Abstract
An aqueous normal-phase high-performance liquid chromatography method was developed to separate cis/trans isomers of 4,5-dihydroxyimidazolidine-2-thione and 4,5-dimethoxyimidazolidine-2-thione on a Luna HILIC 200 Å column containing silica surface covered with cross-linked diol with an eluent acetonitrile/water in the ratio of 95:5 v/v. Changing of the analysis parameters leads to selectivity of cross-linked diol towards analyte with a predominance of adsorption mechanism between the phase and compounds. The separation in reversed-phase and normal-phase modes are unsuccessful. Chromatographic peaks of the cis/trans isomers are identified by the HR-LC–MS and the spectral ratios. The results of the determination of the isomer ratio for 4,5-dihydroxyimidazolidine-2-thione by the HPLC are consistent with the 1H NMR data. The existence of the previously undescribed cis-4,5-dimethoxyimidazolidine-2-thione is confirmed by the HR-HPLC–MS. This method allows providing simultaneous rapid separation and determination of the ratio of isomers in the samples of 4,5-dihydroxyimidazolidine-2-thione and 4,5-dimethoxyimidazolidine-2-thione.
Graphic abstract
Similar content being viewed by others
References
Pihtili G, Tuncer H (2017) Classical and microwave-assisted synthesis of substituted dihydroxy-imidazolidine-2-thiones compounds. Hacettepe J Biol Chem 45(2):163–174. https://doi.org/10.15671/HJBC.2017.149
Nakamura H, Noh JY, Itoh K, Fukata S, Miyauchi A, Hamada N (2007) Comparison of methimazole and propylthiouracil in patients with hyperthyroidism caused by Graves’ disease. J Clin Endocrinol Metabol 92(6):2157–2162. https://doi.org/10.1210/jc.2006-2135.
Mashio Y, Beniko M, Ikota A, Mizumoto H, Kunita H (1988) Treatment of hyperthyroidism with a small single daily dose of methimazole. Acta Endocrinol (Copenh) 119:139–144
Grishchenko SV, Lavrukhina LA, Ketiladze ES, Krylov VF, Ershov FI (1984) Results of combined therapy using levamisole for patients with influenza complicated by pneumonia. Vopr Virusol 29(2):175–179
Tadjarodi A, Adhami F, Hanifehpour Y, Yazdi M, Moghaddamfard Z, Kickelbick G (2007) Structural characterization of a copper (II) complex containing oxidative cyclization of N-2-(4-picolyl)-N’-(4-methoxyphenyl) thiourea, new ligands of 4-picolylthiourea derivatives and the precursor molecular structure of oxidative cyclization of N-(2-pyrid-yl)-N’-(4-methoxyphenyl) thiourea. Polyhedron 26(15):4609–4618. https://doi.org/10.1016/j.poly.2007.06.014
Nelyubina YV, Gazieva GA, Baranov VV, Belyakov PA, Chizhov AO, Lyssenko KA, Kravchenko AN (2009) The synthesis, structure, and electron density distribution in crystals of 4,5-dihydroxyimidazolidin-2-thiones. Russ Chem Bull 58(7):1353–1360
Singh M, Parvari G, Botoshansky M, Keinan E, Reany O (2014) The synthetic challenge of thioglycolurils. Eur J Org Chem 2014:933–940. https://doi.org/10.1002/ejoc.201301672
Lang C, Mohite A, Deng X, Yang F, Dong Z, Xu J, Liu J, Keinan E, Reany O (2017) Semithiobambus[6]uril is a transmembrane anion transporter. Chem Commun 53:7557–7560. https://doi.org/10.1039/C7CC04026A
Singh M, Solel E, Keinan E, Reany O (2015) Dual-functional semithiobambusurils. Chem Eur J 21:536–540. https://doi.org/10.1002/chem.201404210
Zhang Z-F, Zhang J-M, Guo J-P, Qu G-R (2007) Trans-4,5-dihydroxyimidazolidine-2-thione. Acta Cryst E63:2821–2823. https://doi.org/10.1107/S1600536807018429
Kalichkina LE, Nikulina AE, Malkov VS (2016) Method of analysing 4,5-dihydroxymidazoline-2-thione. RU Patent 2(580):289
Jandera P, Hajek T (2018) Mobile phase effects on the retention on polar columns with special attention to the dual hydrophilic interaction–reversed-phase liquid chromatography mechanism, a review. J Sep Sci 41:145–162. https://doi.org/10.1002/jssc.201701010
Yang Y, Lu D, Yin S, Yang D, Chen Y, Li Y, Sun C (2018) A Convenient ultrasound assisted saponification for the simultaneous determination of vitamin E isomers in vegetable oil by HPLC with fluorescence detection. J Sep Sci 41:1–10. https://doi.org/10.1002/jssc.201701393
Dousa M, Srbek J, Stránsky Z, Gibala P, Novakova L (2014) Retention behavior of a homologous series and positional isomers of aliphatic amino acids in hydrophilic interaction chromatography. J Sep Sci 37:739–747. https://doi.org/10.1002/jssc.201301348
Karonen M, Liimatainen J, Sinkkonen J (2011) birch inner bark procyanidins can be resolved with enhanced sensitivity by hydrophilic interaction HPLC-MS. J Sep Sci 34:3158–3165. https://doi.org/10.1002/jssc.201100569
Jandera P, Hajek T (2009) Utilization of dual retention mechanism on columns with bonded PEG and diol stationary phases for adjusting the separation selectivity of phenolic and flavone natural antioxidants. J Sep Sci 32:3603–3619. https://doi.org/10.1002/jssc.200900344
Pesek JJ, Maria T, Matyska MT, Boysen RI, Yang Y, Hearn MTW (2013) Aqueous normal-phase chromatography using silica-hydride-based stationary phases. J Trends Anal Chem 42:64–73. https://doi.org/10.1016/j.trac.2012.09.016
Acknowledgements
The research was supported by The Tomsk State University competitiveness improvement programme.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Mamko, K., Kalichkina, L., Kotelnikov, O. et al. Separation of cis/trans Isomers of 4,5-Dihydroxyimidazolidine-2-thione and 4,5-Dimethoxyimidazolidine-2-thione by Aqueous Normal-Phase HPLC Mode. Chromatographia 83, 1087–1093 (2020). https://doi.org/10.1007/s10337-020-03926-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10337-020-03926-8