ASCORBIС ACID DEGRADATION IN N, N-DIMETHYLFORMAMIDE SOLUTIONS

A. V. SYROESHKIN; T. V. PLETENEVA; E. V. USPENSKAYA; I. I. SAYDINOV; O. V. LEVITSKAYA; T. E. ELIZAROVA; M. A. TRIBOT-LASPIERE; A. I. ODNOVOROV

doi:10.22159/ijap.2020v12i2.36705

Authors

A. V. SYROESHKIN Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
T. V. PLETENEVA Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
E. V. USPENSKAYA Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
I. I. SAYDINOV Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
O. V. LEVITSKAYA Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
T. E. ELIZAROVA Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
M. A. TRIBOT-LASPIERE Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
A. I. ODNOVOROV Department of Pharmaceutical and Toxicological Chemistry, Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation

DOI:

https://doi.org/10.22159/ijap.2020v12i2.36705

Keywords:

Ascorbic acid, Dicyclic monomer, Dimer DHA, N, N-dimethylformamide, Dimethylamine, Enamines

Abstract

Objective: Investigate the mechanisms of L-ascorbic acid transforтmation and formation of coloured enamines in N, N-dimethyl-formamide solutions.

Methods: An automatic polarimeter Atago POL-1/2 was used for polarimetric investigation. Electronic spectra were recorded by UV-spectrometer Cary 60 (Agilent). The statistical analysis was carried out using the OriginPro 9.1 packages.

Results: The Biot’s law violation was found in below 0.1% solutions of L-ascorbic acid (AA) in N, N-dimethylformamide (DMF). During the day, the specific rotation of 1% AA solution varied from+37 to-1.0. Gradually, the solution acquired the red colour, and its intensity depended on the AA concentration. Spectrophotometrically, it was shown that after 15 min AA was absent in the n·10-3% solutions. The decomposition followed the first-order kinetics (k₁=1.83·10^-2с^-1). At the same time, new absorption bands appeared at 273, 390, 533 nm. Model solutions containing dimethylamine (DMA) had a similar spectrum, and the intensity of the absorption bands increased in proportion to the concentration of DMA.

Conclusion: The results show that the first step in the decomposition of ascorbic acid AA in DMF follows first-order kinetics. Numerous decomposition products are optically active compounds and reverse the sign of the optical rotation of the solution. The water resulting from the decomposition of AA is involved in the hydrolysis of the solvent. The hydrolysis product, the secondary amine DMA, interacts with the carbonyl groups of the AA decomposition products to form coloured enamines. Magnesium (II) accelerates the formation of coloured products.

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References

Marsella JA. Kirk-Othmer encyclopedia of chemical technology. Dimethylformamide. New York: John Wiley and Sons; 2003.

Rahman N, Singh M, Hoda MN. Optimized and validated spectrophotometric methods for the determination of lisinopril in pharmaceutical formulations using ninhydrin and ascorbic acid. J Braz Chem Soc 2005;16:1001-9.

Adam MA, Shantier SW, Alfangari SA, Gadkariem EA. Development of a spectrophotometric method for the assay of aminocaproic acid in dosage forms using ascorbic acid. Chem Sci Trans 2015;4:478-82.

El-Obeid HA, Gad-Kariem EA, Al-Rashood KA, Al-Khamees HA, El-Shafie FS, Bawazeer GAM. A selective colourimetric method for the determination of penicillins and cephalosporins with α-aminoacyl functions. Anal Lett 1999;32:2809–23.

El-Shafie FS, Gad-Kariem EA, Al-Rashood KA, Al-Khamees HA, El-Obeid HA. Colourimetric method for the determination of ampicillin and amoxicillin. Anal Lett 1996;29:381-93.

Hayashi T, Terao A, Ueda S, Namiki M. Red pigment formation by the reaction of oxidized ascorbic acid and protein in a food model system of low moisture content. Agric Biol Chem 1985;49:3139-44.

Larisch B, Pischetsrieder M, Severin T. Reactions of dehydroascorbic acid with primary aliphatic amines including nr-acetyllysine. J Agric Food Chem 1996;44:1630-4.

Zhang Y, Xie S, Yan M, Ramström O. Dynamic covalent chemistry of aldehyde enamines: Bi(III)-and Sc(III)-catalysis of amine-enamine exchange. Chem Eur J 2017;23:11908-12.

Juillard J. Dimethylformamide: purification, tests for purity and physical properties. Pure Appl Chem 1977;49:885-92.

Trotta F, Mele A. Nanosponges synthesis and applications. Weinheim: John Wiley and Sons; 2019.

Syroeshkin AV, Pleteneva TV, Uspenskaya EV, Levitskaya OV, Tribot-laspiere MA, Zlatsky IA. Polarimetric research of pharmaceutical substances in aqueous solutions with different water isotopologues ratio. Int J Appl Pharm 2018;10:243-8.

Green MM, Reidy MP, Johnson RD, Darling G, O’Leary DJ, Willson G. Macromolecular stereochemistry: the out-of-proportion influence of optically active comonomers on the conformational characteristics of polyisocyanates. The sergeants and soldiers experiment. J Am Chem Soc 1989;111:6452-4.

Van Dijken DJ, Stacko P, Stuart MCA, Browne WR, Feringa BL. Chirality controlled responsive self-assembled nanotubes in water. Chem Sci 2017;8:1783-9.

Goncharuk VV, Syroeshkin AV, Pleteneva TV, Uspenskaya EV, Levitskaya OV, Tverdislov VA. On the possibility of chiral structure-density submillimeter inhomogeneities existing in the water. J Water Chem Technol 2017;39:319-24.

European Pharmacopoeia 8.0 V.1-2. Strasbourg: Council of Europe; 2014.

U. S. Pharmacopoeia 40-National Formulary 35. USA; 2017.

Japanese Pharmacopoeia. 17th ed. Japon; 2016.

Hvoslef J, Pedersen B. The structure of dehydroascorbic acid in solution. Acta Chem Scand B 1979;33:503-11.

Hvoslef J, Pedersen B. Structure of dehydroascorbic acid isomers in solution. Carbohydr Res 1981;92:9-20.

Hvoslef J, Hope H, Murray BD. On the stability of symmetric dimers of dehydroascorbic acid: a study of the esters in the crystalline and the solute state. Carbohydr Res 1986;147:11-9.

Parfenov EA, Zaikov GE. Biotic type antioxidants: the prospective search area for novel chemical drugs. London: TaylorandFrancic Group; 2000.

Kerber RC. As simple as possible, but not simpler-the case of dehydroascorbic acid. J Chem Educ 2008;85:1237-42.

Tu YJ, Njus D, Schlegel HB. A theoretical study of ascorbic acid oxidation and HOO˙/O2˙-radical scavenging. Org Biomol Chem 2017;15:4417-31.

Syroeshkin AV, Pleteneva TV, Uspenskaya EV, Levitskaya OV, Barsegyun SS, Zlatsky IA, et al. The effect of thermal sterilization and excipients on the stability of ascorbic acid in aqueous solutions. Int J Appl Pharm 2019;11:313-6.

Toral MI, Lara N, Richter P, Tassara A. Simultaneous determination of ascorbic acid and acetylsalicylic acid in pharmaceutical formulations. J AOAC Int 2001;84:37-42.

Tajmir Riahi HA. Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution. J Inorg Biochem 1990;40:181-8.

Enders D, Schaumann E. editors. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations. Vol. 40a. New York: Thieme; 2014.

Christie R. Colour chemistry. Cambridge: Royal Society of Chemistry; 2001.

Klu MW, Addy BS, Oppong EE, Sakyi ES, Mintah DN. Effect of storage conditions on the stability of ascorbic acid in some formulations. Int J Appl Pharm 2016;8:26-31.

Ledl F, Beck J, Seng M, Osiander H, Estendorfer S, Severin T, et al. Chemical pathways of the malliard reaction. Prog Clin Biol Res 1989;304:23-42.

Hsu HY, Tsai YC, Fu CC, Wu JSB. Degradation of ascorbic acid in ethanolic solutions. J Agric Food Chem 2012;60:10696-701.