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ХИМИЧЕСКИЕ НАУКИ
SYNTHESIS OF THE Zn (II) COMPLEX BASED ON BENZOYLACETALDEHYDE PRODUCTS, THEIR STRUCTURE
AND PROPERTIES Sadullaeva G.G.
Sadullaeva Gulmira Gaybullaevna - Assistant, DEPARTMENT OF MEDICAL CHEMISTRY, BUKHARA STATE MEDICAL INSTITUTE, BUKHARA, REPUBLIC OF UZBEKISTAN
Abstract: the author synthesized a Zn (II) complex compound based on benzoylacetaldehyde derivatives, the structure of the obtained new complex compounds was determined and obtained using IR, H1-NMR, analytical methods
Keywords: benzoylacetaldehyde, coordination compounds, 1H-NMR spectroscopy, Acylhydrazone derivatives, 3-phenyl-3-oxopropanal benzoylhydrazone.
СИНТЕЗ КОМПЛЕКСА Zn (II) НА ОСНОВЕ БЕНЗОИЛАЦЕТАЛЬДЕГИДНЫХ ПРОДУКТОВ, ИХ СТРУКТУРА И СВОЙСТВА Садуллаева Г.Г.
Садуллаева Гулмира Гайбуллаевна - ассистент, кафедра медицинской химии, Бухарский государственный медицинский институт, г. Бухара, Республика Узбекистан
Аннотация: автором синтезировано комплексное соединение Zn (II) на основе производных бензоилацетальдегида, структура полученных новых комплексных соединений определена и получена с использованием ИК, Н1-ЯМР, аналитических методов
Ключевые слова: бензоилацетальдегид, координационные соединения, 1Н-ЯМР спектроскопия, производные ацилгидразона, 3-фенил-3-
оксопропанальбензоилгидразон.
UDC 547.61
Due to their unique structure and properties, coordination compounds are widely used in the chemical industry, agriculture and medicine. Today, the synthesis of complex compounds of heterocyclic ligands with 3d metals and the determination of their properties are theoretically and practically relevant. It is important to use such metal complexes in medicine as biologically active substances, antioxidants, dyes, additives and corrosion inhibitors in various industries.
The obtained complex compounds are widely used in gas-liquid chromatography and other fields due to their extragenic properties. These compounds are also used as chelating and gliding reagents in 1H-NMR spectroscopy. In this regard, it is important, on the basis of local raw materials, to produce new types of stimulants that increase the yield of agricultural crops, to synthesize complex compounds of salts of many metals with organic ligands, to determine the structure, electronic structure, reactivity, and physicochemical properties. , biological activity.
Purpose of the study
The aim of the study was to determine the synthesis, structure and properties of Zn(II)complexes of para-exchange hydrazones of benzoic acid of benzoylacetaldehyde. On
the basis of which the new tridentate is intended for the synthesis, tautomerism and complexation of organic ligands in order to determine their structure
Materials and methods:
In the course of the study, Zn (CH3COO)2 the purity level of "p.a" was used for the synthesis of complex compounds. The amount of metals in the synthesized compound was recorded on an atomic absorption spectrophotometer of the analytical company Jena AG (Germany) brand novAA 300. Organic solvents and other reagents used in the studies were purified and dried according to [4-5]. The analysis of metals in complex compounds [6] was carried out on a Perkin-Elmer 3030 V spectrophotometer (USA) by atomic adsorption, nitrogen — by the Dumas method, carbon and hydrogen — by combustion in a stream of Carlo-Erba-1106 oxygen. element. found in the analyzer, analysis data calculated on exposure to HEC-960.
The IR spectrum was recorded on a KBr tablet in the range of 400-4000 cm-1 on an IRTraser-100 spectrometer (400-4000 cm-1) (Institute of Physics and Chemistry of Polymers of the Academy of Sciences of the Republic of Uzbekistan) by Shimadzu [7].
1H-NMR spectra of 5-10% solutions of ligands were obtained on spectrometers Bruker DPX-300 (300.13 MHz) and Unity 400 plus (Option) (Institute of Plant Chemistry of the Academy of Sciences of the Republic of Uzbekistan). Chemical shifts were measured relative to a reference. Tetramethylsilane (TMS), deuterium solvents: CDCl3 and DMSO-d6 were used as standard. Signals corresponding to different tautomeric forms were combined to assess the content of tautomers [6, 8 - 9].
Experiments on RSA analysis were carried out in the scientific laboratory "Physical research methods" of the Institute of Bioorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan on a CCD diffractometer "Xcalibur, Oxford Difference" (CuKa radiation, l = 1.5418). , graphite monochromator). Experimental data were collected using CrysAlisPro. Corrections for swallowing Method of "multiple scan" in the software package CrysAlisPro [10-12]. was carried out with. The structure of the compounds was studied by a direct method using a set of applications [13-14].
Acylhydrazone derivatives with 1,3-diketones of the ketoaldehyde types are linear: hydrazone, jenghydrazine, and ring 5-hydroxypyrazoline are very important starting objects in the study of tautomeric equilibrium. In this study, benzoic acid hydrazines were selected as nucleophilic reagents. Benzoic acetaldehyde was synthesized by the reaction of benzoic acid with ethyl ether and chlorinated acetaldehyde in the presence of sodium ethylate. According to H1-NMR spectroscopy, the keto-yenol tautomer is in an equilibrium state in a ketoaldehyde solution [2, 17-18].
For the synthesis of organic compounds containing H2Lj-3, interactions were carried out in an alcoholic solution of benzoylacetaldehyde in an alcoholic solution of equivalent moles of aroylhydrazones [2].
Synthesis of 3-phenyl-3-oxopropanal benzoylhydrazone.
2.96 g (0.02 mol) of pure distilled benzoylacetaldehyde was added dropwise to a solution of 80 methanol, and 2.72 g (0.02 mol) of benzoic acid hydrazide in a solution of 120 methanol was slowly added with stirring. The reaction mixture was left at room temperature for 2 days. The resulting precipitated polycrystals were first filtered and then washed with a small amount of water, ethanol-hexane. After recrystallization of the obtained polycrystals from a saturated solution of methane, 3.46 g (65%) of benzeneacetabenzoylhydrazone (H2Lj) were obtained. Liquid = 128 °C.
3-phenyl-3-oxopropanalparamethylbenzoylhydrazonisynthesis
1.48 g (0.01 mol) of 3-phenyl-3-oxopropanal was added dropwise to 40 ml of ethanol while stirring 1.50 g (0.01 mol) of para-methylbenzoic acid hydrazide in 90 ml of ethanol. The resulting reaction mixture was left at room temperature for 1 day. The resulting crystals were filtered off and washed with small amounts of ethanol and diethyl ether. After recrystallization from ethanol, 2.02 (72%) of 3-phenyl-3-hydroxypropanal para-methylbenzoylhydrazone (H2L2) was obtained (Scheme 8). Liquid = 157 ° C
C6H5
V
II
O
CH2
H
C
II
O
C6H5 \ /
C
II
^ O
CH2
H
N.
+
-H2O
H3C- C6H4~CO-NH-NH
2
O
4NH
I
^-CeH4-CH3
1-scheme.
An analogous H2L3 was synthesized. Their reaction yield, liquidus temperature and elemental analysis results are presented in Table 1 [3]
Table 1. The reaction product of aroylhydrazones of benzoylacetaldehyde (H2L1-3),Results of analysis of liquid temperature and elemental composition
Connect ions R Unum, % T 1 suyuqi oC Formula Gross Found / Calculated %
C H N
H2L1 C6H5 65 128 C16H14N2O2 71,93/72,16 5,22/5,30 10,68/10,52
H2L2 P-CH3C6H4 72 157 C17H16N2O2 72,86/72,84 5,72/5,75 10,02/9,99
H2L3 m- CH3OC6H4 83 163 C17H16N2O3 68,94/68,91 5,49/5,44 9,63/9,45
Complexes containing ML • NH3 (M2+ = Zn) were synthesized by the interaction of ammonia solutions of metal acetates with alcohol solutions of equivalent amounts of ligands [2, 19]. Has a structure:
II I
N X/
Il M
R=C6H5, A=NH3,M= Zn (Zn LlNH3), A=Py (Zn L^Py), R=«-CH3C6H4,A=Py, M= Zn (II) (Zn L2Py),R=«-CH3°C6H4, A=Py, M= Zn (II) (Zn L3Py),
R=C6H5, A=NH3,M=Zn (ZnL1NH3).
It should be noted that ammonia complexes are readily soluble in organic solvents, but poorly soluble in water, refers to [22]. In the IR spectra of the complexes, there is no absorption line above 1640 cm-1, corresponding to the free carbonyl group. In the IR spectra of all complex compounds in the fields of 1580-1585, 1530-1540, 1470-1480, 14201430, 1395-1400 cm-1, there are a number of absorption lines of medium and strong intensity, which are valence. and stretching-deformation vibrations. The frequency of stretching vibrations of the S - O bond does not decrease by 15-25 cm-1, while the frequency of the C = N bond increases by 5-10 cm-1, confirming that coordination coordination occurs through oxygen atoms [16-18].
As expected in the spectrum of the ZnL1 • Py and ZnL2 • Py complexes, absorption lines are not observed in this area, but a 1600 cm-1valent oscillation line of category n (C = O) appears.
Fig. 1. ZnL1 • IR spectrum of the complex compound NH3 (III), pressed in a KBr tablet Conclusions:
1. New ketoaldehyde, ketoesters were obtained by the Klisen condensation reaction, on the basis of which 3 new organic ligands and 3 and complex compounds of Zn (II) ions were synthesized and crystallized using elemental analysis, IR, 1H-NMR spectroscopy. and RSA methods Determined the composition and structure of the corpus and solutions
2. Complex compounds of trans- [N2O2] complexes .Zn (II) were proved by IQ-, 1H-NMR spectroscopy, consisting of donor atoms, 1 single crystal of the new ligand, 1 complex compound were grown and their structure was confirmed by RSA.
References / Список литературы
1. Oliveira C. et al. Hydroxybenzoic acid derivatives as dual-target ligands: mitochondriotropic antioxidants and cholinesterase inhibitors // Frontiers in chemistry, 2018. Т. 6. Р. 126.
2. Schuster Bernhard and Herrmann Karl. "Hydroxybenzoic and hydroxycinnamic acid derivatives in soft fruits". Phytochemistry 24.11 (1985): 2761 -2764.
3. Bourke, Jean et al. "The synthesis and biological evaluation of mycobacterial p-hydroxybenzoic acid derivatives (p-HBADs)." Organic & biomolecular chemistry 12.7 (2014): 1114-1123.
4. Seidel C. et al. 4-Hydroxybenzoic acid derivatives as HDAC6-specific inhibitors modulating microtubular structure and HSP90a chaperone activity against prostate cancer // Biochemical pharmacology, 2016. Т. 99. Р. 31-52.
5. Herrmann K., Nagel C.W. Occurrence and content of hydroxycinnamic and hydroxybenzoic acid compounds in foods // Critical reviews in food science & nutrition, 1989. Т. 28. №.4. Р. 315-347.
6. Podolesov Bojan. "Oxidation of. beta.-diketones with (diacetoxyiodo) benzene". The Journal of Organic Chemistry 49.14 (1984): 2644-2646.
7. Akhmedov V.N. et al. The method of producing hydrophobic organosilicon polymers based on hydrolyzed polyacrylonitrile // Chemical Journal of Kazakhstan, 2019.
8. Tkach V.V. et al. The Theoretical Description for Fluoxetine Electrochemical Determination, Assisted by CoO (OH)-Nanoparticles, Deposited Over the Squaraine Dye // Orbital: The Electronic Journal of Chemistry, 2021. T. 13. № 1. P. 53-57.
9. Dzhuraev D.R. et al. The spontaneous orientation phase transition in terbium-yttrium ferrite-garnet, 2011.
10. Umarov B.B., Tursunov M.A., Minin V.V. Kompleksy s proizvodnymi ketoal'degidov i ketoefirov. Tashkent. Nishon-noshir, 2016. 350 c.
11. Veygand-Khil'getag. Metody eksperimenta v organicheskoy khimii. Perevod s nem. yazyka pod redaktsiyey prof. N.N. Suvorova. M.: Khimiya, 1968. S. 847-886.
12. Skopenko V.V., Tsivadze A.Yu., Savranskiy L.I., Garnovskiy A.D. Koordinatsionnaya khimiya: uch. posob. M.: IKTS "Akadem kniga", 2007. 487 s.
13. Milway V.A., Niel V., Abedin T.S.M., Xu Z, Thompson L.K., Grove H, Miller D.O., Parsons S.R. Octanuclear and Nonanuclear Supramolecular Copper(II) Complexes with Linear "Tritopic" Ligands: Structural and Magnetic Studies // Inorg. Chem., 2004. V. 43. P. 1874-1884.
14. Reutov O.A., Kurts A.A., Butin K.P. Organicheskaya khimiya. Ucheb. posobiye dlya VUZov. M.: Izd-vo MGU, 1999. Chast' I. 560 s.
15. Pentin YU.A., Vilkov L.V. Fizicheskiye metody issledovaniya v khimii. M.: Mir, 2003. 683 s.
16. Nakamoto K. IK spektry i spektry KR neorganicheskikh i koordinatsionnykh soyedineniy. M.: Mir, 1991. 536 s.
17. Dzhuraev D.R. et al. The spontaneous orientation phase transition in terbium-yttrium ferrite-garnet, 2011.
