vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2019-9-3-366-375vuzbiochemi-209Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESВзаимодействие β-циклодекстрина с толуолсульфохлоридом в водно-щелочной средеInteraction of β-cyclodextrin with tosyl chloride in an aqueous alkaline mediumНовокшоновВ. В.NovokshonovV. V.

научный сотрудник,

г. Иркутск

Researcher,

Irkutsk

vnov1971@gmail.comНгуен Тхи ТхуСуанNguyen Thi ThuXuan

магистрант, Институт высоких технологий,

г. Иркутск

Master Student,

Irkutsk

vironguyen92@gmail.comШаглаеваН. С.ShaglaevaN. S.

д.х.н., профессор кафедры химической технологии,

г. Иркутск

Dr. Sci. (Chemistry), Professor, Department of Chemical Technology,

Irkutsk

shaglaevans@yandex.ruПодгорбунскаяТ. А.PodgorbunskayaT. A.

к.х.н., доцент кафедры химической технологии,

г. Иркутск

Ph.D., (Chemistry), Associate Professor, Department of Chemical Technology,

Irkutsk

tpodgor@istu.eduБаяндинВ. В.BayandinV. V.

к.х.н., доцент кафедры химической технологии,

г. Иркутск

Ph.D. (Chemistry), Associate Professor, Department of Chemical Technology,

Irkutsk

bayandinvv@yandex.ruИркутский институт химии им. А.Е. Фаворского СО РАНРоссияA.E. Favorsky Irkutsk Institute of Chemistry SB RASRussian FederationИркутский национальный исследовательский технический университетРоссияIrkutsk National Research Technical UniversityRussian Federation20190610201993366375Copyright © Новокшонов В.В., Нгуен Тхи Тху С., Шаглаева Н.С., Подгорбунская Т.А., Баяндин В.В., 20192019Новокшонов В.В., Нгуен Тхи Тху С., Шаглаева Н.С., Подгорбунская Т.А., Баяндин В.В.Novokshonov V.V., Nguyen Thi Thu X., Shaglaeva N.S., Podgorbunskaya T.A., Bayandin V.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/209

Региоселективная функционализация циклодекстриновой матрицы позволяет целенаправленно изменить способность циклодекстринов к образованию соединений включения, а также их растворимость, расширяя тем самым спектр их практического применения. Важнейшим и перспективным направлением в области селективной модификации β-циклодекстринов является получение тозильных производных, так как замещение тозильной группы такими нуклеофильными реагентами, как йодид, азид, тиоацетат, гидроксиламин, алкил- или полиалкиламид, приводит к соответствующим монозамещенным производным. В данной работе реализован метод синтеза моно[6-O-(4-толилсульфонил)]-β-циклодекстрина, усовершенствованный путем взаимодействия β-циклодекстрина с тозилхлоридом в водной среде в присутствии основания. Реакцией β-циклодекстрина с тозилхлоридом в водной среде в присутствии щелочи получен моно[6-О-(4- толилсульфонил)]-β-циклодекстрин с выходом 58% с чистотой, не требующей дополнительной очистки продукта. Установлено, что оптимальная концентрация β-циклодекстрина и тозилхлорида составляет 0,0032 моль/л и 0,0015 моль/л соответственно. Показано, что снижение скорости отфильтровывания непрореагировавшего тозилхлорида от реакционной смеси сопровождается возрастанием доли дитозильных производных и моно(3,6-ангидро)-β-циклодекстрина, образующегося в результате внутримолекулярной циклизации моно[6-O-(4-толилсульфонил)]- β-циклодекс-трина в щелочной среде при комнатной температуре. Структура полученного моно[6-О-(4-толилсульфонил)]-β-циклодекстрина подтверждено методом ПМР-спектроскопии. В ПМР-спектре продукта реакции β-циклодекстрина с тозилхлоридом появляются сигналы тозильного радикала при 2,42 м.д. и два дублета от водородов бензольного кольца с радикалами в пара-положении в области 7,41–7,43 м.д. Монозамещение доказано сопоставлением интегральных интенсивностей сигналов протонов циклодекстринового каркаса и протонов ароматической части продукта реакции, при этом их соотношение свидетельствовало о том, что только одна из семи первичных гидроксильных групп β-циклодекстрина была замещена.

The regioselective functionalisation of the cyclodextrin matrix provides the possibility of purposefully altering the ability of cyclodextrins to form inclusion compounds, as well as to ensure their solubility, thus expanding the scope of their practical application [1, 2]. The most significant and promising trend in the selective modification of β-cyclodextrins consists in the preparation of tosyl derivatives, given that the substitution of such nucleophilic reagents as iodide, azide, thioacetate, hydroxylamine, alkylamide or polyalkylamide for the tosyl group results in the corresponding monosubstituted derivatives. In this study, we impl emented a method for the synthesis of mono-6-O-(p-toluenesulphonyl)-β-cyclodextrin, which was improved by β-cyclodextrin reacting with tosyl chloride in an aqueous medium in the presence of a base. The reaction of β-cyclodextrin with tosyl chloride in an aqueous alkaline medium produced a 58% yield of mono -6- O-(p-toluenesulphonyl)-β-cyclodextrin not requiring additional purification. The optimal concentrations of β-cyclodextrin and tosyl chloride were found to be 0.0032 mol/l and 0.0015 mol/l, respectively. It was shown that a decrease in the rate of filtering the unreacted tosyl chloride out of the reaction mixture is acc ompanied by an increase in the proportion of ditosyl derivatives and mono(3,6-anhydro)-β-cyclodextrin resulting from the intramolecular cyclisation of mono-6-O-(p-toluenesulphonyl)-β-cyclodextrin at room temperature under alkaline conditions. The structure of the obtained mono-6-O-(p-toluenesulphonyl)-β-cyclodextrin was confirmed using Proton NMR Spectroscopy. The proton NMR spectrum of the product resulting from the reaction of β-cyclodextrin with tosyl chloride contains signals corresponding to a tosyl radical: a singlet (2.42 ppm) and two doublets (7.41–7.43 ppm) produced by hydrogens of the benzene ring having radicals in the para position. Monosubstitution was confirmed by comparing the integrated intensities of signals produced by the protons of the cyclodextrin skeleton and the protons from the aromatic part of the reaction product. Their ratio indicated that only one of the seven primary hydroxyl groups of β-cyclodextrin was substituted.

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The authors declare that there are no conflicts of interest present.