Abstract
The work presents the obtaining of atropine N-oxide using various peroxyacids (organic monoperoxyacid, diperoxyacids and inorganic peroxyacids). The kinetics of atropine oxidation with various oxidants, for example Oxone, m-chloroperoxybenzoic acid, diperoxysebasic acid and diperoxyazelaic acid, was studied. The optimal conditions for obtaining of atropine N-oxide (oxidation duration, pH) are given in the work. It was established that the best oxidant was potassium peroxymonosulfate, since 100% yield of atropine N-oxide was achieved within 15 min. In this work, we showed that the oxidation reaction of atropine to N-oxide was a second-order reaction. The rate constants of these reactions were established. The electrochemical behavior of atropine N-oxide obtained using potassium peroxymonosulfate and m-chloroperoxybenzoic acid on a mercury dropping electrode was investigated. Atropine N-oxide was reduced forming two peaks. Each reduction peak involved 1 electron and 1 proton.
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References
"Atropine". The American Society of Health-System Pharmacists. Archived from the original on 2015–07–12. Retrieved Aug 13, 2015. https://www.ashp.org/
Ainsworth S (2014) Neonatal formulary: drug use in pregnancy and the first year of life, 7th edn. BMJ Books, London
Bai Y, Desai H, Pelletier S (1995) N-oxides of some norditerpenoid alkaloids. J Nat Prod 58(6):929–933. https://doi.org/10.1021/np50120a01
Belej J (1986) Recent thermodynamic data for some reactions of peroxomonosulphate ion. J Electroanal Chem Interfacial Electrochem 214(1–2):481–483. https://doi.org/10.1016/0022-0728(86)80117-6
Beller V, Bellus D, Chemler Sh, Enders D, Geffken D, Köllner M, Wolfgang (2014) Science of Synthesis. Houben-Weyl Methods of Molecular Transformations Amine N-Oxides, Haloamines, Hydroxylamines and Sulfur Analogues, and Hydrazines. Dieter Enders. Georg Thieme Verlag KG. 40b
Bibire N, Tântaru G, Dorneanu V, Stan M, Apostu M (2003) Membrane-selective electrode forAtropine assay. Rev Med Chir Soc Med Nat Iasi 107(1):218–222
Blazheyevskiy M (2017) Application of derivatization by means of peroxy acid oxidation and perhydrolysis reactions in pharmaceutical analysis. Ivan Franko National University of Lviv, Lviv, Ukraine
Blazheyevskiy M, Batalov A (1999) Oxididimetric determination of alkaloids based on N-oxidation reactions with peroxycarboxylic acids. J Anal Chem 54(1):87–90
Blazheyevskiy M, Riabko D (2014) Application of peroxyacids as disinfectants and sterilization agents. Lap Lambert Academic Publishing, Deutshland
Blazheyevskiy M, Ya Anatska, Kissel O (2012) Voltammetric determination of atropine in the form of N-oxide obtained with potassium hydrogen peroxomonosulfate. Ukr med almans. 15(1):26–29
Brown K, Menemy M, Palmer M, Baker M, Robinson D, Allan P, Dennany L (2019) Utilization of an electrochemiluminescence sensor for atropine determination in complex matrices. Anal Chem 91:12369–12376. https://doi.org/10.1021/acs.analchem.9b02905
Brust J (2004) Neurological aspects of substance abuse, 2nd edn. Elsevier, Philadelphia. https://doi.org/10.1016/B978-0-7506-7313-6.X5001-6
Cai I, Sha M, Guo C, Pan M (2012) Synthesis of tertiary amine N-oxides. Asian J Chem 24(9):3781–3784
Chen H, Chen Y, Du P, Han F, Wang H, Zhang H (2006) Sensitive and specific liquidchromatographic-tandem mass spectrometric assay for Atropine and its eleven metabolites in rat urine. J Pharm and Biomed Anal 40(1):142–150. https://doi.org/10.1016/j.jpba.2005.06.027
Craig J, Purushothaman K (1970) Improved preparation of tertiary amine N-oxides. J Org Chem 35(5):1721–1722. https://doi.org/10.1021/jo00830a121
Dubenska L, Dushna O, Plyska M, Blazheyevskiy M (2020) Method of polarographic determination of platyphylline in a form of N-oxide and its validation in solution for injection. Methods Objects Chem Anal 15(2):83–92. https://doi.org/10.17721/moca.2020.83-92
Dubenska L, Dushna O, Pysarevska S, Blazheyevskiy M (2020a) A new approach for voltammetric determination of nefopam and its metabolite. Electroanalysis 32(3):626–634. https://doi.org/10.1002/elan.201900595
Dubey B, Renu U, Tiwari A, Shukla I (2004) Assay of some ophthalmic drugs with ammonium metavanadate reagent. J Indian Chem Soc 81(6):511–514
European pharmacopoeia.6th edn. (2007) Council of Europe. EDQM Strasbourg. https://www.edqm.eu/
Fawzy A, Zaafarany IA, Tirkistani FA, Asghar BH (2016) Oxidative degradation of atropine drug by permanganate ion in perchloric and sulfuric acid solutions: a comparative kinetic study. Adv Biochem 4(5):58–65. https://doi.org/10.11648/j.ab.20160405.12
Field J, Hazinski M, Sayre M, Chameides L, Schexnayder St, Hemphill R, Samson R, Kattwinkel J, Berg R, Bhanji F, Cave D, Jauch Ed, Kudenchuk P, Neumar R, Peberdy M, Perlman J, Sinz E, Travers A, Berg M, Billi J, Eigel B, Hickey R, Kleinman M, Link M, Morrison L, O'Connor R, Shuster M, Callaway C, Cucchiara B, Ferguson J, Rea Th, Hoek T (2010) Part 1: executive summary: 2010 American Heart Association Guidelines for Cardiopulmonary Resuscitation and Emergency Cardiovascular Care Circulation 122. doi: https://doi.org/10.1161/CIRCULATIONAHA.110.970889
Gosser D (1999) Cyclic voltammetry: simulation and analysis of reaction mechanisms. VCH Publishers Inc, New York. https://doi.org/10.1080/00945719408001398
Lindsley K, Vedula S, Cotter S, Mutti D, Twelker D (2011) Interventions to slow progression of myopia in children. Cochrane Database Syst Rev. https://doi.org/10.1002/14651858.CD004916.pub3
Lu S-T, Wu Y-C, Leou S-P (1987) The oxidation of isoquinoline alkaloids with M-chloroperbenzoic acid. J Chin Chem Soc 34:33–42. https://doi.org/10.1002/jccs.198700006
MTech Lab: http://chem.lnu.edu.ua/mtech/devices.htm
Mandava N, Fodor G (1968) Configuration of the ring nitrogen in N-oxides and the conformation of tropanes. Canad J Chem 46(17):2761–2766
Van Der Meer M, Hundt H, Müller F (1986) The metabolism of Atropine in man. J Pharm Pharmacol 38(10):781–784. https://doi.org/10.1111/j.2042-7158.1986.tb04494.x
Meti MD, Nandibewoor ST, Chimatadar SA (2014) Spectroscopic investigation and reactivities of ruthenium(III) catalyzed oxidation of anticholinergic drug atropine sulfate monohydrate by hexacyanoferrate(III) in aqueous alkaline media: a mechanistic approach. Synth React Inorg, Met-Org, Nano-Met Chem 44(2):263–272. https://doi.org/10.1080/15533174.2012.756027
Moffatt A (1986) Clarke’s isolation and identification of drugs, 2nd edn. Pharmaceutical Press, London. https://doi.org/10.1002/jps.2600760520
Parker W, Winfred E, Witnauer L, Swern D (1957) Peroxides. IV. 2 aliphatic diperacids. J Am Chem Soc 79(8):1929–1931. https://doi.org/10.1021/ja01565a043
Plotycya S, Dubenska L, Blazheyevskiy M, Pysarevska S, Sarahman O (2016) Determination of local anesthetics of amide group in pharmaceutical preparations by cyclic voltammetry. Electroanalysis 28(10):2575–2581. https://doi.org/10.1002/elan.201600134
Plotycya S, Pysarevska S, Dushna O, Dubenska L (2019) On mechanism of reduction on DME of some compounds with local anesthetic activity N-oxides containing tertiary amine. Visnyk Lviv Univ Ser Chem 60(1):191–199. https://doi.org/10.30970/vch.6001.191
Plotycya S, Strontsitska O, Pysarevska S, Blazheyevskiy M, Dubenska L (2018) A new approach for the determination of benzocaine and procaine in pharmaceuticals by single-sweep polarography. Int J Electrochem 2018:10. https://doi.org/10.1155/2018/1376231
Rang H, Dale M, Ritter J, Flower R (2007) Rang and Dale’s pharmacology′ Elsevier. Edinburgh. https://doi.org/10.1002/9781118819494
Rbeida O., Christiaens B., Hubert Ph., Lubda D., Boos K.-S., Crommen J., Chiap P. (2005) Integrated on-line sample clean-up using cation exchange restricted access sorbent for theLC determination of Atropine in human plasma coupled to UV detection. J. Pharm. and Biomed. Anal. 36(5): 947–954.https://doi.org/https://doi.org/10.1016/j.jpba.2004.08.007
Rodrigo G, Rodrigo C (2002) The role of anticholinergics in acute asthma treatment: an evidence-based evaluation. Chest 121:1977–1987. https://doi.org/10.1378/chest.121.6.1977
Steele W, Appelman E (1982) The standard enthalpy of formation of peroxymonosulfate (HSO5−) and the standard electrode potential of the peroxymonosulfate-bisulfate couple. J Chem Thermodyn 14(4):337–344. https://doi.org/10.1016/0021-9614(82)90052-0
Sun S, Lu J (2006) Flow-injection post chemiluminescence determination of Atropine sulfate. Anal chim acta 580(1):9–13. https://doi.org/10.1016/j.aca.2006.07.049
Turkevich M, Vladimirskaya O, Lesyk R (2003) Pharmaceutical chemistry (steroid hormones, their synthetic substitutes and heterocyclic compounds as drugs). Hova Kniga, Vinnytsia
Vaz N, Manjunatha AS, Puttaswamy, (2016) Mechanistic insight into the oxidation of atropine sulfate monohydrate with aqueous acidic chloramine-T: design of kinetic modeling. Bul Chem Commun 48(4):671–677
Wang J (1988) Electroanalytical techniques in clinical chemistry and laboratory medicine. Wiley-VCH, Weinheim
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This work was financed by the Ministry of Education and Science of Ukraine (Grant number 0116U001541).
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Dubenska, L., Dushna, O., Blazheyevskiy, M. et al. Kinetic and polarographic study on atropine N-oxide: its obtaining and polarographic reduction. Chem. Pap. 75, 4147–4155 (2021). https://doi.org/10.1007/s11696-021-01638-3
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DOI: https://doi.org/10.1007/s11696-021-01638-3