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Section 8. Chemistry
https://doi.org/10.29013/AJT-20-9.10-47-52
Kodirov Abduakhad Abdurakhimovich, PhD in chemistry, docent, Qarshi State University, Uzbekistan
E-mail: [email protected] Chuliyev Jamshid Ruzibayevich, scientific researcher, Qarshi engineering- ekonomical institute Mamarakhmonov Mukhamatdin Khomidovich, PhD in chemistry, docent, department of chemistry, Andijan State University, Uzbekistan, Andijan E-mail: [email protected] Askarov Ibragim Rakhmanovich, Doctor of chemical Sciences, professor, Department of Chemistry, Andijan State University, Uzbekistan, Andijan
E-mail: [email protected]
SYNTHESIS, CRYSTAL STRUCTURE OF MONO-AND BIS a-AMINONITRILES AND CLASSIFIATION BASED ON CHEMICAL COMPOSITION
Abstract. This article presents the results of the synthesis of new derivatives of a-aminonitriles. As well as the physicochemical properties of the synthesis products were studied. The crystal structure of the synthesized products was confirmed by X-ray analysis. The chemical composition of the newly obtained products was studied and classified by digital brand codes.
Keywords: a-Aminonitriles, synthesis, anhydrides of acids, biological activity, IR-spectra, X-Ray, Chemistry of goods, classification, digital brand code.
Introduction of the new subject "Chemistry of goods", created in
a-Aminonitriles are the subject of many sci- Uzbekistan in 2017.
entific studies by chemists. This article solves the Experimental
problems of synthesis of new biologically active Impressive reagents in the reaction are a-amino
compounds of a-aminonitriles, study of the spa- nitriles, anhydrides of acids are taken in proportion
tial crystal structure and classification according 1:1 by moles, give mono acyl product, and reaction
to their chemical composition. By us synthesized mainly goes to the free amino group. If reagents tak-
some new products of a-aminonitriles. The classi- en by 2:1 proportion, accordingly, observed that,
fication of goods is done according to the methods reaction give bis-acyl product. In the first case, the
reaction proceeds well at room temperature, while in the second case, the reaction mixture must be heated to the boiling point of the reaction solvent in order to complete the reaction [1-3]. The reaction of N-mono(a-cyanisopropyl) ethylenediamine with
CH3
I 3
H3C—C-NHCH2CH2NH2 + (C6H5CO)2O CN
benzoic acid anhydride is similar to its reaction with acetic acid anhydride. The formation of N-benzoyl-N'-(a-cyanisopropyl) ethylenediamine (I) with high yields was observed when the reactants were obtained in a 1: 1 molar ratio.
1:1
2.1
CH3
I
H3C—c-nhch2ch2nhcoc6h5
CN J
CH3
I 3
H3C—c-nch2ch2nhcoc6h5
CN
II
N, N'-dibenzoil-N- (a -cyanisopropyl)ethylene-diamine (II) was formed with high yields when the reactants were obtained in a ratio ofl: 2 moles and the reaction was carried out at the boiling point of the solvent.
In the IR spectrum of the above compounds (III) the quantities corresponding to the absorption spectra ofthe aromatic ring are 1625-1575 cm-1, and the absorption spectra of the NH- and CN-groups
The results of the study of the primary biological activity of the compound N, N'-bis-(a-cyanisopropyl) ethylenediamine showed that it has a high stimulatory property. In order to obtain
are 3320-3360 cm-1 and 2220-2231 cm-1 was found to be present [4-5].
In the mass spectra of these compounds, the presence of high percentages of the peak corresponding to the molecular ion intensity of the compounds was observed. For example, the molecular ionic peak intensity of N, N'-dibenzoil-N- (a-cyanisopropyl) ethylenediamine (II) was m/z 335, and its percentage was 21%.
CH3 COCH3 CH3 H3C—C- N(CH2)2NH- c— ch3
1:1
CH3 CH3
I 3 I 3
H3C—C-NH(CH2)2 NH- C— CH3 + (CH3CO)2O
CN CN
CN
III
O
CN
2:1
CH3
C CH3 A I 3 /CH3 H3C—C- N(CH2)2N- c—ch3
CN
O
C
\ CN
CH3
IV
new biological active derivatives, we studied the reactions of N, N'-bis-(a-cyanizopropyl)ethylene-diamine with various acid anhydrides. It should be noted that the structure of the compound formed
by the reactions of N, N'-bis-(a-cyanisopropyl)eth-ylenediamine with acid anhydrides depends on the mole ratio of the reacting compounds.
It was observed that N-monoacyl product is formed as a reaction product when reactive reagents are used in the ratio of 1: 1 mol, and bis-acyl product is formed when the reaction is carried out in the ratio of 2: 1 mol. In studying the reactions of N, N'-bis-(a-cyanisopropyl)ethylenediamine with acid anhydrides, we used acetic acid anhydride as the anhydride. Therefore, the formation of N-monoacetyl-N, N'-bis-(a-cyanisopropyl) ethylenediamine (II) as a reaction product was observed. When using reactive reagents in a ratio
of 1: 2 moles, the formation of bis-acetyl product N, N'-diacetyl-N, N'-bis-(a-cyanisopropyl)eth-ylenediamine (III) as a reaction product was observed. In both cases, the reaction was carried out at the boiling temperature of the reaction mixture (solvent).
In the study of the reactions of aromatic acid anhydrides of N, N'-bis-(a-cyanisopropyl) ethylenedi-amine, we used benzoic acid anhydride as an aromatic acid. The reaction was carried out under the same conditions as with acetic acid anhydride, and it was found that with high yields (77%) N-monobenzoyl-N, N'-bis- (a-cyanisopropyl)ethylenediamine was formed (Table 1).
Table 1.- Physicochemical characteristics of mono- and bis-acyl products of some a-aminonitriles
Compounds Ratio,% Tm, melting point, °C Rf Molecular weight Brutto formula
III 75 162-164 0.65 236 с.ВДО
IV 80 174-175 0.78 278 С14Н2Л02
V 77 150-152 0.46 298 С17НЛ0
VI 82 245-247 0.38 402 с24ВД°2
When using reactive reagents in a ratio of 1: 2 (a-cyanisopropyl)ethylenediamine (VI) in high moles, the formation of N, N'-dibenzoil-N, N'-bis- yields as a reaction product was observed.
COC6H5 CH3
Thus, it was observed that the reactions of N, N'-dibenzoil-N, N'-bis-(a-cyanisopropyl)ethylene-diamine with acid anhydrides (vinegar and benzoic acid) proceed under harsh conditions relative to monoamines. This situation is explained by the low degree of basicity of the secondary amino group in
1-1
CH3 CH3
I I
H3C—C-NH(CH2)2 nh- C— CH3 + (C6H5CO)2O-
CN CN
CH3
H3C—C- N(CH2)2NH- c— ch3
CN
CN
2-1
CH
\
V O
C C6H5
да
H3C-C-N(CH2)2N-C-CH3
CN C
VI
CN
the bird state relative to the nitrile group relative to the free amino group, as well as the high CN-group. Therefore, the mono- and diacylation reactions take place under the same conditions, and it was found that the direction of the reaction depends on the mole ratio of the reacting aminonitrile-anhydride reagents.
Materials and methods
In that investigation we used by organic synthesis methods, various analytical observation methods, IR-, Mass- spectral and modern X-Ray crystallographic methods. We studied their structure by X-ray structural analysis in order to analyze the relationship between the structure and chemical properties of some of the a-aminonitrile
derivatives obtained [5-6]. One of these substances, N, N-bis-(a-cyanisopropyl) ethylenedi-amine crystallizes in a triclinic spatial group with a center of symmetry. The asymmetrical part of a crystal cell consists of a single molecule. Although the molecule is symmetrically symmetrical, no symmetry is observed in its spatial structure in the crystalline state.
Figure 1. Spatial structure of N, N-bis-(a-cyanisopropyl)ethylenediamine molecule
In the molecule, the amino-group nitrogen atoms are in the sr3 hybrid state, and their configurations are reflected relative to the mutual plane. The lengths of the bonds in the molecule correspond to the average statistical values. The garden lengths are given in Table 1. The spatial structure of the molecule is shown in Figure 1. Analysis of intermolecular interactions shows that molecular dimers were formed in
the crystal by means of a pair of symmetrical hydrogen bonds of the NH... NC type (Fig. 2).
Elemental cell parameters and diffracted X-ray intensities were determined on a CCD Xcalibur Ruby (Oxford diffraction) diffractometer. The crystallographic computer program SHELXTL was used to find the structure ofthe compound. The crystal cell parameters and calculation results are given in (Table 2).
Table 2.- Bond lengths (A) obtained by X-Ray crystallographic method
Bonds Length, A Bonds Length, A
N1-C3 1.456 (3) C3-C5 1.488 (4)
N1-C1 1.469 (4) C3-C7 1.526 (4)
N2-C4 1.455 (4) C3-C9 1.536 (4)
N2-C2 1.457 (4) C4-C6 1.499 (4)
N3-C5 1.141 (4) C4-C10 1.516 (4)
N4-C6 1.135 (4) C4-C8 1.524 (4)
C1-C2 1.515 (4)
The geometry of the hydrogen bond is as follows: N1 - H1 0.85 (3) A N1 - H1 ... N4 2.46 (3) A N1 . N4 3.290 (4) A N1 H1 N4 angle 169 (3)
Figure 2. Intermolecular hydrogen bonding in a crystal
X-ray structural experiment. X-ray diffraction analysis showed that the crystals of the substance were grown at room temperature from a solution of N, N-bis-(a-cyanisopropyl)ethylenediamine. The results show that a-aminonitriles have the ability to form complex compounds with various biometals. They can also form both intramolecular and intermolecular complexes [7-8].
Results
Various functional groups were obtained by IR-spektral method. In the mass spectra of these compounds, the presence of high percentages of the peak corresponding to the molecular ion intensity of the compounds was observed. Elemental cell parameters and diffracted X-ray intensities were determined on
a CCD Xcalibur Ruby (Oxford diffraction) diffrac-tometer. The crystallographic computer program SHELXTL was used to find the structure of the compound.
Classification on base on chemical composition
a-Aminonitriles and their derivatives are listed as organic compounds in Section VI of the NGFEA. The following new brand codes have been proposed for the compounds of a-aminonitriles and their derivatives studied by us. Code number 292690950 1 for a-aminonitrile derivatives according to the nomenclature of goods in foreign economic activity (NGFEA) was recommended.
Proposed code numbers for a-aminonitriles and their derivatives
2926 The compounds contain a functional group of nitrile
292690950 0 others
292690950 1 a-aminonitriles and their derivatives
292690950 9 others
Conclusion
New a-aminonitrile derivatives synthesized and studied by modern physicochemical research methods. Products of reaction classified according to their chemical composition and obtained the digital product code.
Acnowledgments
The authors would like to thank Bakhtiyorjon Abduganiev, Colonel of the Customs Service of Uzbekistan, PhD in Chemistry, Associate Professor, for his assistance in the implementation of the product codes.
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