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Tulakov Nurullo Kosimovich, Andijan State University Senior Lecturer of the Department of Chemistry E-mail: [email protected] Askarov Ibragim Rahmanovich, Andijan State University Doctor of Chemical Sciences, Professor of the Department of Chemistry Isaev Yusup Tozhimatovich, Andijan State University Candidate of Chemical Sciences, Head of the Department of Chemistry Yusupova Zarifa Atajanovna, Student 3 course direction Chemistry
SYNTHESIS AND SPECTRAL RESEARCH OF POTASSIUM SALT OF FERROCENCARBONIC ACID
Abstract: The method of synthesis of potassium salt of ferrocenic acid is shown in the article, which shows a high biological activity for living organisms. Based on the analysis of the data, the IR and MASS spectra of the starting and derivative reactions were determined that a monosubstitution product was obtained in the reactions.
Keywords: monoacetylferrocene, potassium salt of ferrocenic acid, biostimulant, reactions, spectral studies, biological activity.
Although more than 60 years ago, dicyclopen- As is known, one of the main requirements for
tadienyl iron-ferrocene (Fc) has been discovered, biologically active substances is their solubility in
many of its derivatives are well known, and intensive water. Most ferrocene derivatives are poorly solu-
scientific research is now being carried out to obtain ble in water. To eliminate this deficiency they are
new, practically significant derivatives. transferred to the corresponding sodium or potas-
Among the synthesized derivatives of fer- sium salts. For example, ferrocene-containing sub-
rocene are many biologically active representa- stance introduced into medical practice as an anti-
tives. The biological activity of such ferrocene anemia agent - "Ferroceron" is the sodium salt of
compounds has been proved by many experi- o-carboxybenzoylferrocene [1]. Sodium and potas-
mental studies and some of them have been in- sium salts of p-ferrocenylphenol are proposed as ef-
troduced into practice. fective biostimulators of agricultural plants [2].
o ,—, O
C^^ -OH
K^? COONa
Figure 1. (Ferrocenecarbonyl) sodium benzoate
The literature contains extensive material on the of ferrocene are oxygen-containing compounds, in-synthesis and various transformations of ferrocene cluding carboxylic acids [3; 4]. and its derivatives. One of the important derivatives
O
m
OH
COONa
Figure 2. Ferrocenyl (4-hydroxyphenyl) -methanone
A large number of carboxylic acids containing a ferrocene group have been synthesized. In these compounds, the ferrocene is directly bonded to the carboxyl group or linked via a carbon chain.
Ferrocenecarboxylic acids are obtained in several ways, differing in the method of formation of the carboxyl group: carboxylation of ferrocene, hydrolysis -COCH3
2NaOH , Br
of nitriles, oxidation of substituted ferrocenes [1]. Oxidation methods can be considered more convenient, since they do not require special conditions and equipment. Therefore, in this paper, we used the oxidation of monoacetylferrocene to produce fer-rocenic acid. As an oxidizer, sodium hypobromite was used.
COONa
2
H+
-COOH
rc
■ NaBr , H2O , CO
2
r c
-Na+
rc
Figure 3. Scheme for the preparation of ferrocenecarboxylic acid from acetylferrocene
The potassium salt of ferrocene-carboxylic of the obtained salt was studied by IR and mass acid was prepared by dissolving an acid sample in spectroscopy. Thus, the intense bands at 1661 cm-1
a 0.5 M solution of potassium hydrogen carbonate. This method is widely used for the preparation of salts of organic acids [5]. The structure
and 1653 cm-1 correspond to the asymmetric valence vibration of C=O in the carboxylate ion [6].
-COOH
+ KHCO
COOK
Figure 4. Scheme for the preparation of potassium salt of ferrocenic acid
In this spectrum, two intense absorption bands can be observed in the 1356 and 1388 cm-1 regions, also characteristic of the carboxylate ion (vsymme). The presence of a ferrocenyl group can be established by characteristic absorption bands in the region of 3096, 1005, 1021, and 1105 cm1 [1].
The data are consistent with mass spectroscopy data. Thus, the mass spectrum of the salt contains an intense peak with m/z 229.0478 corresponding to the carboxylate ion and a less intense peak with m/z 186.0267 corresponding to the ferrocenyl cation [7].
Experimental part
Reagents and equipment. The melting points were determined on a SMP10 (Germany) instrument, the IR spectra were recorded on a PerkinElmer Spectrum spectrometer (Version 10.4.2), the mass spectra were recorded with a liquid chromatography mass spectrometer PerkinElmer AxlON 2 TOF MS.
Technique of the experiment. Ferrocenic acid. In a three-necked flask with a volume of 0.5 l, equipped with a thermometer, a dropping funnel and a mechanical stirrer, 4 g (0.1 mole) of sodium hydroxide and 20 ml of water were placed. 4.8 g (0.03 mole)
of bromine were added dropwise to the alkali solution of monoacetylferrocene in 10 ml of dioxane was add-at a temperature ofno more than 10 °C. The tempera- ed dropwise to the reaction mixture. ture was then lowered to 0 °C, and 2.28 g (0.01 mole)
4QQQ J5D0 3000 2500 2000 . 1500 1000
Figure 5. IR spectrum of the potassium salt of ferrocenecarboxylic acid
Figure 6. Chromatomass spectrum of potassium salt of ferrocenic acid
Technique of the experiment. Ferrocenic acid. was added dropwise. The cup was placed in a water
In a three-necked flask with a volume of0.5 l, equipped bath and heated gently with stirring until the wa-
with a thermometer, a dropping funnel and a mechan- ter evaporated completely. After that, the dish was
ical stirrer, 4 g (0.1 mole) of sodium hydroxide and cooled, a dark yellow precipitate was isolated. The
20 ml of water were placed. 4.8 g (0.03 mole) of bro- yield is 0.2 g (87%), T. m. = 284-285 °C. The gross
mine were added dropwise to the alkali solution at a formula is C11FeH9O2K.
temperature of no more than 10 °C. The temperature Thus, we synthesized the potassium salt of fer-
was then lowered to 0 °C, and 2.28 g (0.01 mole) of rocenic acid and established the structures using IR
monoacetylferrocene in 10 ml of dioxane was added and chromatographic mass spectroscopy. We have for
dropwise to the reaction mixture. the first time synthesized the oxidation reaction prod-
Potassium salt of ferrocene-carboxylic acid. uct - ferrocenecarboxylic acid and its salts according
0.23 g (0.01 mol) of ferrocenecarboxylic acid was to the technique that we have improved. Based on the
placed in a porcelain cup. To the acid, 2 ml of a analysis ofthe obtained spectral data, the structure of
0.5.M solution of potassium hydrogencarbonate the products of the reactions was confirmed.
References:
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4. Askarov. I. R., Abdujabbarova M.Sh., Khozhimatov M. M., Tulakov N. K. Synthesis of ferrocenylphenols based on the diazotization reaction. Scientific Bulletin of the ASU. Andijan. Uzbekistan. - 2015. - No. 1. - P. 15-20.
5. Tulakov N. K., Kirghizov Sh. M. Preparation of a water-soluble ferrocene derivative. Materials of the republican scientific-practical conference "Actual problems of chemical science and innovative technologies of its training" (With participation of foreign scientists). Tashkent. March 30-31, - 2016. -158 p.
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