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
[email protected]
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
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.145 hydantoin 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
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.
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
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 2Thiohydantoin 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, selfanticorps) 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 531and 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, antiulcer 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 donoracceptor 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 1415 .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
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 (6311G++ (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.
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).
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+ forcefield (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).
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
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
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
179,989
179,989
179,994
179,994
179,994
179,994
Bond angle (°)
Dihedral angles (°) C4-N3-C2-S6
174,80
III.1 Molecular geometry of Hydantoin
initio/HF and DFT method have been
The molecular structure of hydantoin is
depicted and compared with experimental
shown in (Figure 1). With this structural
parameters
model, hydantoin belongs to Cs point
structure
group
(TableIII.1).
symmetry.
The
optimized
22
obtained from the crystal
analyses
of
hydantoin
in
geometrical parameters of hydantoin by ab
Figure III.1: Conformation 3D of molecular structure and atom numbering adopted in this study for hydantoin (GaussView 09)
Table III. 1: Comparison of the experimental and calculated values of bond lengths and bond angles of Hydantoin
Parameters
Exp.48
ab initio/HF
Bond Length
6-
(A°)
31G+(d,p)
DFT(B3LYP)
6-31G++(d,p)
6-311G++(d,p)
6-31G+(d,p)
6-31G++(d,p)
6311G++(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
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
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
Bond angle(°)
Dihedral angles(°)
Thus, in this work was revealed good
The values experimentals this may be due
between the experimentally obtained
to probably steric of connections to
values data are in good agreement with the
terminals end of the link chain and closing
theoretical calculations for bond lengths,
the cycle of a rotary manner or disrotatory
bond angles but dihedral angles
in synthese reaction of Hydantoin this
N1-C2-N2-C4 made exception the
means that the cycle closes from of
predicts values are not consistent with
C5-N1-C2-N2.
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) ab
initio/HF
,and
at
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° (C5N1-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, CH,C=O,C=S Scissoring, C=O,C=S wagging, C-H rocking The asymmetric CH 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.
Table III.2: Comparison of the experimental and calculated vibration spectra of ThioHydantoin.
Symmetry
EXP. IR27
DFT(B3LYP)/ 6-311G++ (d,p)
Assignment
Mode N0 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
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
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
13
A
14
A
15
530
631
ω C5-H, ωN1-H, ω C=S, ω C=O, ωN3-H,
1006,43
ω C=S, ω C=O ,ω C5-H, ωN1-H,
1156
1058,49
υ C-H, ωN1-H, ωN3-H
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
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
1541,20
υ C4-H,ω C=O, ω C=S, ωN1-H, , ωN3H, 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
1528
1716
IRexp: Experimental Infrared; asym: asymmetric; sym: symmetric; ν: bond stretching δ: scissoring; τ: twisting; ω: wagging; ρ: rocking;
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
The experimental values in good agreement with t obtained from ab-initio/HF theory using
The diatomic molecules have only one link, which can be stretched. The more complex molecules have many
Basis 6-31G+(d,p)set and6-311G++(d,p) .
Connections, and vibration maybe combined, leading toνthe 3 C2=S6 and ν C4=O7 stretching modes were obser infrared absorption at the characteristic frequencies
with I-R intensity at 200, 371623Cm-1
Which can be linked to chemical groups. For example, atoms And frequency 1864, 9723Cm-1These considerations t of CH2, which is commonly found in organic Compounds, can vibrate in six different ways:
provide additional support.
Cyclic imides represent an important class of compou in medicinal chemistry due to its large
Stretching and skew symmetric, scissoring, and rocking,
agitation outside plane wagging and twisting
Spectrum of biological activities
28,42
experimental and predict frequency ν1 (NH) stretching mode for monomer was observed at (moderate intensity) (3283–3197cm–1), the
By simple regression is obtained
absorption in the large 428Cm-1, 429,743428Cm-1 ,429,7797428Cm-1and 433,4412428Cm-1 III.3. Vibration frequencies of
the title molecule have been assigned
Hydantoin
according to the detailed motion of the
IR spectroscopy can give a great deal of
individual atoms.
information on small ring heterocyclic,
All normal modes assigned to one of 21
because of the effects of ring strain on the
types of motion(C–H, C=O, C–H, and N–
frequencies of vibration of substituent's
H stretching's; HCH, CCN, CCH, NC=O,
attached to the ring, and because the ring
CC=O, NCN, CNC, CNH, and NCH
vibrations fall into a readily accessible
bindings, and HNC=O, OCCH, HCNH,
region of the IR spectrum 23, 33 and34.
NCNH, CNC=O, NCCN, CNCC, and
Experimental and theoretical
NCNC twisting) The asymmetric C-H
(DFT_B3LYP/6–31G++ (d, p)) vibrational
stretching frequency decreases with
wave numbers of Hydantoin were given in
increasing ring size, predicted by a
Table III.2.
calculation analysis.
Hydantoin consists of 11 atoms, which has
The results obtained from the calculations
27 normal modes. These normal modes of
show that, while the harmonic corrections
Relation betw
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 abinitio.
Table III. 3: Comparison of the experimental and calculated vibrational spectra of hydantoin.
Mode Symmetry
Assignment
EXP. IR 49
N0
DFT(B3LYP)/ 6-311G++ (d,p)
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
6
A
7
A
580
601.288
8
A
632
624.1676
9
A
670
701.9823
10
A
719
746.5964
νN1_H8,νC2=o6 and νC4=o7 ωC5_H10,ωC5_H11and νN1_H8,N3_H9andτ C2=O6,C4=O7 δC5_H10,δC5_H11 and ν N1_H8 δC5_H10,δC5_H11 and ν N1_H8 δC5_H10,δC5_H11 and νN1_H8 τ N3_H7 and νC5_H10
A
785
882.9414
12
A
899
968.2432
13
A
14
A
990
1072.2072
15
A
1075
1147.0616
16
A
17
A
1197
1265.0279
18
A
1287
1307.5245
19
A
1377
1361.2266
20
A
1429
1392.09
545.114
11
968.2617
1175.6719
ωC5_H10,ωC5_H11and νN1_H8,N3_H9andτC2=O6, C4=O7 ωC5_H10,ωC5_H11and νN1_H8,N3_H9and νC4=O7 τC5_H10, τ C 5_H11 ωC5_H10,ωC5_H11 and ν N1_H8 ωC5_H10,ωC5_H11,ωN1_H8 and ωN3_H9 τ C 5_H10,ƬC5_H11and νC4=O7 ωC5_H10,ωC5_H11,νN1_H8 andνN3_H9 νC2=O7 ωC5_H10,ωC5_H11and νN1_H8,νN3_H9 ω C5_H10,ω
21
A
1426.929
22
A
1696
1822.838
23
A
1774
1863.2827
24
A
2944
2966.5839
25
A
26
A
3130
3554.3144
27
A
3257
3584.495
3006.1303
C5_H11andνC2=O6,νN3_H9, νC4=O7 τC5_H10,ƬC5_H11and νN3_H9 ρC5_H10,ρC5_H11 and νN3_H9 ωC5_H10,ωC5_H11andνN1_ H8,νN3_H9 νN1_H8,νC5_H10and νC5_H11 ωN1_H8, ωC5_H10,ωC5_H11and νC2=O6,νC4=O7 νC5_H10,νC5_H11andνN3_H 9 τN 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;
Figure III.4 DIFFERENTS FIGURES OF 27MODES WITH BOND OF HYDANTOIN RING
MODE N°1
MODE N° 2
MODE N° 3
MODE N° 4
(NH,CH,CN)
(NH,CH,CO,CN)
(CN,NH,CH)
(CO,NH,CH,CN )
MODE N°5
MODE N°6
MODE N°7
MODE N°8
(NH,CN,CH)
(CH,NH,CO,CN)
(CH,NH,CN)
(NH,CO,CH)
MODE
MODE N°10
MODE N°11
MODE N°12
N°9(CO,CN,CH)
(CO,NH,CN,CH)
(NH, CN,NH)
(CN, NH, CH)
MODE
MODE14
MODE15
MODE16
MODE17
13(CN,CH)
(CH,CN,NH)
(CN,CH)
(CH,CN,NH)
(CH,CN,NH)
MODE 18(NH,CN)
MODE19
MODE 20
(NH,CH,CO)
(CN,CH,NH)
MODE22
MODE23
MODE 24
MODE 25
(NH,CO,CN)
(NH,CN,CO)
(CN,CH)
(CH,CN)
MODE 21(CH,CN)
MODE 26(NH,CN)
MODE 27(NH,CN)
The diatomic molecules have only one
using basis 6-31G+(d,p) set and 6-
link, which can be stretched. The more
311G++(d,p) .ν3 C2=O6 and ν C4=O7
complex connections, combined,
molecules and leading
have
many
stretching modes were observed with I-R
vibration
maybe
intensity at 200Cm-1, 371623Cm-1 and
to
the
infrared
frequency
1864,9723Cm-1These
absorption at the characteristic frequencies
considerations thus provide additional
which can be linked to chemical groups.
support.
For example, atoms of CH2, which is
Cyclic imides represent an important class
commonly found in organic compounds,
of compounds in medicinal chemistry due
can vibrate in six different ways: stretching
to its large spectrum of biological activities
and skew symmetric, scissoring, and
23, 35
rocking, agitation outside plane wagging
observed IR spectral data. In conclusion,
and twistingν1 (NH) stretching mode for
the 6-311G++base (d, p) lead to prediction
monomer was observed at (moderate
soft he theoretical molecular conformation
intensity) (3599,8–3570,24 cm–1), ν2 CH2
similar to that given by the experiment in
group (C5-H10,C5-H11) wave numbers
the case of the Hydantoin molecule
symmetric
studied.
and
asymmetric
stretching
; are in a good agreement with the
mode was observed at (2979,43 and
This conclusion is based on the
3023,23Cm-1) with twisting ,waging and
comparative study between the frequencies
scissoring the absorption in the large
calculated internal modes, using the
428Cm-1,
molecular conformation calculated by
,429,7797428Cm-1and
429,743428Cm-1 433,4412428Cm-1
the experimental values in good agreement with that obtained from ab-initio/HF theory
DFT/B3LYP and experimental frequencies.
III.5 Linear regression between
unknown values. in fact our comparison
experimental frequencies (νexp) and
between experimental frequencies and
Predict frequency (νth)
Predict frequencies amounts to a linear
Use linear regression or correlation by
regression method we found36.Following
IBM - SPSS Statistics V19.0. When you
the linear regression models, When you are
want to know whether one measurement
testing a cause-and-effect relationship, the
variable is associated with another
variable that causes the relationship is
measurement variable; you want to
called the independent variable and you
measure the strength of the association
plot it on the THaxis, while the effect is
(r2); or you want an equation that describes
called the dependent variable and you plot
the relationship and can be used to predict
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)
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
explain the main reason argument in the
[cm-1] that are close between
logical ordered way is to the superposition
ThioHydantoin and Hydantoin
of modes it allows us assumed in these
[631-632], [1045.1075], [1377.1381] and
four intervals
[3257.3283] these answers vibration may
(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 In calculate it is possible to assimilate quality by the ratio between two frequencies of two molecules by this relationship (3) VII.Conclusion:
(3)
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
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.
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.
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 [υ predicted frequency ]thiohydantoin =[ 0,781 νPredicted frequency]hydantoin + 47,449 This equation shows the differences between the two frequencies Predicts,is significant,robust and has a good predictive ability.
(3)
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 Each hydantoin molecule or thiohydantoin has the specific properties, but the both molecular
constitute an important class of heterocyclic Hydantoins from calculate it is
and optical with the value chain and closing the cycle rotary manner or disrotatory in syntheses reaction of hydantoin. hydantoins. European Journal of Organic Chemistry. 61796188(2009).
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