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

[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

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

International Scientific Journal Journal of Environmental Science

http://environment.scientific-journal.com/

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



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



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)



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



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.



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;



Fig.III. 2: Different figures of 27 modes with bond of ThioHydantoin ring

Mode 1 Mode 2 Mode 3











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



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


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



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,


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;



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)



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)



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.



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)



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



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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