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Vanadium Pentoxide as a Catalyst for Regioselective Nitration of Organic

Compounds under Conventional and Nonconventional Conditions

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DOI: 10.1080/15533174.2013.790431

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VANADIUM PENTOXIDE AS A CATALYST FOR

REGIOSELECTIVE NITRATION OF ORGANIC COMPOUNDS
UNDER CONVENTIONAL AND NONCONVENTIONAL
CONDITIONS
a a a a
N. Venkatesham , K. Rajendar Reddy , K. C. Rajanna & P. Veerasomaiah
a
Department of Chemistry , Osmania University , Hyderabad , 500 007 , A.P , India
Accepted author version posted online: 24 Sep 2013.

To cite this article: Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2013): VANADIUM
PENTOXIDE AS A CATALYST FOR REGIOSELECTIVE NITRATION OF ORGANIC COMPOUNDS UNDER CONVENTIONAL AND
NONCONVENTIONAL CONDITIONS, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, DOI:
10.1080/15533174.2013.790431

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 ACCEPTED MANUSCRIPT

VANADIUM PENTOXIDE AS A CATALYST

FOR REGIOSELECTIVE NITRATION OF ORGANIC COMPOUNDS

UNDER CONVENTIONAL AND NONCONVENTIONAL CONDITIONS

N. Venkatesham, K. Rajendar Reddy, K. C. Rajanna*, P. Veerasomaiah

Department of Chemistry, Osmania University, Hyderabad – 500 007(A.P) India

E-mail:kcrajannaou@yahoo.com
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Abstract: Vanadium pentoxide is used as an efficient catalyst for regioselective nitration of

aromatic compounds under conventional and nonconventional conditions such as ultrasonically

assisted and microwave assisted reactions. The reactions underwent smoothly and afforded good

yields of products with high regio selectivity. Observed longer reaction times (about 8 hrs.) in

V2O5 catalyzed reactions reduced to (0.5 hrs/30 min) under sonication and (90 sec) in the case of

microwave assisted reactions. When ortho position is blocked para derivatives are obtained as

end products while ortho nitro products are obtained when para position is blocked.

Keywords: Vanadium pentoxide; Sonication; microwave irradiation; Regioselective Nitration;

Rate accelerations

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Introduction

The transition metals are the group of metals in the middle section of the periodic table, which

have ones, three p, and five d orbitals that possess geometrical and energetic features suitable for

bonding with the ligands. The outermost incompletely filled d orbitals facilitate them to accept

and donate electrons. By giving and taking electrons so easily, transition metal catalysts speed up

reactions. In view of this important behavior of transition metals, there has been an upsurge since

the 1940s, in the area of catalysis research in general and transition metal catalysis complexes in
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particular. This also resulted in a rapid development of newer process technologies relevant to

industrial scale reactions for the production of organic compounds using transition metal
[1]
complexes as catalysts . The demand for cheaper and more efficient processes in the industry

necessitated a major explosion of research in the area of synthetic chemistry to develop new
[2] [3] [4]
systems that can act as catalysts . The contributions of Ziegler and Natta , Fischer and
[5]
Wilkinson in this area of chemistry are highly noteworthy. Transition metal-catalyzed

reactions are one of the most powerful and direct approaches for the synthesis of organic

molecules.

Vanadium is a d-transition metal found in Group VA of the Periodic Table. Vanadium’s ground

state electron configuration is [Ar] 3d34s2. When transition elements ionize, they lose their

valence s electrons before losing their d electrons. Vanadium has 5 valence electrons that can be

lost. Vanadium exhibits four common oxidation states +5, +4, +3, and +2 each of which can be

distinguished by its color. Vanadium (V) oxide is commonly known as vanadium pentoxide

(V2O5) or vanadia. Because of its high oxidation state, it is both an amphoteric oxide and an

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oxidizing agent, which catalyses several useful aerobic oxidation reactions, the largest scale of

which underpins the production of sulfuric acid from sulfur dioxide. It is used as an efficient

catalyst for the aerobic and nonaerobic oxidation of alcohols with good regio selectivity. Primary

alcohols were converted to aldehydes and secondary alcohols to ketones with a catalytic amount

of V2O5 in toluene at 100°C.

[6]
Recently Clark and Rothenberg have demonstrated Vanadium-catalysed oxidative

bromination by means of dilute mineral acids, hydrogen peroxide, and alkali bromides. The
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developed methodology was effective for the bromination of activated and non-activated (but not

deactivated) aromatic substrates. An option of using H2SO4, HNO3, HBr, HCl, and (to a lesser

extent) H3PO4 was also suggested option for recycling industrial acid waste. In another method
[7]
Bhattacharjee et al used vanadium (V) or molybdenum (VI), KBr, and hydrogen peroxide in

aqueous medium for electrophilic bromination of organic compounds. Even though several
[8-10]
methods are available on the nitration of organic compounds vanadium pentoxide has not

been explored as a catalyst so far. As a part of our ongoing work on the exploration of transition

metal catalysed organic transformations under conventional and nonconventional conditions [11-
13]
, we wish to present certain interesting results using vanadium pentoxide as a catalyst for

effective nitration of organic compounds under conventional and nonconventional conditions.

1. Experimental Details

1.1. Materials and Methods

Laboratory Grade reagents and substrates were procured from Merck, SD fine chemicals or Alfa

Aesar. Doubly distilled water (distilled over alkaline KMnO4 and acid dichromate in an all glass

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apparatus) was used whenever required. HPLC grade Solvents were used as such. Laboratory

model microwave reactor (CEM – 908010, bench mate model, 300 W equipped with

temperature, pressure and microwave power control units) was used for microwave assisted

reactions in this study.

2.2. Typical Experimental Procedure for Nitration of Organic Compounds under

Conventional Conditions
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In a typical experiment, Phenol (0.094 ml, 1 mmol) and V2O5 (9 mg, 0.005 mmol) were

suspended in dichloroethane (10 ml), followed by the addition of 69% HNO3 (0.063 ml, 1

mmol). The reaction mixture was stirred at room temperature till the completion of reaction as

indicated by TLC. The reaction mixture was filtered off and washed with water; organic layer

was separated out dried over sodium sulphate and evaporated under vacuum. The crude product

was purified by column chromatography using ethyl acetate: hexane (3:7) as eluent. IR, NMR

and Mass Spectroscopic analysis of the product indicated that phenol afforded p-nitrophenol as

the major end product with 85% yield (Exptal m.p 113°C (lit.mp. 114°C).

2.3. Typical Procedure for ultrasonic assisted Nitration (USNAR) of Organic compounds:

Methodology for ultrasonic assisted Nitration (USNR) of Organic compounds is by and large

similar to the one described for conventional method. Reaction flask containing Phenol (0.094

ml, 1 mmol) and V2O5 (9 mg, 0.005 mmol) dissolved in dichloroethane 69% HNO3 (0.063 ml, 1

mmol) was added and placed in ultrasonic Sonicator bath and progress of the reaction was

monitored by TLC. After completion of the reaction, the reaction mixture was filtered and

washed with water. Remaining part of the work up similar to the one adopted for conventional

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approach. All products are characterized by comparison of their IR, 1H-NMR and Mass spectra

and also with their physical data.

2.4. Typical Experimental Procedure for Microwave Assisted Nitration (MWANR) of

Organic Compounds

The microwave reactor used was of CEM make, which was equipped with temperature, pressure

and microwave power control units. An oven-dried microwave vial was charged with a mixture
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containing aromatic compound, V2O5 (9 mg, 0.005 mmol) and 69% HNO3 (0.063 ml, 1 mmol)

and silica gel slurry, and irradiated in a microwave (power input 140 W) at 150°C for few

minutes. After completion of the reaction, as ascertained by TLC, the reaction mixture was

treated with sodium bicarbonate; the organic layer was diluted with dichloromethane (DCM),

and separated from aqueous layer. Crude product mixture was purified with ethyl acetate DCM

mixture. The purity was checked with TLC. The products were identified by characteristic

spectroscopic data.

2. Results & Discussion

In order to optimize the reaction conditions, nitration reactions are performed in different solvent

media using varied amounts of V2O5 (0.001 to 0.01 mol/dm3) as catalyst. Table-1 shows reaction

times and percentage (%) yield of nitration of Phenol under different reaction conditions.

Reaction underwent smoothly in DCE when 0.005 mmol of V2O5 is used as a catalyst. Keeping

this in view 0.005 mol of V2O5 is used throughout the study.

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The nitration of certain organic compounds with V2O5 as catalyst in presence of small amount of

HNO3 and afforded mono nitro derivatives in very good yield (Scheme-1).

A wide range of non-active, moderately active and active aromatic compounds and heterocyclic

compounds are chosen for nitration under conventional and non-conventional conditions;

corresponding results are presented in table-2. The data revealed that nitration of aromatic

compounds underwent smoothly with good regioselectivity in presence of V2O5, which are
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associated with long reaction times (8 to 12 hours), good yields. It is of interest to note that para

substituted compounds (entries 3,5,7,8,13,15-18) underwent nitration only at ortho position ,

while ortho substituted compounds (entries 2,6,14) afforded para derivative in very good yield.

Even though, benzene failed to undergo nitration; it is also of interest to note that aromatic

hydrocarbons such as anthracene, naphthalene, α-naphthol, β –naphthol underwent smooth

nitration with fairly good yields. When this protocol is extended to carbonyl compounds,

nitration underwent smoothly without oxidation or any side. The reaction was clean, no attack

being observed on the alkyl portion of the ketones. To check the regioselectivity of the reaction,

the reaction is carried out with different para substituted aromatic carbonyl and related

compounds, which afforded only meta nitrated product in good yield.

To obtain further advantage of this protocol, the reactions are conducted under nonconventional

activation techniques, such as ultrasonically assisted and microwave assisted methods because

ultrasonically assisted reactions (USAR) microwave assisted reactions (MWAR) have become

stimulus to physical and organic chemists because of their immense importance to promote and

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[14-17]
enhance a broad spectrum of synthetic organic reactions . The use of these non-traditional

tools have been found to of great help in overcoming many of the difficulties associated with
[18]
conventional reactions related and environmental advantages . All the reactions underwent

dramatic rate enhancements followed by achieving the selectivity, ease of experimental

manipulation. The reaction times reduced from 8-12 hours (under conventional conditions) to

about 30 min in USA reactions and about 90 sec in MWA reactions.

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Rate accelerations of the ultrasonically assisted nitration reactions (USNR) in the present study

are due to cavitation, a physical process that creates, enlarges, and implodes gaseous and
[14-16]
vaporous cavities in an irradiated liquid . Cavitation is a process in which mechanical

activation destroys the attractive forces of molecules in the liquid phase. Applying ultrasound,

compression of the liquid is followed by rarefaction (expansion), in which a sudden pressure

drop forms small, oscillating bubbles of gaseous substances. These bubbles expand with each

cycle of the applied ultrasonic energy until they reach an unstable size; they can then collide

and/or violently collapse. Cavitation induces very high local temperatures and the liquid and

enhanced mass transfer.

[17]
On the other hand the observed rate and yield enhancements in MWA reactions attributed to

the bulk activation of molecules due to the selective absorption of microwave (MW) energy by

polar molecules, nonpolar molecules being inert to the MW dielectric loss. This point can be

further supported from the fact that the rate of the reaction has a direct dependence on the

fraction of activated/energized species.

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3. Conclusions

In conclusion, the authors have demonstrated that vanadium pentoxide as an efficient catalyst

regioselective nitration of organic compounds under conventional and nonconventional

conditions such as ultrasonically assisted (USAR) and micro wave-assisted (MWAR) nitration

reactions. The developed methods have several advantages such as simple workup procedure,

good regioselectivity, short reaction times and high product yields. Longer reaction times of
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conventional methods (8-10 hrs) reduced remarkably to about 30 min (0.50hr) in sonicated and

90 sec (< 2min) in case of MWAR. It is noteworthy to mention here that if the ortho position is

engaged, p-nitro derivatives are obtained while o-nitro derivatives are obtained when para

position is engaged.

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Hall: New York. 1981.

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2009, CRC Press: (Taylor and Francis Group).

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4. (a) Cotton, F. A.; Wilkinson; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry:

A Comprehensive Text; Sixth Ed, 1999. (b) Wilkinson, J. Chem. Soc. (A). 1966, 1711.

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Mukherjee, J. J. Chem. Res. Synop. 1995, 80; (c) Bhattacharjee, M.; Mukherjee, J. J. Chem.
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Res. Synop. 1995, 238; (d) Mukherjee, J.; Ganguly, S.; Bhattacharjee, M. Indian J.Chem.,

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9. (a) Schofield, K. “Aromatic Nitrations” Cambridge Univer-sity Press, Cambridge, 1980; (b)

Ridd, J. H. Accounts of Chemical Research, 1971, 4, 248.

10. Fener. H.; Nielson, A. T. “Nitro Compounds: Recent Advances in Synthesis and Chemistry,”

VCH Publishers, New York, 1990.

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1351.

12. Rajanna, K. C.; Satish Kumar, M.; Venkanna, P.; Ramgopal, S.; Venkateswarlu, M.

International J. Org. Chem., 2011, 1, 250.

13. (a) Rajanna, K. C.; Ali, M. M.; Sana, S.; Saiprakash, P. K. Chemistry Lett., 2000, 29, 48.; (b)

Rajendar Reddy, K.; Sana, S.; Uppalaiah, K.; Rajanna, K. C.; Veerasomaiah, P.

International J. Org. Chem., 2012, 2, 254; (c) Abdulla; Amina, S.; Arun Kumar, Y.;

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Arifuddin, M.; Rajanna, K. C. Synth. Comm., 2011, 41, 2946; (d) Sana, S.; Rajanna, K. C.;

Rajendar Reddy, K.; Bhooshan, M.; Venkateswarlu, M.; Satish Kumar, M.; Uppalaiah, K.

Green. Sust. Chem., 2012, 2, 97 (e) Srinivas, P.; Rajanna K. C.; Satish Kumar, M.; Rajendar

Reddy, K. Synth. React. Inorg. Metal-Org. Nanomet. Chem., 2013 (In press)

14. (a) Einhorn, C.; Einhorn, J.; Luche, J. Synthesis, 1989, 787; (b) Ley, S.V.; Low, C.M.R.

"Ultrasound in Synthesis", Springer, Berlin, 1989; (c) Richards, W.T.; Loomi, A. L. J. Am.

Chem. Soc., 1927, 49, 3086.

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15. (a) Suslick, K.S. Science, 1990, 249, 1439; (b) Mason, T. J.; Lorimer, J. P. "Sonochemistry,

Theory, Applications and Uses of Ultrasound in Chemistry", John Wiley and Sons, New

York, 1988; (c) Mason, T. J. Chem. Soc. Rev., 1997, 26, 443; (d) Singh, V.; Kaur, K. P.;

Khurana, A.; Kad, G. L. Resonance, 1998, 56.

16. (a) Mason, T. J. "Chemistry with Ultrasound", Elsevier Science Publishers Ltd., England

1990; (b) Kottrorearou, A.; Hoffman, M. R. J. Phys. Chem., 1991, 95, 3630; (c) Margulis, M.

A. "Advances in Sonochemistry", ed. by Mason, T. J. Greenweich Connection. JA., London,

1990, 1, 49.

17. (a) Kappe, C. O. Angew. Chem. Int Ed. 2004, 43, 6250; (b) Kappe, C. O.; Stadler, A.

Microwaves in Organic and Medicinal Chemistry, Wiley, 2005; (c) Loupy, A. Microwaves in

Organic Synthesis, Wiley, 2005.

18. (a) Varma, R. S. Green Chemistry, 1993, 43; (b) Anastas, P. T., Levy, I. J., Parent, K. E., ed.

(2009). Green Chemistry Education: Changing the Course of Chemistry. ACS Symposium

Series. 1011. Washington, DC: American Chemical Society; (c) Linthorst, J.A. Foundations

of Chemistry, 2010, 12, 55–68.

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Spectroscopic Data

1. 2-Nitrophenol: 1H NMR (300 MHz, CDCl3) δ 9.52 (s, 1H), 8.15 (dd, J=8.5Hz, J=8Hz,

1H), 8.12 (d, J=8Hz, 1H), 7.55 (dd, J=8Hz J=7.5Hz, 1H) 6.95 (d, J=8.5Hz, 1H); ESI-MS

m/z = 139.
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2. 2-Me- 4-NO2 Phenol: 1H NMR (300 MHz, CDCl3) δ 10.55 (s, 1H), 8.25 (dd, J=8.5Hz,

J=7.5Hz, 1H), 8.12 (d, J=8.5Hz, 1H), 2.35 (s, 3H), 6.85 (d, J=8.5Hz, 1H); ESI-MS m/z =

153.

3. 2-NO2 4-Me Phenol: 1H NMR (300 MHz, CDCl3) δ 10.42 (s, 1H), 7.92(s, 1H), 7.32 (d,

J=8Hz, 1H), 7.12(d, J=8Hz, 1H), 2.42 (s, 3H); ESI-MS m/z = 153.

4. 3-Me- 6-NO2 Phenol: 1H NMR (300 MHz, CDCl3) δ10.86 (s, 1H), 8.12(d, J=8Hz, 1H),

7.16(d, J=8Hz, 1H), 6.64 (s 1H) 2.32 (s, 3H); ESI-MS m/z = 153.

5. 4-Cl-2-NO2 phenol: 1H NMR (300 MHz, CDCl3) δ10.54 (s, 1H), 7.82(d, J=8Hz, 1H), 8.36

(s 1H) 7.12 (d, J=8Hz, 1H); ESI-MS m/z = 174.

6. 4-NO2 2-Cl Phenol: 1H NMR (300 MHz, CDCl3) δ10.66 (s, 1H), 8.34(s, 1H), 8.12(d,

J=8.5Hz, 1H), 7.15(d, J=8.5Hz, 1H); ESI-MS m/z = 174.

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7. 2-NO2 4-Br Phenol: 1H NMR (300 MHz, CDCl3) δ10.45 (s, 1H), 8.25(s, 1H), 7.72(d,

J=8Hz, 1H), 7.10(d, 1H, J=8Hz, 1H); ESI-MS m/z = 218.

8. 2- NO2 Benzene-1, 4-diol: 1H NMR (300 MHz, CDCl3) δ10.26(s, 2H), 7.14(d, J=8.5Hz,

1H), 6.92(d, J=8.5Hz, 1H), 7.48(s, 1H); ESI-MS m/z = 155.

9. 2- NO2-1-Naphthol: 1H NMR (300 MHz, CDCl3) δ12.24(s, 1H), 8.58(d, J=8.5Hz, 1H),
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8.15(d, J=8.5Hz, 1H), 8.05(d, J=8.5Hz, J=4Hz, 1H), 7.76(m, J=8.5Hz J=7.25Hz, 1H),

7.66(m, 1H, J=8Hz, J=7.25Hz, 1H), , 7.44(d, J=9Hz, 1H); ESI-MS m/z = 189.

10. 1- NO2-2-Naphthol: 1H NMR (300 MHz, CDCl3) δ12.18(s, 1H), 8.65(d, J=9Hz, 1H),

8.10(m, J=7.75Hz, J=5Hz, 1H), 7.80 (m, J=8.25Hz J=7.25Hz, 1H), 7.68(d, J=8.25Hz

J=5Hz, 1H), 7.58 (m, J=7.5Hz, J=7.25Hz, 1H), 7.20(d, J=9Hz, 1H); ESI-MS m/z = 189.

11. 4-Cl-3- NO2 benzaldehyde: 1H NMR (300 MHz, CDCl3) δ 10.16 (s, 1H), 8.22 (s, 1H), 7.90

(d, J = 3.1 Hz,

1H), 7.55 (d, J = 3.1 Hz, 1H); ESI-MS m/z = 185.

12. 3-OH-4 NO2 acetophenone: 1H NMR (300 MHz, CDCl3) δ 10.68 (s, 1H), 8.10 (m, J = 8.5

Hz, J = 3.5Hz, 1H), 7.62 (d, J = 8.5Hz, 1H), 7.52 (d, J = 3.5Hz, 1H), 2.38 (s, 3H); ESI-MS

m/z = 181.

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13. 4-NH2-2- NO2 Phenol: 1H NMR (300 MHz, CDCl3) 9.92 (s, 1H) 7.24 (s, 1H), 6.76 (d, J =

8Hz, 1H), 6.82 (d,

J = 8Hz, 1H), δ 4.45 (s, 2H); ESI-MS m/z = 154.

14. 2-OH 5-NO2 Benzaldehyde: 11.24δ (s 1H, OH) 10.45δ (s 1H, CHO) 7.18δ (d 1H, J=8Hz)

8.36δ (d 1H, J=8Hz), 8.72δ (s 1H); m/z = 167

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15. 4-OH 3-NO2 Benzaldehyde: 11.28δ (s 1H, OH) 10.34δ (s 1H, CHO) 7.26δ (d6, 1H, dd,

J=7.5Hz)

7.64δ (d 1H, d J=7.5Hz) 8.38δ (s 1H); m/z = 167

16. 4-Cl-3- NO2 benzaldehyde: 1H NMR (300 MHz, CDCl3) δ 10.16 (s, 1H), 8.22 (s, 1H), 7.90

(d, J = 3.1 Hz,

1H), 7.55 (d, J = 3.1 Hz, 1H); ESI-MS m/z = 185.

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Table-1: Effect of Solvent and V2O5 on Nitration of Phenol under conventional conditions

S. No Solvent V2O5 Time Yield

(mmol) (hr) (%)

0.001 08 65
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0.002 08 70

1 DCE 0.005 08 80

0.01 08 77

0.001 11 65

0.002 11 68

2 ACN 0.005 11 75

0.01 11 70

0.001 13 60

3 MeOH 0.002 13 63

0.005 13 65

0.01 13 60

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Table-2: Nitration of Aromatic Compounds in Presence of V2O5

S. Substrate Product Conventi Sonication Microwav

No onal e

RT Yiel RT Yiel RT Yiel

(hrs d (min d (sec d

) (%) ) (%) ) (%)

OH OH
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NO2
89 98 08 98 :8 98

OH OH
CH3 CH3

89 98 08 98 :8 98
NO 2
2

OH OH
NO2

88 98 08 98 :8 90
CH 3 CH 3
3

OH OH
O2N
89 87 08 98 :8 98
CH3
CH3
4

OH OH
NO 2

89 89 08 89 :8 98
Cl Cl
5

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OH OH
Cl
Cl
89 87 08 98 :8 98
NO 2
6

OH OH
NO2

89 87 08 88 :8 89
Br Br
7

OH OH
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NO 2
89 89 08 98 :8 98
OH OH
8

OH OH
NO2
89 87 08 89 :8 89

NO2
OH
OH 89 88 08 87 :8 87

10

CHO CHO

89 88 08 88 :8 88
NO2
11 Cl Cl

COCH 3 COCH 3

8: 79 08 88 :8 87
OH OH
12 NO 2

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OH OH
NO2
88 78 78 77 898 79

13 NH2 NH2

CHO CHO
HO HO
88 78 87 88 888 88
NO2
14

CHO CHO
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88 88 08 88 888 87
NO2
15 OH OH

CHO CHO

8: 79 08 88 :8 87
NO2
Cl Cl
16

OH OH
NO2
8: 87 08 87 :8 98
NO2 NO2
17

COCH 3 COCH 3

8: 88 08 88 :8 98
NO2
18 Cl Cl

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X X

V2O5
NO2
HNO3 / DCE
Y i) Conventional Y
Downloaded by [Osmania University] at 03:22 04 October 2013

ii) Sonication
iii) Microwave
where X = OH, NH2, CHO, COCH3
Y= EWG or EDG

Scheme: 1 Nitration of Aromatic Compounds in Presence of V2O5

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