Comparison property geometry, electron charge and...
Transcript of Comparison property geometry, electron charge and...
Comparison property geometry, electron charge and vibrational
Of Heterocyclic's hydantoin and thiohydantoin with statistic
Lazhar Bouchlaleg*
Group of Computational and Pharmaceutical Chemistry, LMCE Laboratory, University of Biskra,
Faculty of Sciences, Department of Chemistry, 07000 Biskra, Algeria
Laboratory Ecodesign and Earthquake Engineering in Construction Innovation,, Mechanical
Department, Faculty of Technology, University of Batna,05000,Batna,Algeria
ABSTRACT
A comparative study was made the best from
molecular to medicine geometry
optimization , vibrtional frequencies ,
Hydantoin and thiohydantoin are
measured, we have been calculated and
performed by using the molecular
mechanics, Quantum mechanics method
(Parametric method Density Functional
Theory developed by Becke, Lee, Yang, and
Parr method DFT/B3LYP method) basis set
in order to obtain optimized geometrical
parameters are in good agreement with
experimental values and allow and can
explain more or less the optical activity.
Comparison by statistical regression of the
obtained fundamental vibrational
frequencies of hydantoin result by
DFT/B3LYP (6-311G++ (d, p)) method,
are in a close agreement with the
experimental data. Detailed vibrational
wave number shifts and vibrational mode
analyses were reported and can explain the
biological activities.
Keywords: in silico, Hydantoin,
imidazolinide-2, 4-dione, ThioHydantoin
vibrational frequencies, DFT.
I- Introduction
Closely related analogues of hydantoins
are the thiohydantoins, which may have
one or both of the carbonyl oxygen atoms
exchanged for a sulfur atom. These
compounds undergo analogous reactions in
the presence of similar reagents.1-
45hydantoin and thiohydantoin are the most
notable with a large number of medicinal
and industrial applications.2-45Hydantoin
(2, 4-imidazolidinedione, glycol urea) was
first discovered by Bayer in 1861 as a
hydrogenation product of all Antoin and its
derivatives are important intermediates in
the synthesis of several amino acids3-44 and
are also used as anticonvulsants or
antibacterial12. The hydantoin, also
known2, 4-imidazolidinedione is a
saturated heterocyclic imidazole derivative
compound. It has two functions lactams
(cyclic amide). The Hydantoin can be
obtained from urea or glycine. It can be
seen as the product of the condensation of
urea twice and glycolic acid. Additionally,
2-Thiohydantoins have been used as
reference standards for the development of
C-terminal protein sequencing14-15 , as
reagents for the development of dyes 21-25
preparative methods for 2-Thiohydantoins
include the reactions between thiourea and
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benzil 13-31, amino amide and
diimidazolethiocarbonate 21-31, and
others45.However, the above methods often
suffer from one or more synthetic
limitations for large-scale preparation of 2-
Thiohydantoin derivatives due to their use
of expensive, moisture sensitive and/or
highly toxic starting materials and
reagents. Moreover, the methods
developed for combinatorial synthesis and
used to prepare 2-Thiohydantoin
derivatives in small quantities for purposes
like biological testing may not be feasible
when operated on a large scale 5-19and 43.
Hydantoin properties are relatively similar
to those of the imidazolidine (completely
saturated derivative of imidazole),
although having carbonyl functions on
carbons 2 and 4 of the cycle. Cases of
inflammatory syndromes induced by
Hydantoin (lymphadenopathy, self-
anticorps) are reported6-10. We called
Hydantoins substituted Hydantoin
derivatives. These compounds shave
relatively similar properties to that of
imidazolidines, saturated derivatives of
imidazoles. They are used in pharmacy as
antiepileptic these include among
pharmaceutical compounds Hydantoin
category ethotoin, phenytoin, mephenytoin
and fosphenytoin. Hydantions are
biologically active molecules widely used
in medicine as antiepileptic,
antischisto_somal, antiarythmic,
antibacterial and tuberculostatic drugs 5-
31and 46. It is also an effective medication for
the treatment of metastatic prostate cancer.
It is the parent compound of antiepileptic
drug biphenyl hydantoin 4-41. A Hydantoin
derivative shows biological activity against
human parasites like trematodeos21-41.
Beside its medical usage it's also used as
herbicides and fungicides 9- 19.
Among the known these molecules are
most due of their wide applications as
hypolipidemic3-7, anticarcinogenic 12-38,
antimutagenic13-39, antithyroidal 20-40
antiviral (e.g., against herpes simplex
virus, HSV) 25-29, human
immunodeficiency virus (HIV) 25-37 and
tuberculosis 16-37), antimicrobial
(antifungal and antibacterial) 17-26, anti-
ulcer and anti-inflammatory agents8- 18, as
well as pesticides11-19.
In recent years, the theoretical study of
geometry and electronic structures has
proved to be very efficient to predict the
physical-chemistry properties of large
systems 3-5. The theoretical calculation of
vibrational properties is used to understand
the spectra’s of large number of donor-
acceptor systems 12-13. Consequently, these
calculations can be performed at different
accuracy levels depending on the aim of
the theoretical study. The substituents
attached to the molecular framework can
enhance or diminish the reactivity45.
The mechanistic conclusions based on the
linear relationships with free energy have
been extremely fruitful. The substituent's
were variable donating and with drawing
to study the effect of such change on the
geometric, vibrational properties of the
studied molecules. Accordingly, changes
in reactivity in one reaction series caused
by changes in substitution are related to
changes in equilibrium or reactivity 14-
15.Accordingly, objective of the present
research is to study the geometric,
vibrational spectra will characterize and
predict the molecular and spectroscopic
properties of hydantoin. Thus, in this work
we have studied of the substituent groups
effects at different positions in the
hydantoin ring. In this study, we have
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calculated the structure of hydantoin and
derivatives by using DFT/B3LYP methods 36-17.On the other hand I studied the
Molecular geometry optimization of
Thiohydantoin, vibrational frequencies,
Hydantoin and ThioHydantoin at the
ground state, in present work, we have
been calculated and performed by using
the Molecular Mechanic DFT/B3LYP
methods basis set in order to obtain
optimized geometrical parameters are in
good agreement with experimental values.
Comparison of the obtained fundamental
vibrational frequencies of Hydantoin and
ThioHydantoin result by DFT/B3LYP (6-
311G++ (d, p)) method, are in a close
agreement with the experimental data. Ab
initio/HF with 6-31G basis set was used to
investigate the effects of a variety of
substituants (methyl ,dimethyl, trimethyl
,and chloride ,dichloride ,trichloride ) on
properties of ThioHydantoin derivatives.
Detailed vibrational wave number shifts
and vibrational mode analyses were
reported.
Hydantoins and Thiohydantoins are sulfur
analogs of ThioHydantoin and derivatives
with one or both carbonyl groups replaced
by thiocarbonyl groups24-27.
I.1COMPUTATIONAL DETAILS
Initial calculations were optimized using
HyperChem 8.03 software 20-4. The
geometries of ThioHydantoin and its
derivatives; were first fully optimized by
molecular mechanics, with MM+ force-
field (rms = 0.001 Kcal/Å). Further,
geometries were fully re-optimized by
using PM3 method 30- 17 and 31. In the next
step, a parallel study has been made using
Gaussian 09 program package 27- 5, at
various computational the best level DFT/
B3LYP/6-311G++ (d,p).
The calculated results have been reported
in the present work.
II. RESULTS AND DISCUSSION
II.1 Molecular geometry of
ThioHydantoin The molecular
structure of Thiohydantoinis shown in
(Figure 1). With this structural model,
Thiohydantoin 31-22 and 20. The
optimized geometrical parameters of
Thiohydantoin by ab initio/HF and
DFT method have been depicted and
compared with experimental
parameters 45 obtained from the crystal
structure analyses of Thiohydantoin in
(Table II.1).
Fig. II.1: Conformation 3D of molecular
structure and atom numbering adopted in this
study for ThioHydantoin (GaussView 09)
Thus, in this work was revealed good
between the experimentally obtained
values data are in good agreement with the
theoretical calculations for bond lengths,
bond angles and dihedral angles. The
nearly of the calculated geometries from
the experimental parameters are 1,633A°
(S6-C2)and 1,396A° (C2–N1) at
B3LYP/DFT, 1,37A°(C2–N3) and
1,205A°(C4-O7) at ab initio/HF,and
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1,37A°(N3-C2)at B3LYP/DFT or ab
initio/HF for the bond lengths and
131,5°(S6-C2-N1),122,8°(S6-C4-N3) at ab
initio/HF also 125,5°(O7-C4-N3)or
128,2°(O7-C4-N3)basis sets for the bond
angles. On the other hand, dihedral angles
174, 8° (O4-C4-C5-N1) which is close to
the currently accepted experimental values
this confirms our structure has a flat geometry.
Table II. 1: Comparison of the experimental and calculated values of bond lengths and bond angles of
ThioHydantoin
Parameters Exp.32
ab initio/HF DFT(B3LYP)
6-31G+(d,p) 6-31G++(d,p) 6-311G++(d,p) 6-31G+(d,p) 6-31G++(d,p) 6-311G++(d,p)
Bond Length(A°)
S6-C2 1,633 1,62136 1,62136 1,62136 1,62136 1,62135 1,62136
N1-C2 1,396 1,39612 1,39612 1,39612 1,39612 1,39606 1,39612
O7-C4 1,205 1,21096 1,21096 1,21096 1,21096 1,2109 1,21096
N3-C2 1,37 1,41999 1,41999 1,41999 1,41999 1,41999 1,43513
Bond angle (°)
S6-C2-N1 131,5 127,430 127,430 127,430 127,430 127,433 127,430
S6-C2-N3 122,8 127,297 127,297 127,297 127,292 127,292 127,297
O7-C4-N3 125,5 122,529 122,529 122,529 122,529 122,530 122,529
O7-C4-C5 128,2 130,847 130,847 130,847 130,847 130,849 130,847
Dihedral angles (°)
C4-N3-C2-S6 174,80 179,989 179,989 179,994 179,994 179,994 179,994
III.1 Molecular geometry of Hydantoin
The molecular structure of hydantoin is
shown in (Figure 1). With this structural
model, hydantoin belongs to Cs point
group symmetry. The optimized
geometrical parameters of hydantoin by ab
initio/HF and DFT method have been
depicted and compared with experimental
parameters 22 obtained from the crystal
structure analyses of hydantoin in
(TableIII.1).
Figure III.1: Conformation 3D of molecular structure and atom numbering adopted in this
study for hydantoin (GaussView 09)
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Table III. 1: Comparison of the experimental and calculated values of bond lengths and bond
angles of Hydantoin
Thus, in this work was revealed good
between the experimentally obtained
values data are in good agreement with the
theoretical calculations for bond lengths,
bond angles but dihedral angles
N1-C2-N2-C4 made exception the
predicts values are not consistent with
The values experimentals this may be due
to probably steric of connections to
terminals end of the link chain and closing
the cycle of a rotary manner or disrotatory
in synthese reaction of Hydantoin this
means that the cycle closes from of
C5-N1-C2-N2.
Parameters
Exp.48
ab initio/HF DFT(B3LYP)
Bond Length
(A°)
6-
31G+(d,p) 6-31G++(d,p) 6-311G++(d,p) 6-31G+(d,p) 6-31G++(d,p)
6-
311G++(d,p)
C2-O6 1,222 1,19183 1,19188 1,18516 1,21581 1,21583 1,20705
C2-N1 1,371 1,3556 1,35556 1,35568 1,36382 1,36379 1,36137
C2-N3 1,393 1,3899 1,38991 1,39025 1,40388 1,40390 1,40267
N3-C4 1,367 1,3662 1,3662 1,36635 1,36987 1,36987 1,36775
C4-O7 1,225 1,18847 1,18850 1,18216 1,21483 1,21482 1,20641
C4-C5 1,460 1,5218 1,52188 1,52148 1,51962 1,51967 1,51714
C5-N1 1,457 1,4433 1,44329 1,44259 1,43253 1,43253 1,43006
Bond angle(°)
O6-C2-N1 128,2 128,3769 128,373 128,438 128,646 128,649 128,752
O6-C2-N3 124,4 125,744 125,745 125,761 126,085 126,083 126,115
N3-C2-N1 107,4 105,879 105,883 105,801 105,269 105,268 105,133
C4-N3-C2 111,67 113,309 113,310 113,406 113,430 113,432 113,578
O7-C4-C5 125,3 127,070 127,075 127,089 127,121 127,120 127,125
C5-C4-N3 106,8 105,770 105,768 105,655 105,259 105,257 105,117
N1-C5-C4 104,7 101,820 101,823 101,919 102,843 102,842 102,926
C2-N1-C5 109,4 113,221 113,217 113,219 113,199 113,202 113,246
Dihedral angles(°)
C5-N1-C2-N2 4,1 4,5 4,6 5,4 4,0 4,0 3,0
N1-C2-N2-C4 6,7 3,6 3,7 4,3 1,9 1,9 3,0
O2-C2-N1-C5 176,1 179,985 179,984 176,984 179,978 179,978 176,979
O4-C4-C5-N1 176,0 179,989 179,991 179,985 176,0 179,987 179,987
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The nearly of the calculated geometries
from the experimental parameters are
1,364A° (C2–N1) at B3LYP/DFT,
1,39A°(C2–N3) and 1,517A°(C4-C5) at
ab initio/HF ,and 1,367A°(N3-C4)at
B3LYP/DFT or ab initio/HF for
the bond lengths and
128,373°(O6-C2-N1),105,77°(C5-C4-N3)
at ab initio/HF basis sets for the bond
angles.
On the other hand dihedral angles 4° (C5-
N1-C2-N2) and 176,978° (O4-C4-C5-N1)
which is close to the currently accepted
experimental values .which confirms that
the structure of the hydantoin is planar
geometry between 0 ° and 180°.
III.2 Vibration frequencies of
ThioHydantoin IR spectroscopy can give
a great deal of information on small ring
heterocyclic, because of the effects of ring
strain on the frequencies of vibration of
substituent's attached to the ring, and
because the ring vibrations fall into a
readily accessible region of the IR
spectrum 47-20and 42.
Experimental and theoretical vibration
wave numbers of ThioHydantoin were
given in Table 2.ThioHydantoin consists of
11 atoms, which has 27 normal modes.
These normal modes of the title molecule
have been assigned according to the
detailed motion of the individual atoms.
All normal modes assigned to one of 13
types of motion(C–H, C=O,C=S, C–H, and
stretching's; HCH, CCN, CCH,
NC=S,NC=O, CC=O, NCN, CNC, CNH,
and NCH bindings, and HNC=O, OCCH,
HCNH, NCNH, CNC=S, NCCN,
CNCC,NCNC and NH twisting, C-
H,C=O,C=S Scissoring, C=O,C=S
wagging, C-H rocking The asymmetric C-
H stretching frequency decreases with
increasing ring size, predicted by a
calculation analysis. The results obtained
from the calculations show that, while the
harmonic corrections of wave numbers are
closer to the experimental ones rather than
wave numbers of forms gave the best fit to
the experimental ones. The vibration wave
numbers of the forms of ThioHydantoin
obtained from the DFTcalculations are
almost the most the same.
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Table III.2: Comparison of the experimental and calculated vibration spectra of
ThioHydantoin.
Mode
N0
Symmetry
EXP.
IR27
DFT(B3LYP)/ 6-311G++ (d,p) Assignment
1 A
98,78 υ C4-H
2 A
137,76 υ C4-H
3 A
278,35 υ C4-H,ω C=O, ω C=S, ωN1-H,
4 A
391,51 υ C4-H
5 A 530 494,68 υC4-H, ωN1-H, υ C=O, υ C=S
6 A
515,83 υ C4-H,ω C=O, ω C=S, ωN1-H,
7 A
546,58 υ C4-H,ω C=O, ω C=S, ωN1-H,
8 A 631 592,88 υC4-H, υ N1-H, δ C5-H
9 A
651,20 υ C4-H,ω C=O, ω C=S, ωN1-H,
10 A
674,37 υ C5-H
11 A 964 871,93 υ C4-H,ω C=O, ω C=S, ωN1-H,
12 A 1045 969,51 ω C5-H, ωN1-H,
ω C=S, ω C=O, ωN3-H,
13 A
1006,43 ω C=S, ω C=O ,ω C5-H, ωN1-H,
14 A 1156 1058,49 υ C-H, ωN1-H, ωN3-H
15 A 1223 1163,48 υ C4-H,ω C=O, ω C=S, ωN1-H,
16 A 1298 1189,33 υ C4-H,ω C=O, ω C=S, ωN1-H,
17 A 1381 1199,55 υ C5-H, ωN1-H, ωN3-H,
18 A
1302,38 ω C=O ,ω C5-H, ωN1-H,
19 A 1528 1363,98 υ C4-H,ω C=O, ω C=S, ωN1-H,
υ N3-H
20 A
1390,58 υ C4-H,ω C=O, ω C=S, ωN1-H
21 A
1483,30 υ C4-H,ω C=O, ω C=S, ωN1-H
22 A 1716 1541,20 υ C4-H,ω C=O, ω C=S, ωN1-H, , ωN3-
H, ω C5-H
23 A
1830,66 δ C=S,δ C=O , υ C4-H, υ N1-H
24 A 3197 3039,31 ω C5-H, ω N3-H
25 A 3283 3076,47 υ C4-H, ω N3-H, τ N3-H, ρ C5-H
26 A
3638,27 δ N3-H
27 A
3664,92 δ N3-H
IRexp: Experimental Infrared; asym: asymmetric; sym: symmetric; ν: bond stretching
δ: scissoring; τ: twisting; ω: wagging; ρ: rocking;
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Fig.III. 2: Different figures of 27 modes with bond of ThioHydantoin ring
Mode 1 Mode 2 Mode 3
Mode 4 Mode 5 Mode 6
Mode 7 Mode 8 Mode 9
Mode 10 Mode 11 Mode 12
Mode 13 Mode 14 Mode 15
Mode 16 Mode 17 Mode 18
Mode 19 Mode 20 Mode 21
Mode 22 Mode 23 Mode 24
Mode 25 Mode 26 Mode 27
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in medicinal chemistry due to its large
experimental and predict frequency
(moderate intensity) (3283–3197cm–1), the
absorption in the large 428Cm-1, 429,743428Cm-1
,429,7797428Cm-1and 433,4412428Cm-1
The experimental values in good agreement
with that obtained from ab-initio/HF theory using
The diatomic molecules have only one link, which can be stretched. The more complex molecules have many
Connections, and vibration maybe combined, leading to the infrared absorption at the characteristic frequencies
Which can be linked to chemical groups. For example, atoms
of CH2, which is commonly found in organic
Compounds, can vibrate in six different ways: Stretching and skew symmetric, scissoring, and rocking, agitation outside plane wagging and twisting ν1 (NH) stretching mode for monomer was observed at
Basis 6-31G+(d,p)set and6-311G++(d,p) .
ν3 C 2=S6 and ν C4=O7 stretching modes were
observed
with I-R intensity at 200, 371623Cm-1
And frequency 1864, 9723Cm-1These considerations thus
provide additional support. Cyclic imides represent an important class of
compounds
Spectrum of biological activities 28,42
Relation between
III.3. Vibration frequencies of
Hydantoin
IR spectroscopy can give a great deal of
information on small ring heterocyclic,
because of the effects of ring strain on the
frequencies of vibration of substituent's
attached to the ring, and because the ring
vibrations fall into a readily accessible
region of the IR spectrum 23, 33 and34.
Experimental and theoretical
(DFT_B3LYP/6–31G++ (d, p)) vibrational
wave numbers of Hydantoin were given in
Table III.2.
Hydantoin consists of 11 atoms, which has
27 normal modes. These normal modes of
the title molecule have been assigned
according to the detailed motion of the
individual atoms.
All normal modes assigned to one of 21
types of motion(C–H, C=O, C–H, and N–
H stretching's; HCH, CCN, CCH, NC=O,
CC=O, NCN, CNC, CNH, and NCH
bindings, and HNC=O, OCCH, HCNH,
NCNH, CNC=O, NCCN, CNCC, and
NCNC twisting) The asymmetric C-H
stretching frequency decreases with
increasing ring size, predicted by a
calculation analysis.
The results obtained from the calculations
show that, while the harmonic corrections
By simple regression is obtained
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of wave numbers are closer to the
experimental ones rather than wave
numbers of forms gave the best fit to the
experimental ones.
The vibrational wave numbers of the forms
of hydantoin obtained from the DFT
calculations are almost the same except
one value 429,743Cm-1of mode 4 at ab-
initio.
Table III. 3: Comparison of the experimental and calculated vibrational spectra of hydantoin.
Mode
N0
Symmetry
EXP.
IR 49
DFT(B3LYP)/ 6-311G++ (d,p)
Assignment
1 A 128.5824 ν N1_H8
2 A 144.7564 νN3_H9
3 A 385.3754 νasC5_H10 andνasC5_H11
4 A 428 389.9752 νsymC5_H10 and C5_H11
5 A 554 540.4346 νN1_H8,νC2=o6 and νC4=o7
6 A 545.114
ωC5_H10,ωC5_H11and
νN1_H8,N3_H9andτ
C2=O6,C4=O7
7 A 580 601.288 δC5_H10,δC5_H11 and ν
N1_H8
8 A 632 624.1676 δC5_H10,δC5_H11 and ν
N1_H8
9 A 670 701.9823 δC5_H10,δC5_H11 and
νN1_H8
10 A 719 746.5964 τ N3_H7 and νC5_H10
11
A 785 882.9414
ωC5_H10,ωC5_H11and
νN1_H8,N3_H9andτC2=O6,
C4=O7
12 A 899 968.2432 ωC5_H10,ωC5_H11and
νN1_H8,N3_H9and νC4=O7
13 A 968.2617 τC5_H10, τ C 5_H11
14 A 990 1072.2072 ωC5_H10,ωC5_H11 and ν
N1_H8
15 A 1075 1147.0616 ωC5_H10,ωC5_H11,ωN1_H8
and ωN3_H9
16 A 1175.6719 τ C 5_H10,ƬC5_H11and
νC4=O7
17 A 1197 1265.0279 ωC5_H10,ωC5_H11,νN1_H8
andνN3_H9
18 A 1287 1307.5245 νC2=O7
19 A 1377 1361.2266 ωC5_H10,ωC5_H11and
νN1_H8,νN3_H9
20 A 1429 1392.09 ω C5_H10,ω
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C5_H11andνC2=O6,νN3_H9,
νC4=O7
21 A
1426.929 τC5_H10,ƬC5_H11and
νN3_H9
22 A 1696 1822.838 ρC5_H10,ρC5_H11
and νN3_H9
23 A 1774 1863.2827 ωC5_H10,ωC5_H11andνN1_
H8,νN3_H9
24 A 2944 2966.5839 νN1_H8,νC5_H10and
νC5_H11
25 A
3006.1303
ωN1_H8,
ωC5_H10,ωC5_H11and
νC2=O6,νC4=O7
26 A 3130 3554.3144 νC5_H10,νC5_H11andνN3_H
9
27 A 3257 3584.495
τ N
1_H8,ρC5_H10,ρC5_H11and
ωN3_H9
IRexp: Experimental Infrared; asym: asymmetric; sym: symmetric; ν: bond stretching δS:
scissoring; τ: twisting; ω: wagging; ρ: rocking;
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Figure III.4 DIFFERENTS FIGURES OF 27MODES WITH BOND OF HYDANTOIN
RING
MODE N°1
(NH,CH,CN)
MODE N° 2
(NH,CH,CO,CN)
MODE N° 3
(CN,NH,CH)
MODE N° 4
(CO,NH,CH,CN
)
MODE N°5
(NH,CN,CH)
MODE N°6
(CH,NH,CO,CN)
MODE N°7
(CH,NH,CN)
MODE N°8
(NH,CO,CH)
MODE
N°9(CO,CN,CH)
MODE N°10
(CO,NH,CN,CH)
MODE N°11
(NH, CN,NH)
MODE N°12
(CN, NH, CH)
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MODE
13(CN,CH)
MODE14
(CH,CN,NH)
MODE15
(CN,CH)
MODE16
(CH,CN,NH)
MODE17
(CH,CN,NH)
MODE 18(NH,CN) MODE19
(NH,CH,CO)
MODE 20
(CN,CH,NH)
MODE 21(CH,CN)
MODE22
(NH,CO,CN)
MODE23
(NH,CN,CO)
MODE 24
(CN,CH)
MODE 25
(CH,CN)
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MODE 26(NH,CN) MODE 27(NH,CN)
The diatomic molecules have only one
link, which can be stretched. The more
complex molecules have many
connections, and vibration maybe
combined, leading to the infrared
absorption at the characteristic frequencies
which can be linked to chemical groups.
For example, atoms of CH2, which is
commonly found in organic compounds,
can vibrate in six different ways: stretching
and skew symmetric, scissoring, and
rocking, agitation outside plane wagging
and twistingν1 (NH) stretching mode for
monomer was observed at (moderate
intensity) (3599,8–3570,24 cm–1), ν2 CH2
group (C5-H10,C5-H11) wave numbers
symmetric and asymmetric stretching
mode was observed at (2979,43 and
3023,23Cm-1) with twisting ,waging and
scissoring the absorption in the large
428Cm-1, 429,743428Cm-1
,429,7797428Cm-1and 433,4412428Cm-1
the experimental values in good agreement
with that obtained from ab-initio/HF theory
using basis 6-31G+(d,p) set and 6-
311G++(d,p) .ν3 C2=O6 and ν C4=O7
stretching modes were observed with I-R
intensity at 200Cm-1, 371623Cm-1 and
frequency 1864,9723Cm-1These
considerations thus provide additional
support.
Cyclic imides represent an important class
of compounds in medicinal chemistry due
to its large spectrum of biological activities
23, 35; are in a good agreement with the
observed IR spectral data. In conclusion,
the 6-311G++base (d, p) lead to prediction
soft he theoretical molecular conformation
similar to that given by the experiment in
the case of the Hydantoin molecule
studied.
This conclusion is based on the
comparative study between the frequencies
calculated internal modes, using the
molecular conformation calculated by
DFT/B3LYP and experimental
frequencies.
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III.5 Linear regression between
experimental frequencies (νexp) and
Predict frequency (νth)
Use linear regression or correlation by
IBM - SPSS Statistics V19.0. When you
want to know whether one measurement
variable is associated with another
measurement variable; you want to
measure the strength of the association
(r2); or you want an equation that describes
the relationship and can be used to predict
unknown values. in fact our comparison
between experimental frequencies and
Predict frequencies amounts to a linear
regression method we found36.Following
the linear regression models, When you are
testing a cause-and-effect relationship, the
variable that causes the relationship is
called the independent variable and you
plot it on the THaxis, while the effect is
called the dependent variable and you plot
it on the EXP axis. (Figure III.4).
νExperimental = 0,904 νPredict + 62,776 (1) with a good agreement Predicted values
R = 0,997
FigIII.4: Simple linear regression Tiohydantoin between the experimental frequencies
and predict
υ experimental frequency = 9.253 + 1.002 υ predicted frequency 46
( 2)
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νExperimental = 0,904 νPredict + 62,776 45 with a good agreement Predicted values
FigIII .5 Hydantoin linear regression between frequencies (experimental (νexp) and
Predict (νth))
On the other hand The frequency ranges in
[cm-1] that are close between
ThioHydantoin and Hydantoin
[631-632], [1045.1075], [1377.1381] and
[3257.3283] these answers vibration may
explain the main reason argument in the
logical ordered way is to the superposition
of modes it allows us assumed in these
four intervals
(1) = (2)
[υ experimental frequency ]thiohydantoin = [νExperimental frequency ]hydantoin
[9.253 + 1.002 υ predicted frequency] thiohydantoin = [0,904 νPredict + 62,776] hydantoin
Hence one can see the proportionality
between the two frequencies predicts in
order to the relationship.
[υ predicted frequency ]thiohydantoin =[ 0,781 νPredicted frequency]hydantoin + 47,449 (3)
In calculate it is possible to assimilate
quality by the ratio between two
frequencies of two molecules by this
relationship (3)
VII.Conclusion:
This study and comparison allows us in
ordre to explain the biological, optical and
steric activities , we have been calculated
and performed by using in Molecular
geometry the Molecular Mechanics, PM3,
ab initio/HF and DFT/B3LYP methods
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basis set in order to obtain optimized
geometrical parameters are in good
agreement with experimental values. The
propriety study has that the aim qualitative;
the proprieties of Hydantoin and
ThioHydantoin, throw computational
methods.The nearly of calculated
geometries from the experimental
parameters and predicted values are in
good agreement for bond lengths, bond
angles with the dihedral angles of
Hydantoin have most values possibility
than Thiohydantoin .But dihedral angles of
hydantoin N1-C2-N2-C4 made exception
the predicts values are not consistent with
the value chain and closing the cycle rotary
manner or disrotatory in syntheses reaction
of hydantoin this means the cycle closes
from of C5-N1-C2-N2.
The vibrational frequencies of infrared
intensities with the stretching wave
numbers calculated by DFT/B3LYP
method agree satisfactorily with
experimental results. On the basis of
agreement between the calculated and
experimental results, assignments of all the
fundamental vibrational modes of
ThioHydantoin and Hydantoin or
Hydantoins were examined and proposed
in this investigation. This study
demonstrate that scaled are different
DFT/B3LYP calculations are powerful
approach for understanding the vibrational
spectra of medium sized organic
compounds.
On the other hand The frequency ranges in
[cm-1] that are close between
ThioHydantoin and Hydantoin
[631-632], [1045.1075], [1377.1381] and
[3257.3283] these answers vibration may
explain the superposition of modes it
allows us assumed in these four intervals.
Hence one can see the proportionality
between the two frequencies predicts in
order to offers the relationship linear
between a predicted frequency of
Thiohydantoin and Hydantoin.
[υ predicted frequency ]thiohydantoin =[ 0,781 νPredicted frequency]hydantoin + 47,449 (3)
This equation shows the differences
between the two frequencies Predicts,is
significant,robust and has a good
predictive ability.
Each hydantoin molecule or thiohydantoin has
the specific properties, but the both molecular
constitute an important class of
heterocyclic Hydantoins from calculate it is
possible to assimilate quality by the ratio
between two frequencies of two molecules by
this relationship (3) wich offer interesting
activity biological in medicinal chemistry
and optical with the value chain and
closing the cycle rotary manner or
disrotatory in syntheses reaction of
hydantoin.
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