Oxidation of Anilines with Hydrogen Peroxide and Selenium Dioxide as ­Catalyst

Abstract

A variety of substituted anilines are selectively oxidized to afford high yields of azoxyarenes by using 30% hydrogen peroxide and selenium dioxide as catalyst in methanol at room temperature. The oxidation of 4-alkoxyanilines under the same reaction conditions furnishes the corresponding 4-alkoxy-N-(4-nitrophenyl)anilines in reasonable yields, alongside other oxidation by-products. The structure of 4-methoxy-N-(4-nitrophenyl)aniline is elucidated by X-ray crystal structure analysis. From these results, some general aspects of the reaction pathways of aniline oxidation are discussed.

Key words

azoxyarenes - oxidation - anilines - hydrogen peroxide - selenium dioxide

References

• 1 Murahashi S.-I. Angew. Chem., Int. Ed. Engl.  1995,  34:  2443 
• 2 Thiel WR. Coord. Chem. Rev.  2003,  245:  95 
• 3 Rück-Braun K. Priewisch B. In Science of Synthesis   Vol. 31b:  Georg Thieme Verlag; Stuttgart: 2007.  p.1321 
• 4 Rück-Braun K. Dietrich S. Kempa S. Priewisch B. In Science of Synthesis   Vol. 31b:  Ramsden C. A. Georg Thieme Verlag; Stuttgart: 2007.  p.1425 
• 5 Rück-Braun K. Priewisch B. In Science of Synthesis   Vol. 31b:  Ramsden C. A. Georg Thieme Verlag; Stuttgart: 2007.  p.1401 
• 6 Yamamoto H. Kawasaki M. Bull. Chem. Soc. Jpn.  2007,  80:  595 
• 7 Rau H. In Photoreactive Organic Thin Films   Sekkat Z. Knoll W. Academic Press; San Diego: 2002.  p.3 
• 8 Takahashi H. Ishioka T. Koiso M. Hashimoto Y. Biol. Pharm. Bull.  2000,  23:  1387 
• 9 Yu B.-C. Shirai Y. Tour JM. Tetrahedron  2006,  62:  10303 
• 10 Tsutsumi O. Ikeda T. Science  1995,  268:  1873 
• 11 Campbell D. Dix LR. Rostron P. Dyes Pigm.  1995,  29:  77 
• 12 Aronzon D. Levy EP. Collings PJ. Chanishvili A. Chilaya G. Petriashvili G. Liquid Crystals  2007,  34:  707 
• 13a For RuCl₃, see: Barak G. Sasson Y. J. Org. Chem.  1989,  54:  3484 
• 13b For vanadium silicalite, see: Reddy JS. Sayari A. Catal. Lett.  1994,  28:  263 
• 13c For NaWO₄, see: Mel’nikov EB. Suboch GA. Belyaev EYu. Russ. J. Org. Chem.  1995,  31:  1640 
• 13d For Fe(III)-pyridine, see: Costas M. Romero I. Martínez MA. Llobet A. Sawyer DT. Caixach J. J. Mol. Catal. A: Chem.  1999,  148:  49 
• 13e For polyoxometalate, see: Sloboda-Rozner D. Witte W. Alster PL. Neumann R. Adv. Synth. Catal.  2004,  346:  339 
• For recent advances in the synthesis of azoxyarenes, see:
• 14a Rezaeifard A. Jafapour M. Naseri MA. Shariati R. Dyes Pigm.  2008,  76:  840 
• 14b Sakaue S. Tsubakino T. Nishiyama Y. Ishii Y. J. Org. Chem.  1993,  58:  3633 
• 15 Seok KW. Meyer TJ. Inorg. Chem.  2004,  43:  5205 
• 16 Huynh MHV. Meyer TJ. Chem. Rev.  2007,  107:  5004 
• 17 Schmittel M. Burghart A. Angew. Chem., Int. Ed. Engl.  1997,  36:  2550 
• 18 Priewisch B. Rück-Braun K. J. Org. Chem.  2005,  70:  2350 
• 19 Murahashi S.-I. Shiota T. Tetrahedron Lett.  1987,  28:  2383 
• 20a Crich D. Barba GR. Org. Lett.  2000,  2:  989 
• 20b ten Brink G.-J. Fernandes BCM. van Vliet MCA. Arends IWCE. Sheldon RA. J. Chem. Soc., Perkin Trans. 1  2001,  224 
• 20c ten Brink G.-J. Vis J.-M. Arends IWCE. Sheldon RA. J. Org. Chem.  2001,  66:  2429 
• 20d ten Brink G.-J. Vis J.-M. Arends IWCE. Sheldon RA. Tetrahedron  2002,  58:  3977 
• 21 Zhao D. Johansson M. Bäckvall J.-E. Eur. J. Org. Chem.  2007,  4431 
• 22 Barton DHR. Lester DJ. Ley SV. J. Chem. Soc., Chem. Commun.  1978,  276 
• 23 Lin D.-S. Yang SM. J. Appl. Polym. Sci.  2005,  98:  1198 
• 24 Nabid MR. Sedghi R. Entezami AA. J. Appl. Polym. Sci.  2007,  103:  3724 
• 25 Lindqvist T. Mellin C. Hillver S.-E. Acta Pharm. Nord.  1991,  3:  191 
• 26 Greci L. Tommasi G. Astolfi P. Petrucci R. Marrosu G. Trazza A. Sgarabotto P. Righi L. J. Chem. Soc., Perkin Trans. 2  2000,  1749 
• 27 Got M. Otsuka K. Chen X. Tao Y. Oyama M. J. Phys. Chem. A  2004,  108:  3980 
• 28 Hays JT. Young HL. Espy HH. J. Org. Chem.  1967,  32:  158 
• 29 Perrin DD. Armarego WLF. Purification of Laboratorial Chemicals   Wiley-VCH; Weinheim: 1998. 
• 32 Vowinkel E. Bartel J. Chem. Ber.  1974,  107:  1221 
• 33 Meyer F. Dahlem K. Justus Liebigs Ann. Chem.  1902,  331 
• 34 Defoin A. Geffroy G. Le Nouen D. Spileers D. Streith J. Helv. Chim. Acta  1989,  72:  1199 
• 35 Ferreira LM. Lobo AM. Prabhakar S. Teixeira AC. Tetrahedron  1999,  55:  3541 
• 36 Hou Z. Fujiwara Y. Taniguchi H. J. Org. Chem.  1988,  53:  3118 
• 37 Suresh S. Joseph R. Jayachandran B. Pol AV. Vinod MP. Sudalai A. Sonawane HR. Ravindranthan T. Tetrahedron  1995,  51:  11305 
• 38 McKillop A. Raphael RA. J. Org. Chem.  1970,  35:  1670 
• 39 Abramovitsch RA. Davis BA. J. Chem. Soc. C  1968,  119 
• 40 Merz MPL. inventors; French Pat. Appl. FR  1376778.  ; Chem. Abstr. 1964, 63, 3134

30

SCALE3 ABSPACK and CrysAlisRed (Version 1.171.29.10), Oxford Diffraction Ltd, Abingdon, Oxford, England, 2006

31

Sheldrick, G. M. SHELX97, Program package for the solution and refinement of crystal structures, Release 97-2, University of Göttingen, Germany, 1997