Organic Chemistry International

Organic Chemistry International / 2009 / Article

Research Letter | Open Access

Volume 2009 |Article ID 792967 | 4 pages | https://doi.org/10.1155/2009/792967

Catalytic Oxidative Cleavage of C=N Bond in the Presence of Zeolite H-NaX Supported C u ( N O 3 ) 2 , as a Green Reagent

Academic Editor: Pierre Esteves
Received28 Apr 2009
Accepted20 Jun 2009
Published15 Jul 2009

Abstract

Copper(II) nitrate supported on faujasite zeolites such as H-NaX is employed as solid acid catalysts for the clean and less hazardous catalytic oxidative cleavage of C=N bond under mild conditions. The reactions proceed very smoothly, and the yields are excellent.

1. Introduction

Increasing awareness of environmental hazards forces chemists to look for “eco-friendly” reaction conditions. In this connection, the use of heterogeneous catalysts involving solid reagents supported on high surface area materials, obtained by introduction of the reagent onto or into an organic polymeric or an inorganic porous or layered support material meets the fundamental challenges in the protection of the environment. These supported reagents have advantages such as easy handling, good dispersion of active sites leading to improved reactivity, safer and milder reaction conditions and minimal pollution [1, 2]. Oximes, hydrazones, and semicarbazones are useful as preferred derivatives for the identification and characterization of carbonyl compounds [3]. Several reagents have been reported for the regeneration of the carbonyl groups from the mentioned derivatives [49]. Although some of the methods involve mild reaction conditions, most of them require strong acidic media, long reaction time, a strong oxidizing agent (which causes over oxidation), and expensive and not readily available reagents.

Anhydrous metallic nitrates with a bidentate covalent coordination and with the available lower intermediate oxidation state for the metal, find maximum reactivity, and wider applicability [10, 11]. Their use, however, in organic syntheses is limited by solubility problems.

Laszlo et al. have used the K10-montmorillonite clay-supported copper(II) nitrate (claycop) and iron(III) nitrate (clayfen) for many of the organic reactions like oxidation of alcohols, oxidative coupling of thiols, hydrolytic cleavage of imine derivatives of carbonyl compounds, cleavage of tosylhydrazones, phenyl hydrazones, 2,4-dinitrophenylhydrazones and semicarbazones [12]. K10-montmorillonite supported Thallium nitrate is used for the oxidative rearrangement of alkyl aryl ketones into alkyl aryl carboxylates [13]. Pyridinium chlorochromate [14], potassium dichromate [15] and sodium metaperiodate [16] are some alumina-supported oxidants used for the chemoselective oxidation of alcohols and sulfides. In this paper we report a general method for the oxidative cleavage of C=N to their carbonyl derivatives in excellent yields without using any microwave or ultrasonic irradiation. To the best of our knowledge, this is the first report using a zeolite-supported cupric nitrate as the reagent for the regeneration of carbonyl group from oximes, hydrazones and semicarbazones. Moreover, copper-salts are inexpensive, easy to handle and environmentally friendly.

2. Experimental

2.1. Preparation of Zeolite H-Nax Supported Copper(II) Nitrate

To a solution of C u ( N O 3 ) 2 3 H 2 O (0.483 g, 2 mmoL) in acetone (15 mL), activated zeolite H-NaX (1 g) (obtained by activating N H 4 -NaX form of zeolite which has been prepared by partial exchange of sodium with ammonium salt in commercially available NaX) was added at once with stirring over a magnetic stirrer for 2 hours. Then the solvent was removed in a rotary evaporator. The blue powder formed was dried further at 130°C under reduced pressure. 1 g of H-NaX zeolite supported copper(II) nitrate reagent contains about 0.326 g of C u ( N O 3 ) 2 (1.35 mmoL).

2.2. General Procedure for the Oxidative Cleavage of C=N

0.05 g of substrate was ground with 0.25 g of activated supported reagent using mortar and pestle and refluxed using 10 mL of dichloromethane as solvent for specified time. The reaction mass was cooled to room temperature, filtered the catalyst and washed with dichloromethane twice. The filtrate was washed with distilled water thrice. After drying over anhydrous sodium sulphate, the solvent was evaporated to give the product. Percentage conversion of deprotection was checked by GC analysis.

3. Results and Discussions

The results illustrated in Table 1 indicate that the reaction is successful for a variety of aliphatic and aromatic oximes, phenylhydrazones, p-nitrophenylhydrazones and semicarbazones (Scheme 1). All these carbonyl derivatives were converted back to their corresponding aldehydes and ketones in dichloromethane as the optimal solvent, among the tested solvents including: methanol, ethanol, and acetonitrile taking benzaldehyde oxime as a representative example where the yields are found to be 79%, 81%, 72%, respectively. The reaction is found to be general with compounds having variety of functional groups like chloro, nitro, phenolic hydroxyl, and methoxy groups.


EntrySubstrateProductTime (h)Yield %

1Benzaldehyde oximeBenzaldehyde0.592
22-chlorobenzaldehyde oxime2-chlorobenzaldehyde0.2578
34-chlorobenzaldehyde oxime4-chlorobenzaldehyde0.2589
44-nitrobenzaldehyde oxime4-nitrobenzaldehyde0.2588
5Furfural oximeFurfural0.588
62-hydroxy 4-methoxy benzaldehyde oxime2-hydroxy4-methoxy benzaldehyde0.587
7Acetophenone oximeAcetophenone189
8Benzophenone oximeBenzophenone189
94-hydroxyacetophenone oxime4-hydroxyacetophenone179
10Cyclohexanone oximeCyclohexanone0.590
11Benzaldehyde phenylhydrazoneBenzaldehyde166
12Acetophenone phenylhydrazoneAcetophenone279
13Benzophenone phenylhydrazoneBenzophenone269
14 Benzaldehydes 2,4-dinitrophenylhydrazoneBenzaldehyde165
15Acetophenone 2,4-dinitrophenylhydrazoneAcetophenone386
16Benzophenone 2,4-dinitrophenylhydrazone Benzophenone379
17Furfural 2,4-dinitrophenylhydrazoneFurfural1.575
18Cyclohexanone 2,4-dinitrophenylhydrazoneCyclohexanone287
194-chlorobenzalde 2,4-dinitrophenylhydrazone4-chlorobenzalde366
202-chlorobenzalde 2,4-dinitrophenylhydrazone2-chlorobenzaldehyde278
212-hydroxy -4-methoxy benzaldehyde 2,4-dinitrophenylhydrazone2-hydroxy -4-methoxy benzaldehyde 0.569
222-hydroxy -4-methoxy benzaldehyde semicarbazone2-hydroxy -4-methoxy benzaldehyde178
23Benzaldehyde semicarbazoneBenzaldehyde291
24Acetophenone semicarbazoneAcetophenone278
25Benzophenone semicarbazone Benzophenone276


RunSolid acid supportYield of Benzaldehyde %

1H-NaX91
2NaX20
3NaY24
4ZSM-534
5MCM-4112
6 S i O 2 14
7None

792967.sch.001

As evident from the results, aldehyde derivatives were generally deprotected relatively faster than keto derivatives. It was also interesting to note that by controlling the amounts of the reagent, it was possible to avoid further oxidation of the liberated aldehydes to the corresponding carboxylic acids (entries 1–6), while we have demonstrated a facile aromatic nitration reaction with cupric nitrate in the presence of solid support [17], we did not observe any nitration of aromatic substrates during the cleavage reaction when we used optimum ratio of substrates and oxidants. Prolonged reaction time as well as excess of supported reagent in the case of aldehydes leads to further oxidation to the respective acids. The reaction failed to produce the ketones without cupric nitrate or H-NaX zeolite.

The superiority of H-NaX supported cupric nitrate as catalyst has been proved by the inefficiency in the regeneration of carbonyl groups from benzaldehyde semicarbazones by simple NaX supported C u ( N O 3 ) 2 or with unsupported C u ( N O 3 ) 2 , revealing the involvement of acidic sites present in the solid support. The optimum ratio of substrate to oxidant ( 1 5 ) was determined for complete conversion of oximes, semicarbazones and phenyl hydrazones to the corresponding carbonyl compounds. The recovered catalyst was verified for three times to catalyze the deprotection of benzaldehyde oxime. The efficiency of catalyst decreases considerably during the successive reusability tests.

Regarding the mechanism of the deprotection, it is proposed that the diffusion of the cupric ions into the zeolite H-NaX surface lattices and the subsequent formation of N 2 O 4 finally lead to the generation of N O 3 and N O + ions. The presence of these ions has been confirmed by comparison of IR spectra of C u ( N O 3 ) 2 and C u ( N O 3 ) 2 -loaded zeolite, which shows strong peaks around 1 0 3 0 1 0 7 0 c m 1 due to symmetric stretching of nitrate ion, 1 3 7 4 c m 1 due to asymmetric stretching of nitrate ion, 8 1 0 c m 1 due to in-plane deformation of nitrate ion and 7 1 0 c m 1 due to out of-plane deformation of nitrate ion, and peak around 2 3 3 2 2 4 1 5 c m 1 due to N O + . The nitrosonium ion may act as an electrophile, giving the corresponding carbonyl compounds. Based on the observations, the proposed mechanism for cleavage of the carbon–nitrogen double bond in oximes is presented in Scheme 2.

792967.sch.002

4. Conclusions

In conclusion, from commercially available NaX zeolite, a facile heterogeneous catalytic method, involving the more acidic form, namely, H-NaX with cupric nitrate has been employed for oxidative cleavage of C=N for the regeneration of carbonyl compound. It will be obvious that advantages of heterogeneous catalysis in terms of easy separation; and consistent yields are noteworthy. The operational simplicity, selectivity and cheapness, and good yields in very short times make this procedure a useful, attractive alternative to previously available methods.

Acknowledgment

K. Sivakumar thanks Jawaharlal Nehru Memorial Fund (JNMF) for the award of fellowship.

References

  1. P. Lazslo, Preparative Chemistry Using Supported Reagents, Academic Press, San Diego, Calif, USA, 1987.
  2. J. H. Clark, A. P. Kybett, and D. J. Macquarrie, Supported Reagents: Preparation, Analysis and Applications, VCH, New York, NY, USA, 1992.
  3. N. D. Cheronis and J. B. Entrikin, Identification of Organic Compounds, Interscience, New York, NY, USA, 1963.
  4. M. M. Heravi, L. Ranjbar, F. Derikvand, H. A. Oskooie, and F. F. Bamoharram, “Catalytic oxidative cleavage of C=N bond in the presence of mixed-addenda vanadomolybdophosphate, H6PMo9V3O40 as a green and reusable catalyst,” Journal of Molecular Catalysis A, vol. 265, no. 1-2, pp. 186–188, 2007. View at: Publisher Site | Google Scholar
  5. S. B. Shim, K. Kim, and Y. H. Kim, “Direct conversion of oximes and hydrazones into their ketones with dinitrogen tetroxide,” Tetrahedron Letters, vol. 28, no. 6, pp. 645–648, 1987. View at: Publisher Site | Google Scholar
  6. B. P. Bandgar, L. B. Kunde, and J. L. Thote, “Deoximation with N-haloamides,” Synthetic Communications, vol. 27, no. 7, pp. 1149–1152, 1997. View at: Publisher Site | Google Scholar
  7. M. Giurg and J. Młochowski, “Regeneration of carbonyl compounds from azines with cerium(IV) ammonium nitrate,” Synthetic Communications, vol. 29, no. 24, pp. 4307–4313, 1999. View at: Publisher Site | Google Scholar
  8. M. M. Heravi, D. Ajami, M. Tajbakhsh, and M. Ghassemzadeh, “Clay supported bis-(trimethylsilyl)-chromate: an efficient reagent for oxidative deoximation,” Monatshefte für Chemie, vol. 131, no. 10, pp. 1109–1113, 2000. View at: Publisher Site | Google Scholar
  9. M. M. Heravi, D. Ajami, and M. M. Mojtahedi, “Regeneration of carbonyl compounds from oximes on clayfen under conventional heating and microwave irradiation,” Journal of Chemical Research, vol. 2000, no. 3, pp. 126–127, 2000. View at: Google Scholar
  10. C. C. Addison, N. Logan, S. C. Wallwork, and C. D. Garner, “Structural aspects of co-ordinated nitrate groups,” Quarterly Reviews, Chemical Society, vol. 25, no. 2, pp. 289–322, 1971. View at: Publisher Site | Google Scholar
  11. C. C. Addison, “The relation between chemical reactivity of ligands and the nature of the metal-ligand bond: nitrato-complexes,” Coordination Chemistry Reviews, vol. 1, no. 1-2, pp. 58–65, 1966. View at: Publisher Site | Google Scholar
  12. A. Cornelis and P. Laszlo, “Clay-supported copper(II) and iron(III) nitrates: novel multi-purpose reagents for organic synthesis,” Synthesis, vol. 10, p. 909, 1985. View at: Publisher Site | Google Scholar
  13. E. C. Taylor, C.-S. Chiang, A. McKillop, and J. F. White, “Oxidative rearrangements via oxythallation with thallium(III) nitrate supported on clay,” Journal of the American Chemical Society, vol. 98, no. 21, pp. 6750–6752, 1976. View at: Publisher Site | Google Scholar
  14. D. Savoia, C. Trombini, and A. Umani-Ronchi, “Synthesis of 2-(6-carboxyhexyl)cyclopent-2-en-1-one, an intermediate in prostaglandin synthesis,” Journal of Organic Chemistry, vol. 47, no. 3, pp. 564–566, 1982. View at: Publisher Site | Google Scholar
  15. J. H. Clark, A. P. Kybett, P. Landon, D. J. Macquarrie, and K. Martin, “Catalytic Oxidation of Organic Substrates using Alumina Supported Chromium and Manganese,” Journal of Chemical Society., Chemical Communication, p. 1355, 1989. View at: Google Scholar
  16. G. W. Kabalka and M. Richard, “Organic reactions on alumina,” Tetrahedron, vol. 53, pp. 7999–8065, 1997. View at: Google Scholar
  17. A. Lalitha and K. Sivakumar, “Zeolite H-Y-supported copper(II) nitrate: a simple and effective solid-supported reagent for nitration of phenols and their derivatives,” Synthetic Communications, vol. 38, no. 11, pp. 1745–1752, 2008. View at: Publisher Site | Google Scholar

Copyright © 2009 A. Lalitha et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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