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Our present work reports the IR spectra of amino substituted salicylic acids recorded by FTIR spectro-
meter and also simulated theoretically. The simulation was performed using GF matrix and AM1, PM3,
DFT method. In this work, the following steps were taken: optimizing the geometry, computing the IR
spectra and comparing it with experimental spectra. Assuming Cs point symmetry, vibrational assign-
ments for the observed frequencies have been proposed. The spectra exhibit distinct features
originating from low frequency vibrational modes caused by intra-molecular motion.
Key words: o-amino salicylic acid, m-amino salicylic acid, p-amino salicylic acid, FTIR spectra, vibrational
spectra, AM1, PM3, DFT, G-F Matrix.
INTRODUCTION
Salicylic acid contains both a hydroxyl and a carboxyl tions with a harmonic analysis (Bakker et al., 2004). Due
group, which react with either an acid or an alcohol. Sali- to deficiencies of the quantum chemical calculations and /
cylic acid has strong antiseptic and germicidal properties or due to the neglect of an harmonic effect, these freque-
because it is a carboxylated phenol. The presence of the ncies are typically a few percent higher than the observed
carboxyl group appears to enhance the antiseptic pro- ones.
perty. Many hair tonics and remedies for athlete’s foot, Marck et al. (2002) studied theoretical simulation of the
corns and warts employ the keratolytic action of salicylic
.
νs stretching band for salicylic acid taking into account
acid adiabatic couplings between the high-frequency O-H
Volvo et al. (1983) calculated normal coordinates for stretching and the low-frequency intermolecular O.......O
salicylic acid molecule and proposed the assignment of stretching modes. Jadrijevic et al (2004) analyzed the
the observed Raman and IR spectra. They found that structures and the spectral properties of salicylic acid and
C=O stretching modes are accounted for by specific inte- benzoic acids by means of FT-IR (Figures 1-3 and NMR
ractions due to the symmetry characteristics and possi- spectro-scopy.
ble conformational changes in the solution. We compared experimental results with calculated fre-
With the availability of powerful computers and the ad- quentcies of amino-salicylic acids using force matrix me-
vent of efficient density functional theory (DFT) methods thod and AM1, PM3 and DFT method. These methods
implemented in standard codes, structure and dynamics were able to account breadth of spectrum as well as de-
of systems containing a few tens o f atoms (even more) scription of vibrational modes to encourage the applica-
are now within reach. Vibrational spectra of small mole- tion of a similar procedure to a larger and more complex
cules of biological or pharmaceutical relevance are rou- group.
tinely treated combining DFT electronic structure calcula-
EXPERIMENTAL
3N
G tt’= =1 St . St’
Calculated Wavenumbers (cm-1) 4000
Where dot represents the scalar product of two vectors and =
3500 AM1 Method
1/m , the reciprocal of the mass of atom .
PM3 Method
3000 The AM1 and PM3 semi empirical approaches were performed
as implemented in MOPAC program (1997) and the precise key-
2500
words were used. DFT calculations were performed using HYPER
2000 CHEM program (2002) at the B3LYP (1993) levels of theory with 6-
1500
31G* basis set (1989). The vibrational IR spectra were calculated at
the B3LYP/ 6-31G* levels of theory. We have transformed the har-
1000 monic force fields, determined initially in the cartesian coordinates,
500 were transformed to the force fields in the internal local coordinates.
The force fields obtained were used to calculate the potential ener-
0 gy distribution (PED, 2001). Contributions greater than 10% are
0 1000 2000 3000 4000 given.
Experimental Wavenumbers (cm-1)
4000 Florio EL, Sibert EL, Zwier TS. (2001), Fluorescence-dip IR spectra of
Calculated W avnum bers
jet-cooled benzoic acid dimer in its ground and first excited singlet
3500
states. Faraday Discuss. 118: 315.
3000 Florio M, Zwier TS, Sibert EL (2003). Theoretical modeling of the OH
2500 stretch infrared spectrum of carboxylic acid dimers. J. Chem. Phy.
(cm -1)
118: 4.
2000 Here WJ, Random, L, Schlyer PVR, Pople JA (1989). Ab initio
1500 Molecular- Orbital Theory, Wiley, New York. pp 112-121
Hyperchem Package 7 for molecular modeling, (2002) Hypercube Inc.
1000 http:// www.wavefun.com
500 Jadrijevic M, Takac M, Topic D, (2004). FT-IR and NMR spectroscopic
studies of salicylic acid derivatives. Acta Pharm. 54: 177-197
0 Marek B, Wojcik MJ, Zieba A (2002). Theoretical model fora tetrad of
0 1000 2000 3000 4000 hydrogen bonds and its applications of infrared spectra of salicylic
acid. Chem. Phys. 124: 084306
Experimental Wavenumbers (cm-1) Volvo V, Colombo L, Furic K (1983). Vibrational spectrum and normal
coordinate calculations of the salicylic acid molecule. J. Raman
Spect. 14(5): 347-352.
Figure 6. Correlation diagram for experimental Vs calculated Williams and Wilkins (2002). Foye’s Principle of Medicinal Chemistry,
frequencies (DFT method) for 3-amino salicylic acid. 5th, Edition, New York. pp 118-129
Win MOPAC- Molecular Orbital Program, (1997) Fujitsu Limited http://
www.software.fujitsu.com/jp/winmopac
ACKNOWLEDGEMENTS
REFERENCES