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. 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 Anisoles 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 intramolecular 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 EXPERIMENTAL atoms are in the same plane. R. Reimann et al
4

had

done

experimental and theoretical investigations of vibrational spectra of anisole. O. Desyatnyk et al

5

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 .

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 hosts . Furthermore, the orientation of its methyl group was found to be important in governing the pharmacological properties of drugs . Owen and Hester
3 2

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 1004000 cm-1 in liquid phase on a Jobin Yvon Ramanor HG 25 spectrometer.

carried

out

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.

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

____________________________________
Address for correspondence: Yogendra P. Singh, PhD, Department of Physics, Govt. Polytechnic College, Sagar (MP), INDIA; Tel.: 91-7582-237187; Fax: 91-7582-237470; E-mail: y_p_s_2k@yahoo.com.

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

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 were reproduced within 2.7%

C-OCH 3 Group Modes The OCH 3 stretching mode

frequencies as shown in table 2.

(asymmetric and symmetric) has been assigned by Balfour and Hester

10 3

NO 2 Group Modes In the presence of NO 2 group in

3004 cm 1 and 2834 cm 1 .Owen and Balfour

10

have assigned the

1

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.

frequencies 1040 & 1039 cm

for O-CH 3

stretch. Ramana Rao et al9 have assigned this at 1000-1100 cm 1 . Balfour

10

and Ramana Rao9 have

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 17001900 cm-1. R.B. Singh12 observed in-plane

assigned the C-OCH 3 in-plane-bending near 230 cm .Owen and Hester

1

have assigned O1

CH 3 in-plane-bending at 100 cm

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 . Campagnaro and Wood
11
1

have assigned

a frequency of 285 cm 1 to O-C-H in-plane bending. Balfour 10 has assigned C-OCH 3 out-ofplane bending at 210 cm
1

bending mode at 890 cm 1 and he didnt get bending asymmetric mode. He observed wagging mode at 728 cm 1 and torsion mode at 158 cm 1 . Our assignments are in good

. Ramana Rao has

assigned it at 160 cm 1 . Owen and Hester has assigned a frequency of 100 cm out-of-plane bending mode.
1

agreement with those of earlier workers 7-8. In the present study, we get these frequencies as shown in table 3.

for O-CH 3

Table 1

Assumed Bond Length and Bond angle in Anisole and Nitro- anisole 5
0

Bond

Bond length (A ) By abExperimental inito method 15 1.399 1.399 1.392 1.399 1.390 1.400 1.372 1.372 1.089 1.096 1.096 1.104 1.029 1.387 1.407 1.392 1.398 1.392 1.396 1.372 1.417 1.071 0.942

Bond Angle (Degree ) By MOPAC Calculation 1.400 1.399 1.400 1.399 1.400 1.399 1.103 0.549 1.060 0.806 1.024 1.103 1.028 Bond Angle By ab-inito method 120.1 119.2 120.0 121.0 120.4 119.3 115.0 124.0 116.6 143.5 121.0 136.5 148.1 119.0 95.3 118.1 Experimental By MOPAC Calculation 120.0 119.9 119.9 120.0 120.0 119.0 116.0 124.5 118.0 144.9 120.0 138.6 147.5 120.0 92.4 120.2 179.7 115.8 60.0 63.9 123.9 120.2 115.8 10.2

C1 C 2 C2 C3 C3 C 4 C 4 C5 C5 C6 C 6 C1 C1 O1 O1 C 7 C7 H5 C7 H6 C7 H7 CN NO

C 6 C1C 2 C1C 2 C 3 C1C 6 C 5 C2 C3C 4 C 4 C5C6 C3C 4 C5 C 6 C1O1 C 2 C1O1 C1O1C 7 C1C 2 N C3C2 N CNO 2 CNO 3 O 1 NO 2 O1C 7 H 5 O1C 7 H 6 O1C 7 H 7 H5C7 H6 H6C7 H7 H5C7 H7 H 5 C 7 O1 H 7 C 7 O1 H 6 C 7 O1

121.1 118.7 119.5 121.0 120.5 119.2 114.8 124.3 117.5 144.2 120.0 137.2 147.2 119.8 90.2 119.3 180.0 115.0 62.0

Table 2 Internal Vibrations of OCH 3 Group

Mode of Vibration OCH 3 Stretching (asymmetric) OCH 3 Stretching (symmetric) a C-OCH 3 in-plane bending O-CH 3 in-plane bending H-C-H in-plane angle bending O-C-H in-plane angle bending 164(E) 160.3(GF) 176.2(M) 640(E) 642.6(GF) 637.6(M) 241(E) 230.1(GF) 238.4(M) 161(E) 179.5(GF) 183.1(M) Anisole (cm 3101(E) 3151.1(GF) 3149.1(M) 3094(E) 3060.8(GF) 3078.7(M) 614(E) 610.1(GF) 604.2(M) 241(E) 230.1(GF) 238.4(M)
1

o-Nitro Anisole (cm 3100(E) 3151.2(GF) 3147.3(M) 3086(E) 3070.5(GF) 3076.6(M) 611(E) 619.1(GF) 624.5(M) 263(E) 274.6(GF) 298.7(M) 1312(E) 1310.2(GF) 1312.7(M) 160(E) 155.3(GF) 182.2(M) 664(E) 641.2(GF) 649.6(M) 241(E) 261.2(GF) 257.5(M) 174(E) 189.2(GF) 189.3(M)
1

m-Nitro ) Anisole(cm 3101(E) 3140.2(GF) 3148.3(M) 3081(E) 3081.7(GF) 3077.6(M) 672(E) 640.9(GF) 633.5(M) 287(E) 312.6(GF) 301.3(M) 1288(E) 1268.2(GF) 1271.5(M) 170(E) 180.5(GF) 183.8(M) 631(E) 626.3(GF) 621.2(M) 237(E) 235.7(GF) 240.2(M) 179(E) 180.6(GF) 183.3(M)
1

p- Nitro ) Anisole(cm 3118(E) 3126.3(GF) 3148.6(M) 3082(E) 3075.9(GF) 3078.6(M) 651(E) 647.3(GF) 694.7(M) 289(E) 294.6(GF) 293.4(M) 1299(E) 1300.7(GF) 1297.6(M) 173(E) 189.3(GF) 188.8(M) 643(E) 640.8(GF) 643.3(M) 301(E) 300.1(GF) 296.9(M) 151(E) 153.9(GF) 161.2(M)
1

Wagging

C-OCH 3 out-of plane bending O-CH 3 out-of-plane bending

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 N-O stretching (asymmetric) N-O stretching (symmetric) a NO 2 in-plane symmetric bending mode NO 2 in-plane asymmetric bending mode a NO 2 out-of-plane wagging mode NO 2 Torsion mode o-Nitro Anisole (cm 2011(E) 2040.6(GF) 2055.7(M) 1789(E) 1800.2(GF) 1791.4(M) 651(E) 651.9(GF) 660.0(M) 459(E) 472.2(GF) 464.9(M) 792(E) 771.3(GF) 786.2(M) 480(E) 488.1(GF) 491.2(M)
1

m-Nitro ) Anisole(cm 2047(E) 2052.2(GF) 2059.7(M) 1795(E) 1800.8(GF) 1792.9(M) 642(E) 633.2(GF) 596.5(M) 438(E) 431.6(GF) 410.8(M) 788(E) 762.3(GF) 756.3(M) 491(E) 487.3(GF) 183.5(M)
1

p- Nitro ) Anisole(cm 2046(E) 2050.6(GF) 2054.7(M) 1791(E) 1800.8(GF) 1798.9(M) 651(E) 647.3(GF) 694.7(M) 487(E) 493.5(GF) 604.2(M) 752(E) 760.1(GF) 763.1(M) 483(E) 477.8(GF) 496.7(M)
1

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)