Monatshefte für Chemie - Chemical Monthly

, Volume 146, Issue 4, pp 697–704 | Cite as

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

  • Nenad Maraš
  • Marijan KočevarEmail author
Original Paper


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.

Graphical Abstract


Chlorination Catalysis Electrophilic substitutions Regioselectivity DABCO 



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.

Supplementary material

706_2014_1383_MOESM1_ESM.pdf (494 kb)
Supplementary material 1 (PDF 493 kb)


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Copyright information

© Springer-Verlag Wien 2014

Authors and Affiliations

  1. 1.Faculty of Chemistry and Chemical TechnologyUniversity of LjubljanaLjubljanaSlovenia
  2. 2.Lek Pharmaceuticals d.d.Sandoz Development Center Slovenia, API DevelopmentMengešSlovenia

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