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Effects of tertiary amine catalysis on the regioselectivity of anisole chlorination with trichloroisocyanuric acid

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Abstract

Tertiary amines and their salts in dichloromethane were found to induce a strong para regioselectivity in the chlorination of anisole as the model substrate with trichloroisocyanuric acid (TCCA). Using a catalyst loading of 6 mol % trimethylammonium chloride gave a para vs. ortho selectivity of 38:1. This effect is attributed to the in situ formation of N-chlorotrialkylammonium salts, which chlorinate alkyl aryl ethers with a high regioselectivity. The regioselectivity and monochlorination selectivity for anisole chlorination with TCCA in numerous solvents are reported. The chlorination of a few related benzenoid substrates under selected conditions is described.

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References

  1. Urch CJ (2003) Vinyl and Aryl Halides. In: Ley SV (ed) Comprehensive Organic Functional Group Tansformations, vol 2. Elsevier, Amsterdam, p 605

    Google Scholar 

  2. Stanforth SP (2004) Vinyl and Aryl Halides. In: Ramsden C (ed) Organic Functional Group Tansformations II, vol 2. Elsevier, Amsterdam, p 561

    Google Scholar 

  3. Larock RC (1999) Comprehensive organic transformations. Wiley, New York, p 619

    Google Scholar 

  4. Cowdrey WA, Davies DS (1952) Q Rev. Chem Soc 6:358

    CAS  Google Scholar 

  5. Bay E, Bak DA, Timony PE, Leone-Bay A (1990) J Org Chem 55:3415

    Article  CAS  Google Scholar 

  6. Wu H, Hynes J Jr (2010) Org Lett 12:1192

    Article  CAS  Google Scholar 

  7. Sheppard TD (2009) Org Biomol Chem 7:1043

    Article  CAS  Google Scholar 

  8. Norman ROC, Radda GK (1961) J Chem Soc 3610

  9. Harvey DR, Norman ROC (1961) J Chem Soc 3604

  10. Smith K, Butters M, Paget WE, Goubet D, Fromentina E, Nay B (1999) Green Chem 1:83

    Article  CAS  Google Scholar 

  11. Smith K, El-Hiti GA (2011) Green Chem 13:1579

    Article  CAS  Google Scholar 

  12. Kodomari M, Takahashi S, Yoshitomi S (1987) Chem Lett 16:1901

    Article  Google Scholar 

  13. Yang L, Lu Z, Stahl SS (2009) Chem Commun 6460

  14. Wang H, Wen K, Nurahmat N, Shao Y, Zhang H, Wei C, Li Y, Shen Y, Sun Z (2012) Beilstein J Org Chem 8:744

    Article  CAS  Google Scholar 

  15. Kamigata N, Satoh T, Yoshida M, Matsuyama H, Kameyama M (1988) Bull Chem Soc Jpn 61:2226

    Article  CAS  Google Scholar 

  16. Guy A, Lemaire JP, Guetté M (1982) Tetrahedron 38:2339

    Article  CAS  Google Scholar 

  17. Dijkstra D, Grol CJ (1992) Bioorg Med Chem Lett 2:115

    Article  CAS  Google Scholar 

  18. Hirano M, Yakabe S, Monobe H, Clark JH, Morimoto T (1997) J Chem Soc Perkin Trans 1:3081

    Article  Google Scholar 

  19. Hirano M, Yakabe S, Monobe H, Morimoto T (1997) Can J Chem 75:1905

    Article  CAS  Google Scholar 

  20. Yoshida M, Mochizuki H, Kamigata N (1988) Chem Lett 17:2017

    Article  Google Scholar 

  21. Watson WD (1985) J Org Chem 50:2145

    Article  CAS  Google Scholar 

  22. Olah GA, Ohannesian L, Arvanaghi M (1986) Synthesis 868

  23. Smith JRL, McKeer LC (1983) Tetrahedron Lett 24:3117

    Article  Google Scholar 

  24. Smith JRL, McKeer LC, Taylor JM (1987) J Chem Soc Perkin Trans 2:1533

    Article  Google Scholar 

  25. Smith JRL, McKeer LC, Taylor JM (1988) J Chem Soc Perkin Trans 2:385

    Article  Google Scholar 

  26. Smith JRL, McKeer LC, Taylor JM (1989) J Chem Soc Perkin Trans 2:1529

    Article  Google Scholar 

  27. Smith JRL, McKeer LC, Taylor JM (1989) J Chem Soc Perkin Trans 2:1537

    Article  Google Scholar 

  28. Smith JRL, McKeer LC, Taylor JM (1989) Org Synth 67:222

    Article  Google Scholar 

  29. Minisci F, Vismara E, Fontana F, Platone E, Faraci G (1989) J Chem Soc Perkin Trans 2:123

    Article  Google Scholar 

  30. Carloni P, Eberson L, Greci L, Stipa P, Tosi G (1991) J Chem Soc Perkin Trans 2:1779

    Article  Google Scholar 

  31. Ogata Y, Takagi K, Kondo Y, Hsin SC, Woo WI, Chen FC (1983) J Chin Chem Soc 30:261

    Google Scholar 

  32. Smith K, Butters M (1988) Tetrahedron Lett 29:1319

    Article  CAS  Google Scholar 

  33. Fujisaki S, Eguchi H, Omura A, Okamoto A, Nishida A (1993) Bull Chem Soc Jpn 66:1576

    Article  CAS  Google Scholar 

  34. Gnaim JM, Sheldon RA (1995) Tetrahedron Lett 36:3893

    Article  CAS  Google Scholar 

  35. Saper NI, Snider BB (2014) J Org Chem 79:809

    Article  CAS  Google Scholar 

  36. Kovacic P, Lowery MK, Field KW (1970) Chem Rev 70:639

    Article  CAS  Google Scholar 

  37. Maraš N, Polanc S, Kočevar M (2008) Tetrahedron 64:11618

    Article  Google Scholar 

  38. Maraš N, Polanc S, Kočevar M (2010) Acta Chim Slov 57:29

    Google Scholar 

  39. Maraš N, Perdih F, Kočevar M (2011) Cent Eur J Chem 9:904

    Article  Google Scholar 

  40. Maraš N, Polanc S, Kočevar M (2012) Org Biomol Chem 10:1300

    Article  Google Scholar 

  41. Tilstam U, Weinmann H (2002) Org Process Res Dev 6:384

    Article  CAS  Google Scholar 

  42. Hiegel GA, Pozzi G, AnuMahadevan (2013) Trichloroisocyanuric acid. e-EROS encyclopedia of reagents for organic synthesis. Wiley, USA. doi:10.1002/047084289X.rt209.pub3

  43. Mendonca GF, de Mattos MCS (2013) Curr Org Synth 10:820

    Article  CAS  Google Scholar 

  44. Juenge EC, Beal DA, Duncan WP (1970) J Org Chem 35:719

    Article  CAS  Google Scholar 

  45. Rosevear J, Wilshire JFK (1980) Aust J Chem 33:843

    Article  CAS  Google Scholar 

  46. Manschand PS, Coffen DL, Belica PS, Wong F, Wong HS, Berger L (1994) Heterocycles 39:833

    Article  Google Scholar 

  47. Mendonça GF, Magalhães RR, de Mattos MCS, Esteves PM (2005) J Braz Chem Soc 16:695

    Article  Google Scholar 

  48. Maraš N (2011) SyntheticPage 483. doi:10.1039/SP483

  49. Vražič D, Jereb M, Laali KK, Stavber S (2013) Molecules 18:74

    Google Scholar 

  50. Burakevich JV (1979) Cyanuric and isocyanuric acids. In: Kirk-Othmer encyclopedia of chemical technology, 3rd edn, vol 7. Wiley, New York, p 397

  51. Radhakrishnamurti PS, Rath NK, Panda RK (1987) Indian J Chem 26:407

    Google Scholar 

  52. Ogata Y, Kimura M, Kondo Y (1984) J Chem Soc Perkin Trans 2:451

    Article  Google Scholar 

  53. van Summeren RP, Romaniuk A, IJpeij EG, Alsters PL (2012) Catal Sci Technol 2:2052

  54. Baidya M, Kobayashi S, Brotzel F, Schmidhammer U, Riedle E, Mayr H (2007) Angew Chem Int Ed 46:6176

    Article  CAS  Google Scholar 

  55. Baghernejad B (2010) Eur J Chem 1:54

    Article  CAS  Google Scholar 

  56. Kranjc K, Kočevar M (2008) Synlett 2613

  57. Juranovič A, Kranjc K, Perdih F, Polanc S, Kočevar M (2011) Tetrahedron 67:3490

    Article  Google Scholar 

  58. Juranovič A, Kranjc K, Polanc S, Perdih F, Kočevar M (2012) Monatsh Chem 143:771

    Article  Google Scholar 

  59. Banks RE, Mohialdin-Khaffaf SN, Sankar Lal G, Sharif I, Syvret RG (1992) Chem Commun 595

Download references

Acknowledgments

We thank the Ministry of Education, Science and Sport of the Republic of Slovenia and the Slovenian Research Agency for financial support (P1-0230-0103). Dr. B. Kralj and Dr. D. Žigon (Center for Mass Spectroscopy, ‘Jožef Stefan’ Institute, Ljubljana, Slovenia) are gratefully acknowledged for the mass measurements.

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  1. Nenad Maraš

    Present address: Lek Pharmaceuticals d.d., Sandoz Development Center Slovenia, API Development, Kolodvorska 27, 1234, Mengeš, Slovenia

Authors and Affiliations

  1. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna Pot 113, 1000, Ljubljana, Slovenia

    Nenad Maraš & Marijan Kočevar

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  1. Nenad Maraš
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  2. Marijan Kočevar
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Correspondence to Marijan Kočevar.

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Maraš, N., Kočevar, M. Effects of tertiary amine catalysis on the regioselectivity of anisole chlorination with trichloroisocyanuric acid. Monatsh Chem 146, 697–704 (2015). https://doi.org/10.1007/s00706-014-1383-6

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  • DOI: https://doi.org/10.1007/s00706-014-1383-6

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