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Phosphorylated Calix[4,8]Arenes Improve the RP HPLC Separation of Benzene Derivatives Aim

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Phosphorylated Calix[4,8]Arenes Improve the RP HPLC Separation of Benzene Derivatives Aim ISSN 2518-1548 (Online) Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71) ISSN 2308-8303 (Print) UDC 547.03+547.562 https://doi.org/10.24959/202706 O. I. Kalchenko, M. O. Vysotsky, S. O. Cherenok Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine 5, Murmanska str., Kyiv, 02094, Ukraine. E-mail: [email protected] Phosphorylated calix[4,8]arenes improve the RP HPLC separation of benzene derivatives Aim. To study the effect of 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]- arene and oсtаkis(diethoxyphosphoryloxy)-tert-butylcalix[8]аrene additives to the MeCN – H2O mobile phase (86:14) on the selectivity of the separation of aromatic compounds by the reversed-phase high performance liquid chro- matography (RP HPLC) using a Separon SGX C18 support. Results and discussion. The process of complexation of phosphorylated calix[4,8]arenes with benzene derivatives in the mobile phase plays a key role in the RP HPLC separation of analytes. The stability constants of the inclusion complexes and the chromatographic separation coefficients of the analytes depend on the nature of the aromatic compounds and the cavity size of the calixarene macrocycle. Experimental part. The HPLC analysis was performed in acetonitrile – water (86:14) solution using a Separon SGX C18 column. The stability constants of the calixarene complexes were determined using the dependence of 1/k’ chromatographic parameters of benzene derivatives on the calixarene concentration in the mobile phase. Molecular modelling of the calixarene complexes was carried out using a Hyper Chem 8.0 program. Conclusions. The phosphorus-contained calixarenes due to their ability to form supramolecular complexes with aromatic molecules can be used as additives to the RP HPLC mobile phase and improve separation of benzene derivatives. Key words: calixarenes; benzene derivatives; inclusion complexes; stability constants; separation selectivity; RP HPLC; molecular modelling O. I. Kaльчeнкo, М. О. Висоцький, С. O. Черенок Інститут органічної хімії НАН України, Україна Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену Мета. Дослідити вплив добавок 5,11,17,23-тетракіс(діізопропоксифосфоніл)-25,26,27,28-тетрапропокси- калікс[4]арену і октакіс(діетоксифосфорилокси)-трет-бутилкалікс[8]арену до рухомої фази складу MeCN – H2O (86:14) на селективність розділення ароматичних сполук методом обернено-фазної високоефективної рі- динної хроматографії (ОФ ВЕРХ) з використанням насадки Separon SGX C18. Результати та їх обговорення. Процес комплексоутворення фосфорильованих калікс[4,8]aренів з по- хідними бензену у мобільній фазі відіграє ключову роль у ОФ ВЕРХ розділенні цих аналітів. Константи стійкості комплексів включення та коефіцієнти хроматографічного розділення аналітів залежать від при- роди ароматичних сполук та розміру порожнини каліксаренового макроциклу. Експериментальна частина. ОФ ВЕРХ аналіз проводили у розчині ацетонітрил – вода (86:14) з вико- ристанням колонки з насадкою Separon SGX C18. Константи стійкості каліксаренових комплексів визначали із залежності хроматографічних параметрів 1/k’ похідних бензену від концентрації каліксарену в рухомій фазі. Молекулярне моделювання комплексів каліксаренів виконано за програмою Hyper Chem, версія 8.0. Висновки. Добавки фосфоровмісних калікс[4,8]аренів до рухомої фази завдяки здатності утворю- вати комплекси включення з ароматичними молекулами покращують їх ОФ ВЕРХ розділення на насадці Separon SGX C18. Ключові слова: каліксарени; похідні бензену; комплекси включення; константи стійкості; селективність розділення; ОФ ВЕРХ; молекулярне моделювання Copyright © 2020, O. I. Kalchenko, M. O. Vysotsky, S. O. Cherenok This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0) Calix[n]arenes – macrocyclic oligomers consisting calix[4]arene 1 of phenolic units linked by methylene spacers are well tert 2 mobile phase on and the oсtаkis(diethoxyphosphoryloxy)- selectivity of the HPLC separa -butylcalix[8]аrene to the acetonitrile – water molecularknown complexаnts complexes that with separate analyte different molecules; molecu- they tives improve the separation due to the formation of- haveles in beensolutions applied [1 – 9]. for Thesethe design compounds of stationary form supra chro- tion of some benzene derivatives. The calixarene addi- ter of the plots of 1/k’ νs the calixarene concentration le phases [17] that improve the HPLC separation of- inthe the host–guest mobile phaseinclusion allows complexes. calculating The linear the stability charac- matographic phases [10 – 16], and as additives to mobi- constants КА the separation selectivity induced by the calixarene organic or inorganic analytes. In this paper we report additives with of athe ratio complexes. of the stability The correlations constants of the effect of the additives of 5,11,17,23-tetrakis(di- isopropoxyphosphonyl)-25,26,27,28-tetrapropoxy- 43 ISSN 2308-8303 (Print) Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71) ISSN 2518-1548 (Online) Me Me Me iPr O iPr Me Me Me Me O P O Me Me OR OR RO iPr O OPr O iPr Me Me O P OPr PrO P O Me OR RO Me iPr OPr O Me Me O iPr OR RO OR O P O Me Me iPr O Me Me Me Me iPr OEt Me Me R: P O Me OEt 1 2 Fig. 1. Tetrakis(diisopropoxyphosphonyl)tetrapropoxycalix[4]arene 1 and octakis(diethoxyphosphoryloxy)-tert-butylcalix[8]arene 2 constants КА: bythe log host–guestP inclusion complexes of benzene deri- using the equation (1) for calculation of their stability vatives were found. The complexation is influenced 1/k’ = 1/k0’ + KA × [CA]/k0’ , the volume and other parameters of analytes Results and discussion (Fig. 1). k0’ k’ are capacity factors of the benzene , deriva(1) Complexation of calix[4]arene 1 tives determined in the absence and in the presence ne 2 with benzene derivatives was studied by the RP HPLC whеre: і - and calix[8]are- 1 2 were characterized by linear nesof calix[4,8]arenes to the mobile phase in the improves mobile phase. the separation se method described in papers [18, 19]. Calix[4]аrеne It has been shown that the addition of calixare- and calix[8]arene 1) calculated as the ratio of the re- adsorption isotherms (Fig. 2, 3) that indicated1, 2 are poten their tentionlectivity times of benzene of the pair analytes of analytes (Таbles depends 1, 2). onThe the sepa size- reversible adsorption by the column surface. Due to ration coefficient (α - these characteristics, calix[4,8]arenes - tity and position of the substituent in the molecules tial selectors for the RP HPLC separationk’ of benzene of analytes. deriva of the macrocyclic skeleton, as well as the nature, quan- tivesThe due calixarene to the formation additives of theto the host–guest mobile phase inclusion de- crease the capacity coefficient 1/k’ νs - tionof aromatic of phosphorylated analytes. calix[4]arene 1 to the mobile According to the data presented in Table1 0 1, the addi- catecomplexes. the formation The linear of the plots host–guest of inclusion the calix[4]- com arene and calix[8]arene concentration (Fig. 4, 5) indi- phase increases the analytep separation (αvs/α iodobenzene = 1.10 – 2.05). - The best separation has been observed for the pairs -1 -1 g plexes. g 0.25 with stoichiometry in the ratio of 1:1. It allows of. analytes,14 such as -aminophenol mol mol 12 m m 0.2 10 0.15 8 0.1 6 4 0.05 2 0 0 020406080 100 120 140 160 Calixarene adsorption, Calixarene adsorption, 020406080 100 120 140 160 -1 -1 Calixarene concentration,mmol . mL Calixarene concentration,mmol . mL Fig. 2. The adsorption isotherm of tetraphosphorylated Fig. 3. The adsorption isotherm of octaphosphorylated calix[4]arene 1 (R2 = 0.99) calix[8]arene 2 (R2 = 0.99) 44 ISSN 2518-1548 (Online) Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71) ISSN 2308-8303 (Print) 0.3 0.3 0.25 0.26 0.2 0.22 k' k' 0.15 1/ 1/ 0.18 0.1 0.14 0.05 0.1 0 -1 1357 -1 1357 [CA], . 10-4 M -3 [CA], . 10 M p-bromophenol p-fluorophenol chlorobenzene veratrol guaiacol phenol p-chlorophenol trichlorometh m-xylene benzene toluene trifluorometh p-aminophenol Fig. 4. Plots of 1/k’ for some benzene derivatives: Fig. 5. Plots of 1/k’ for some benzene derivatives: p-bromophenol, veratrol, guaiacol, phenol, benzene, toluene p-fluorophenol, chlorobenzene, p-chlorophenol, and trichloromethylbenzene νs the calix[4]arene 1 trichloromethylbenzene, m-xylene and p-aminophenol νs concentration in the mobile phase the calix[8]arene 2 concentration in the mobile phase (R2 = 0.95 – 0.99) (R2 = 0.95 – 0.99) 1 0 vs p 1 0 lex b veratrole vs 1 0 m vs gen bond with an oxygen atom of the phosphonyl N(αN/α = 1.78), pphenol -aminophenol1 0 (α /α m= 2.05), (Fіg. 8b), the phenolic group forms cthe hydro- ne vs guaiacol (α1 /α0 = 1.42), -toluidine the phenolic group creates the hydrogen bond with lytes, -dimethyl- were separated-toluidine by calixarene (α /α = 1.42), 1 and -xyle- group at the upper rim. In the complex (Fіg. 8c), chlorobenzene2 additive(α /α = to1.36). the Othermobile pairs phase of anaalso- 2 less effectively. isan larger ether by oxygen size with atom free at rotationthe lower of rim.the aromatic frag Calix[8]arene1 0 mentsOctaphosphorylated around Ar–CH –Ar calix[8]arene bonds changes (Fіg. its 9a)confor that observedimproves thefor separationthe following selectivity analytes: of benzeneresorcinol deri- vs - 2 vatives (α /α = 1.06 – 1.74). The1 0 best separation wasvs - 1 0 vs p mation after complexation with phenol. A phenol mo- trichloromethylbenzene1 0 (α /α = 1.74), vs toluene lecule is located in the center of the calixarene cavi- resorcinol (α /α = 1.71), toluene -methylphenol vs veratrol ty and forms the hydrogen bond Рh–О–Н···О(Р=O)Ar 1 0 Еxperimental part (α1/α0 = 1.58), trichloromethylbenzene trifluoro- with an ether oxygen аtоm (Fіg.
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