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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. Womenâ€™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

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Anisole Monomer and its Nitro Substitutents in Ground Electronic States

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.

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

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 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

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

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)

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

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)

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