J.Inst.

Chemists, 79 (3), 2007, 75-80

Spectroscopic and Inter Molecular Studies of Pharmaceutically Important

Anisole Monomer and its Nitro Substitutents in Ground Electronic States

Y.P.Singha*, R.A.Singhb and Ratnesh Dasc

a
Department of Physics, Govt. Women’s Polytechnic College, Sagar (MP), INDIA
470001.E-mail: Y_P_S_2k@Yahoo.com
b
Department of Physics, Dr. H.S.Gour University, Sagar (MP), INDIA, 470001
c
Department of Chemistry, Dr. H.S.Gour University, Sagar (MP), INDIA, 470001,
E-mail: ratnesh_das@breakthru.com

ABSTRACT

The electronic absorption spectra of Anisole’s Monomer molecules and its nitro
substitutents have been studied using GF matrix and MOPAC method. Assuming Cs point
symmetry, vibrational assignments for the observed frequencies have been proposed. The spectra
exhibit distinct features originating from low frequency vibrational modes caused by intra-
molecular motion. Normal modes have been calculated and an assignment of the observed
spectra has been proposed. Experimental frequencies are compared with those obtained by
G.F.Matrix and MOPAC method.

Keywords : Anisole, Nitro-anisole, FTIR Spectra, Monomer

INTRODUCTION
Anisole (methoxybenzene) is one of the simplest aromatic compound to which ether
group is linked. Anisole, C6H5OCH3 (methyl phenyl ether), is a clear liquid that is soluble in
ether and alcohol; insoluble in water; boiling point 155 C. Anisole and its derivatives are used as
solvents and in perfumery. It is a part of cresol class antiseptic compounds and used as an insect
repellent. Their derivatives are also widely used in chemical reaction as intermediates to obtain
target materials such as dyes, pharmaceuticals, perfumes, photo initiators and agrochemicals 1.
Anisole is interesting because it contains an electronegative oxygen atom as a H-bond
acceptor. In addition, it is the simplest analog of the main structural component of a number of
macro cyclic hosts2. Furthermore, the orientation of its methyl group was found to be important
in governing the pharmacological properties of drugs .
3
. Owen and Hester carried out vibrational analysis of spectra of anisole and its
derivatives. He calculated torsional barriers restricting rotation about the phenyl and showed that

in the anisole molecule, except the hydrogen atoms of the CH 3 group, all the remaining atoms
are in the same plane.
4
R. Reimann et al had done experimental and theoretical investigations of vibrational
5
spectra of anisole. O. Desyatnyk et al studied rotational spectra and molecular structure of
anisole.
In the present study we report results on intra-molecular force fields of Anisole and Nitro-
anisole .

EXPERIMENTAL

Anisole and its nitro substitutents were purchased from Sigma Chemical Co (USA).
Anisole forms a colourless liquid with a pleasant smell. Nitroanisole is a yellowish liquid
insoluble in water.
Polarized Raman spectrum were recorded at room temperature in the range 100-4000
cm-1 in liquid phase on a Jobin Yvon Ramanor HG 25 spectrometer.
I.R. Spectrum has been recorded in the liquid phase in the range 400-4000cm-1 on Perkin-
Elmer spectrometer Model 397. The accuracy of the measurements was estimated to be within
3cm-1 and the resolution was better than 2cm-1 through the entire range for both the spectra.
RESULTS AND CALCULATIONS

For normal modes of Benzene ring modes, initial constants were chosen as per earlier
studies2-4,6. Frequencies of ring modes were reproduced satisfactorily. All the frequencies were
reproduced within 2.7%
C-OCH 3 Group Modes
The OCH 3 stretching mode (asymmetric and symmetric) has been assigned by Balfour 10

3004 cm −1 and 2834 cm −1 .Owen and Hester 3 and Balfour 10 have assigned the frequencies 1040

& 1039 cm −1 for O-CH 3 stretch. Ramana Rao et al9 have assigned this at 1000-1100 cm −1 .

Balfour 10 and Ramana Rao9 have assigned the C-OCH 3 in-plane-bending near 230 cm −1

.Owen and Hester 3 have assigned O-CH 3 in-plane-bending at 100 cm −1 and Ramana Rao have

assigned it at 58 cm −1 .Ramana Rao et al 9 have assigned H-C-H in-plane angle bending at 1170
cm −1 whereas Balfour have assigned it at 1180 cm −1 .
Campagnaro and Wood 11
have assigned a frequency of 285 cm −1 to O-C-H in-plane
bending.
Balfour 10
has assigned C-OCH 3 out-of-plane bending at 210 cm −1 . Ramana Rao has

assigned it at 160 cm −1 . Owen and Hester has assigned a frequency of 100 cm −1 for O-CH

3 out-of-plane bending mode.

OCH 3 wagging mode appear in the region 950 in the study of Ramana Rao. Balfour has

assigned it at 1170 cm −1 .
In the present study, we get these frequencies as shown in table 2.
NO 2 Group Modes
In the presence of NO 2 group in substituted benzene, N-O1 and N-O2 stretching
vibration (symmetric and asymmetric) has been predicted to appear with strong intensity by
several workers 7-8.
Based on what we observed for the CH2 and NH2 stretch, we would expect a symmetric
and an asymmetric stretch for the N-O bond in the nitro group halfway between the N=O and N-
O stretches. Since both of those functional groups are not covered in this discussion, we will
need to assume for the present that this is correct. Two strong bands are observed, one at 2000-
2200 cm-1 and a second between 1700-1900 cm-1. R.B. Singh12 observed in-plane bending
mode at 890 cm −1 and he didn’t get bending asymmetric mode. He observed wagging mode at
728 cm −1 and torsion mode at 158 cm −1 . Our assignments are in good agreement with those
of earlier workers 7-8.
In the present study, we get these frequencies as shown in table 3.

Table 1 Assumed Bond Length and Bond angle in Anisole and Nitro- anisole 5

Bond length (A 0 ) Bond Angle (Degree )

Bond By ab- Experimental By Bond Angle By ab-inito Experimental By MOPAC
inito MOPAC method Calculation
method 15 Calculation
C1 – C 2 1.399 1.387 1.400 C 6 C1 C 2 120.1 121.1 120.0
C2 – C3 1.399 1.407 1.399 C1 C 2 C 3 119.2 118.7 119.9
C3 – C 4 1.392 1.392 1.400 C1 C 6 C 5 120.0 119.5 119.9

C 4 – C5 1.399 1.398 1.399 C2 C3C 4 121.0 121.0 120.0

1.390 1.392 1.400 120.4 120.5 120.0
C5 – C6 C 4 C5C6
1.400 1.396 1.399 119.3 119.2 119.0
C 6 – C1 C3C 4 C5
1.372 1.372 1.103 115.0 114.8 116.0
C1 – O1 C 6 C1 O1
1.372 1.417 0.549 124.0 124.3 124.5
O1 – C 7 C 2 C1 O1
1.089 1.071 1.060 116.6 117.5 118.0
C7 – H5 C1 O1 C 7
1.096 0.942 0.806 143.5 144.2 144.9
C7 – H6 C1 C 2 N
1.096 1.024 121.0 120.0 120.0
C7 – H7 C3C2 N
1.104 1.103 136.5 137.2 138.6
C–N CNO 2
N–O 1.029 1.028 148.1 147.2 147.5
CNO 3 119.0 119.8 120.0
O 1 NO 2 95.3 90.2 92.4
O1 C 7 H 5 118.1 119.3 120.2
O1 C 7 H 6 180.0 179.7
O1 C 7 H 7 115.0 115.8
H5C7 H6 62.0 60.0
H6C7 H7 63.9

H5C7 H7 123.9

H 5 C 7 O1 120.2
115.8
H 7 C 7 O1
10.2
H 6 C 7 O1
Table 2 Internal Vibrations of OCH 3 Group

Mode of Vibration Anisole (cm −1 ) o-Nitro m-Nitro p- Nitro

Anisole (cm −1 ) Anisole(cm −1 ) Anisole(cm −1 )
OCH 3 Stretching 3101(E) 3100(E) 3101(E) 3118(E)
3151.1(GF) 3151.2(GF) 3140.2(GF) 3126.3(GF)
(asymmetric)
3149.1(M) 3147.3(M) 3148.3(M) 3148.6(M)
OCH 3 Stretching 3094(E) 3086(E) 3081(E) 3082(E)
3060.8(GF) 3070.5(GF) 3081.7(GF) 3075.9(GF)
(symmetric)
3078.7(M) 3076.6(M) 3077.6(M) 3078.6(M)
a’ C-OCH 3 in-plane bending 614(E) 611(E) 672(E) 651(E)
610.1(GF) 619.1(GF) 640.9(GF) 647.3(GF)
604.2(M) 624.5(M) 633.5(M) 694.7(M)
O-CH 3 in-plane bending 241(E) 263(E) 287(E) 289(E)
230.1(GF) 274.6(GF) 312.6(GF) 294.6(GF)
238.4(M) 298.7(M) 301.3(M) 293.4(M)
H-C-H in-plane angle 1312(E) 1288(E) 1299(E)
bending 1310.2(GF) 1268.2(GF) 1300.7(GF)
1312.7(M) 1271.5(M) 1297.6(M)
O-C-H in-plane angle 164(E) 160(E) 170(E) 173(E)
bending 160.3(GF) 155.3(GF) 180.5(GF) 189.3(GF)
176.2(M) 182.2(M) 183.8(M) 188.8(M)

Wagging 640(E) 664(E) 631(E) 643(E)

642.6(GF) 641.2(GF) 626.3(GF) 640.8(GF)
637.6(M) 649.6(M) 621.2(M) 643.3(M)
a” C-OCH 3 out-of plane 241(E) 241(E) 237(E) 301(E)
230.1(GF) 261.2(GF) 235.7(GF) 300.1(GF)
bending
238.4(M) 257.5(M) 240.2(M) 296.9(M)
O-CH 3 out-of-plane 161(E) 174(E) 179(E) 151(E)
179.5(GF) 189.2(GF) 180.6(GF) 153.9(GF)
bending
183.1(M) 189.3(M) 183.3(M) 161.2(M)

E :- Experimental frequencies
GF:- Theoretical frequencies calculated by GF Matrix method
M:- Theoretical frequencies calculated by MOPAC method
 Table 3: Internal Vibrations of NO 2 Group

Mode of Vibration o-Nitro m-Nitro p- Nitro

Anisole (cm −1 ) Anisole(cm −1 ) Anisole(cm −1 )
N-O stretching 2011(E) 2047(E) 2046(E)
(asymmetric) 2040.6(GF) 2052.2(GF) 2050.6(GF)
2055.7(M) 2059.7(M) 2054.7(M)
N-O stretching 1789(E) 1795(E) 1791(E)
(symmetric) 1800.2(GF) 1800.8(GF) 1800.8(GF)
a’ 1791.4(M) 1792.9(M) 1798.9(M)
NO 2 in-plane symmetric 651(E) 642(E) 651(E)
651.9(GF) 633.2(GF) 647.3(GF)
bending mode
660.0(M) 596.5(M) 694.7(M)
NO 2 in-plane asymmetric 459(E) 438(E) 487(E)
472.2(GF) 431.6(GF) 493.5(GF)
bending mode
464.9(M) 410.8(M) 604.2(M)
a” NO 2 out-of-plane 792(E) 788(E) 752(E)
771.3(GF) 762.3(GF) 760.1(GF)
wagging mode
786.2(M) 756.3(M) 763.1(M)
NO 2 Torsion mode 480(E) 491(E) 483(E)
488.1(GF) 487.3(GF) 477.8(GF)
491.2(M) 183.5(M) 496.7(M)

E :- Experimental frequencies
GF:- Theoretical frequencies calculated by GF Matrix method
M:- Theoretical frequencies calculated by MOPAC method
REFRENCES

1. www.chemicalland21.com. (2006)
2. L.C.Gronen and D.N.Reinhourdt, Supramolecular Chemistry, Kluwer Academic, Dor cle
cht, (1991)
3. Nil Owen and R.E.Hester; Spectrochim Acta , 25A, 340-343, (1969)
4. B.Reimann, K.Buchhold and B.Brutschy, J. Chemical Physics, 117, 19, (2002)
5. O. Desyatnyk, S. Thorwirth and Z. Kisiel, www.rcs.org/pccp, DOI 10.1039/b501041a,
(2005)
6. E.B.Wilson Jr, J.C. Decius and P.C.Cross, Molecular Vibrations, Mc Graw Hill
Book Co; New York (1955).
7. G.M.Barrow, Molecular Spectroscopy, Mc Graw Hill Book Co; New York, (1962)
8. F. Albert Cotton, Chemical Applications of Group Theory, Interscience Publishers, New
York, (1964)
9. G.Ramana Rao and D. Vijaya Kumar , Ind. J. Pure and App. Phys; 25, 58, (1987)
10. W.J.Balfour, Spectrochim Acta, 39A, 795-800, 1983Owen and Hester, Spectrochim Acta,
25A, 343, (1969)
11. G.E.Campagnaro and J.L.Wood, J. Mol. Structure, 6, 117, (1970)
12. R.B.Singh, Ph.D. Thesis, Banaras Hindu University, Banaras, India (1980)