy gidratacii blagorodnyh gazov. Zhurn. strukturnoy himii. 2005. T. 46. № 2. S. 262-272.
51. Hurgin Yu.I., Kudryashova V.A., Zavizion V.A. Issledovanie mezhmolekulyarnyh vzaimodeystviy metodom millimetrovoy spektroskopii. Otricatel'naya i polozhitel'naya gidrataciya v vodnyh rastvorah mocheviny. Izv. akad. nauk SSSR. Ser. him. 1990. № 2. S. 314-320.
52. Ivanov E.V., Abrosimov V.K., Batov D.V. Vliyanie temperatury na H/D- izotopnye effekty v ental'pii gidratacii tetrametil-bis-karbamida. Izv. Akad. nauk. Ser. him. 2006. № 4. S. 715-717.
53. Korolev V.P., Kustov A.V., Batov D.V., Smirnova N.L., Lebedev Yu.A. Effekty gidrofil'nyh i gidrofobnyh grupp gidratacii tetrametilbismocheviny i N,N’-dimetilpropilenmocheviny v rastvorah. Biofizika. 2008. T. 53. № 4. S. 544-549.
54. Ivanov E.V., Batov D.V., Gazieva G.A., Kravchenko A.N., Abrosimov V.K. D2O‒H2O solvent isotope effects on the enthalpies of bicaret hydration and dilution of its aqueous solutions at different temperatures. Thermochim. Acta. 2014. V. 590. N 1-2. P. 145-150. DOI:https://doi.org/10.1016/j.tca.2014.05.011.
55. Ivanov E.V., Batov D.V., Kravchenko A.N. (D2O–H2O) solvent isotope effects on some thermodynamic properties of the Albicar dissolution (hydration) between T = (278.15 and 313.15) K at ambient pressure. J. Chem. Thermodyn. 2016. V. 97. P. 341-347. DOI:https://doi.org/10.1016/j.jct.2016.02.012.
56. Kustov A.V., Batov D.V., Usacheva T.R. Kalorimetriya rastvorov neelektrolitov: teoreticheskie osnovy, eksperiment, analiz dannyh. M.: Krasand, 2016. C. 32-36 (288 s.).
57. Nakamura M., Tamura K, Murakami S. Isotope effects on thermodynamic properties: mixtures of x(D2O or H2O) + (1‒x)CH3CN at 298.15 K. Thermochim. Acta. 1995. V. 253. P. 127-136. DOI:https://doi.org/10.1016/0040-6031(94)02086-4.
58. Jelinska-Kazimierczuk M., Szydlowski J. Physicochemical properties of solutions of amides in H2O and in D2O. J. Solution Chem. 2001. V. 30. N 7. P. 623-640. DOI:https://doi.org/10.1023/A:1010454929640.
59. Phillip P.R., Perron G., Desnoyers J.E. Apparent molal volumes and heat capacities of urea and methyl-substituted ureas in H2O and D2O at 25°C. Can. J. Chem. 1974. V. 52. N 9. P. 1709-1713. DOI:https://doi.org/10.1139/v74-246.
60. Abrosimov V.K., Chumakova R.V. Termodinamika vodnyh rastvorov uglevodov: Mono- i disaharidy. Biologicheski aktivnye veschestva v rastvorah: Struktura, termodinamika, reakcionnaya sposobnost'. Ser. «Problemy himii rastvorov». M.: Nauka, 2001. S. 47-109.
61. Abrosimov V.K., Ivanov E.V., Batov D.V. Ental'pii perenosa Mebikara iz vody v vodnye rastvory karbamida i ego metilzameschennyh proizvodnyh pri 298.15 K. Zhurn. fiz. himii. 2006. T. 80. № 11. S. 2016-2019.
62. Abrosimov V.K., Ivanov E.V., Batov D.D. Osobennosti mezhmolekulyarnyh vzaimodeystviy v vodnyh rastvorah metilproizvodnyh mocheviny. Dokl. Akad. nauk. 2006. T. 407. № 6. S. 785-788.
63. Ivanov E.V., Batov D.V. Enthalpy-related interaction parameters in H/D isotopically distinguishable aqueous solutions of tetramethylurea cyclic derivatives at 298.15 K. Thermochim. Acta. 2011. V. 523. N 1-2. P. 253-257. DOI:https://doi.org/10.1016/j.tca.2011.05.019.
64. Ivanov E.V., Batov D.V. Effect of the H/D solvent isotope substitution on enthalpy-related interaction parameters in aqueous solutions of the racemic Albicar at T = 298.15 K and ambient pressure. J. Chem. Thermodyn. 2016. V. 102. P. 9-11. DOI: 10.1016/ j.jct.2016.06.020.
65. Franks F., Pedley M., Reid D.S. Solute interactions in dilute aqueous solutions: part 1 – microcalorimetric study of the hydrophobic interaction. J. Chem. Soc. Faraday Trans. 1. 1976. V. 72. N. 2. P. 359-367. DOI:https://doi.org/10.1039/F19767200359.
66. Barone G., Cacace P., Castronuovo G., Elia V. Interactions in aqueous solutions of urea-like compounds: heats of mixing of urea, monomethylurea and thiourea at 298.15 K, J. Chem. Soc. Faraday Trans. 1. 1981. V. 77. N 7. P. 1569-1577. DOI: 10.1039/ F19817701569.
67. Ivanov E.V., Abrosimov V.K. D2O‒H2O Solvent isotope effects on the apparent molar volumes of tetramethyl-bis-urea (Mebicarum) solutions. J. Solution Chem. 2007. V. 36. N 3. P. 313-325. DOI:https://doi.org/10.1007/s10953-006-9118-x.
68. Ivanov E.V., Lebedeva E.Yu., Abrosimov V.K. Volumetric properties of Bicaret (tetra-N-ethylglycoluril) solutions in ordinary and heavy water at temperatures from (278.15 to 318.15) K and ambient pressure. J. Chem. Eng. Data. 2015. V. 60. N 7. P. 2079-2089. DOI:https://doi.org/10.1021/acs.jced.5b00154.
69. Ivanov E.V., Lebedeva E.Yu., Kravchenko A.N. Standard volumetric properties of a chiral pharmaceutical Albicar in water H/D isotopologues in the temperature range from (278.15 to 318.15) K and at ambient pressure. J. Chem. Thermodyn. 2017. V. 115. P. 148-155. DOI:https://doi.org/10.1016/j.jct.2017.07.034.
70. Wüzburger S., Sartorio R., Guarino G., Nisi M. Volumetric properties of aqueous solutions of polyols between 0.5 and 25°C. J. Chem. Soc. Faraday Trans. 1. 1988. V. 81. N 7. 2279-2287. DOI:https://doi.org/10.1039/F19888402279.
71. Abrosimov V.K., Ivanov E.V. Densimetriya rastvorov. Teoreticheskie i eksperimental'nye metody himii rastvorov. Ser. «Problemy himii rastvorov». M.: Prospekt, 2011. S. 425-463.
72. Fitzgerald D. Technical Assessment of the Anton Paar DMA 5000 Density Meter. Wales (UK): L&D Fitzgerald Ltd. 2000. P. 2–8. URL: https://density.co.uk.
73. Lepori L., Gianni P. Partial molar volumes of ionic and nonionic organic solutes in water: A simple additivity scheme based on the intrinsic volume approach. J. Solution Chem. 2000. V. 29. N 5. P. 405-447. DOI:https://doi.org/10.1023/A:1005150616038.
74. Kuz'min V.S., Kacer S.B. Raschet van-der-vaal'sovyh ob'emov organicheskih molekul. Izv. Akad. nauk. Ser. him. 1992. № 4. S. 922-931.
