Volume 04 Issue 07-2024
22
International Journal of Advance Scientific Research
(ISSN
–
2750-1396)
VOLUME
04
ISSUE
07
Pages:
22-29
OCLC
–
1368736135
\
A
BSTRACT
This study investigates the structure of the product resulting from the reaction between ferrocene-
carboxylic acid and o-aminobenzoic acid. To achieve this, we employed a combined approach of quantum-
chemical calculations and IR-spectroscopy. Optimized structures of the reaction product were obtained
using the "Gaussian 98" program. By analyzing the results from both methods, this study provides an
energetic justification for the product's structure and elucidates the relationship between its structure and
properties.
K
EYWORDS
Ferrocene carbonic acid, o-aminobenzoic acid, diazotization IK-spectroscopy, quantum chemistry, hetero-
annular, Harty energies.
Journal
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Research Article
JUSTIFICATION OF THE STRUCTURE OF THE REACTION
PRODUCT BETWEEN FERROCARBON AND O-AMINOBENZOIC
ACID USING QUANTUM-CHEMICAL AND IR-SPECTROSCOPY
METHODS
Submission Date:
July 21,
2024,
Accepted Date:
July 26, 2024,
Published Date:
July 31, 2024
Crossref doi:
https://doi.org/10.37547/ijasr-04-07-05
Askarov Ibrahimjon Rakhmanovich
Doctor of Chemistry, Professor, Department of Chemistry, Andijan State University, Andijan, Uzbekistan
Tolakov Nurillo Kasimovich
Doctor of Philosophy in Chemistry (PhD), Associate Professor, Department of Chemistry, Andijan State
University, Andijan, Uzbekistan
Abduraimov Zukhriddin Kholboevich
Doctor of Philosophy in Chemistry (PhD), Senior Teacher, Department of Chemistry, Andijan State
University, Andijan, Uzbekistan
Volume 04 Issue 07-2024
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International Journal of Advance Scientific Research
(ISSN
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2750-1396)
VOLUME
04
ISSUE
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Pages:
22-29
OCLC
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1368736135
I
NTRODUCTION
To date, significant progress has been made in
modern chemistry, as in many other fields. The
reason for this is the improvement of the methods
of analysis of chemical processes based on
complex mechanisms, initially using chemical
computer programs with high capabilities, based
on quantum-chemical calculation. Currently,
using the methods in practice, there are
opportunities to theoretically study the
mechanism of chemical reactions, the reactivity of
substances, the location of active centres, the
yield of products, the spatial and graphic
structure of initial and formed substances, and
their spectroscopic inspection indicators. This
causes time and resources to be saved during the
synthesis of the substance, optimization of the
conditions of the synthesis process, and
conducting theoretically based, small number of
specific experiments [1].
M
ETHODS
The software package "Gaussian 09w" is widely
used in the theoretical calculation of the spatial
structure, valence angles, energy values of atoms
and vibrational spectra of ferrocene and
ferrocene derivative molecules [2].
When choosing the theoretical calculation
method suitable for ferrocene and its derivatives,
the molecular and spatial structure of ferrocene,
ionization energies, electron density distribution
in atoms and other physical and chemical
indicators were carried out by quantum-chemical
calculation [3].
In order to further expand the sphere of influence
of ferrocene carbonic acid, a number of works
have been carried out on the synthesis of its new
derivatives [4].
In order to continue the research on obtaining
new compounds based on ferrocene carbonic
acid, we carried out the arylation reaction of
ferrocene carbonic acid with the help of
aminobenzoic acid isomers by the diazotization
method. The reaction of diazotization of
ferrocene carbonic acid with o-aminobenzoic acid
was carried out in an ethereal environment in the
presence of sodium nitrite and hydrochloric acid.
As a result, a hetero-annular substituted
compound of ferrocene carbonic acid was formed.
Using the quantum chemical calculation method,
the structures of all possible isomers of the
reaction product between ferrocene carbonic
acid and o-aminobenzoic acid were constructed.
Schemes of the structures of these isomers are
given below (Fig. 1.):
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International Journal of Advance Scientific Research
(ISSN
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2750-1396)
VOLUME
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Pages:
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OCLC
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C
O
O
H
C
O
O
H
C
O
O
H
C
O
O
H
COOH
COOH
Fe
Fe
Fe
N
H
H
C
O
O
H
Fe
HOOC
+
(2)
(4)
(5)
(6)
(7)
Ferrotsenkarbon
kislota
(3)
C
O
O
H
HOOC
Fe
C
O
O
H
HOOC
Fe
(1)
C
O
O
H
HOOC
Fe
C
O
O
H
HOOC
Fe
o-aminobenzoy kislota
Figure 1. Models of possible isomers 1, 2, 3, 4, 5, 6 and 7 of the reaction products between
ferrocene-carboxylic acid and o-aminobenzoic acid
In order to determine which isomer corresponds
to the structure of the product, the Hartree
energies (EHart) of the optimized structures of
possible isomers 1, 2, 3, 4, 5, 6, and 7 were
calculated using the DFT/B3LYP hybrid method
3-21G basis of the Gaussian 98 software package
was calculated and the differences (DE) between
them were determined. The calculation results
are presented in the table below.
Table 1. Hartree energies of the optimized structures of the isomers of the reaction product
between ferrocene carbonic acid and o-aminobenzoic acid and their differences
Isomers
EHart., kJ/mol
DE, (J)
Dipole moment
1
-2247.5369
0
2.6130
2
-2247.5217
0.0152
2.9867
3
-2247,1289
0.408
2.8818
4
-2247.1177
0.4192
2.9798
5
-2247.0689
0.468
3.1015
6
-2247.1215
0.4154
4.5084
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7
-2247,1247
0.1247
2.6864
The calculation results showed that among the
isomers 1, 2, 3, 4, 5, 6 and 7 of the reaction
product between ferrocene carbonic acid and o-
aminobenzoic acid, the energy of 1 is smaller than
the others. Based on the results, it can be
concluded that the main product of the reaction of
ferrocene carbonic acid with o-aminobenzoic acid
corresponds to structure 1.
The reaction products were initially screened by
thin-layer chromatography and separated by
column chromatography. In order to more
accurately study the molecular structure of the
synthesized compounds, their infrared spectra
were taken and analyzed. The wavenumber
values
of
absorption
peaks
observed
experimentally in the IR spectrum of the product
were compared to the wavenumber values of the
maxima of the absorption fields calculated
quantum-chemically for the corresponding
vibrations in the molecule. The results are
presented in Table 2.
From the analysis of the results, it was found that
the values of the wavenumbers of the absorption
regions in the experimentally measured IR-
spectrum of o-(2`-carboxyferrocenyl)benzoic
acid correspond to the quantum-chemically
calculated values for the molecule with the
structure we assumed.
Figure 2. IR spectrum of o-(2`-carboxy ferrocenyl) benzoic acid
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Figure 3. Quantum-chemical calculated IR-spectrum of o-(2`-carboxy ferrocenyl) benzoic
acid (Gaussian 98)
The absorption lines at 1108 and 1029 cm-1 of
the IR spectrum belong to the ferrocenyl group
from the heteroannular dialyzer, the absorption
lines at 914 cm-1 are due to the pentadienyl ring
substituted for the ferrocene residue, the
absorption lines at 2869, 2626 cm-1 belong to the
–
ON group of the carboxyl group, the spectrum at
834 cm-1 The absorption line characteristic of the
deformation vibrations of the 1,4-disubstituted
benzene ring in the region 1, as well as the
absorption line at 3560 cm-1 of the deformation
vibration (OH) group, and the absorption lines
corresponding to the vibrations of the >S=O
group of
–
SOON at 1650 cm-1 gives [5,6]. The IR
spectrum of the synthesized compound is shown
in Fig. 2.
Synthesized
o-(2`-
carboxyferrocenyl)benzoinacidA
quantum-
chemically calculated IR spectrum was obtained
to compare the wavenumber values of the
absorption peaks observed in the experiment
(Fig. 3).
Table 2. Wavenumber of experimentally observed peaks in the IR-spectrum of o-(2`-carboxy
ferrocenyl) benzoic acid and calculated values of the maximum wavenumber of the branch
corresponding to the corresponding vibration of different isomers of the molecule cm
-1
No
Type of
vibration
Absorption field maximum wave number, cm-1
Calculated
Measured
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1
2
3
4
5
6
7
1.
Fc n(CCC)
382
375
380
381
381
431
380
386
2.
Fc n(C-Fe)
429
421
447
449
420
445
417
425
3.
Fc n(CCC)
511
516
500
500
515
522
518
509
4.
Fc n(CCC)
561
564
568
569
561
560
539
563
5.
n(COOH)
597
618
705
602
616
623
582
598
6.
nCp(CH)
740
739
739
740
727
743
736
740
7.
dCp(CH)
783
780
777
787
779
792
786
783
8.
s nCp2(CH)
838
848
845
842
816
823
812
834
9.
nCp2(CH)
914
915
915
921
914
917
897
914
10.
dCp(CC)
939
958
957
959
957
943
927
935
11.
dCp2(CC)
1053
1035
1042
1028
1037
1043
1036
1052
12.
nsp(CH)
1108
1123
1121
1123
1123
1097
1138
1108
13.
nCp2(CH)
1213
1199
1193
1196
1193
1196
1192
1220
14.
s nCp1(CH)
1277
1255
1273
1257
1254
1274
1262
1279
15.
as n d (CO)
1651
1595
1593
1597
1594
1591
1593
1650
16.
d(OH)
3565
3418
3418
3418
3400
3400
3408
3560
The data presented in Table 2 are o-(2`-
carboxyferrocenyl) benzoic acidacid. The
wavenumbers of the absorption areas in the
spectrum obtained in the experiment confirm
that the absorption areas in the spectrum
obtained as a result of quantum-chemical
calculations correspond to the wavenumbers.
Figure 4. Computationally optimized molecular structure of o-(2`-carboxy ferrocenyl)
benzoic acid
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O-(2`-carboxyferrocenyl)benzoin as a result of
the diazotization reaction based on the results of
the analysis can see that an acid (product 1) is
formed.
Based on the spectral data, it can be shown that
the formation of the obtained substance proceeds
according to the following reaction equation:
C
O
O
H
C
O
O
H
C
O
O
H
C
O
O
H
H
HOOC
C
O
O
H
HOOC
Fe
Fe
COOH
COOH
NH
2
Cl
-
N
2
HNO
2
2H
2
O
HCl
Fe
Fe
Cl
-
N
2
COOH
2H
2
O
N
N
Cl
-
2H
2
O
Fe
HCl
N
2
2H
2
O
+
+
+
-5
o
C
+
34
o
C
+
+
34
o
C
+
+
34
o
C
+
+
+
+
C
ONCLUSION
In conclusion, it can be said that the structure of
the product of the diazotization reaction between
ferrocene carbon and o-aminobenzoic acid was
obtained based on energetics. On this basis, the
diazotization reaction scheme with ferrocene
carbon and o-aminobenzoic acid and the
structures of all possible isomeric products were
constructed. In order to determine which isomer
the structure of the product corresponds to, the
optimized structures of the possible homo- and
hetero-annular state isomers were calculated
using the Hartree Energies (EHart.) "Gaussian 98"
software package using the DFT/B3LYP hybrid
method 3-21G basis.
From the analysis of the results o-(2`-
carboxyferrocenyl), benzoinacidIt was proved
that the values of the wavenumbers of the
absorption fields in the IR-spectrum measured
experimentally correspond to the quantum-
chemically calculated values.
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EFERENCES
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Khozhimatov M.M.Synthesis of biologically
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Zhan Ch-G., Nichols J.A., and Dixon D.A.
Ionization Potential, Electron Affinity,
Electronegativity, Hardness, and Electron
Excitation Energy: Molecular Properties from
Density Functional Theory Orbital Energies //
J. Phys Chem. A. 2003. − vol. 107. − p. 4184
-
4195.
Volume 04 Issue 07-2024
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International Journal of Advance Scientific Research
(ISSN
–
2750-1396)
VOLUME
04
ISSUE
07
Pages:
22-29
OCLC
–
1368736135
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Mamarakhmanov M.Kh. "Quantum-chemical
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carbonic
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