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Pure Appl. Chem., 2012, Vol. 84, No. 3, pp. 411-423

Published online 2012-02-24

Chlorine-free synthesis: An overview*

Pietro Tundo

Department of Environmental Sciences, Informatics and Statistics, Ca’ Foscari University of Venice, Dorsoduro 2137, 30123 Venice, Italy

Abstract: Since the Industrial Revolution, chlorine has featured as an iconic molecule in process chemistry even though its production by electrolysis of sodium chloride is very energy-intensive. Owing to its high energy and reactivity, chlorine allows the manufacture of chlorinated derivatives in a very easy way: AlCl3, SnCl4, TiCl4, SiCl4, ZnCl2, PCl3, PCl5, POCl3, COCl2, etc. in turn are pillar intermediates in the production of numerous everyday goods. This kind of chloride chemistry is widely used because the energy is transferred to these intermediates, making further syntheses easy. The environmental and health constraints (toxicity and eco-toxicity, ozone layer depletion) and the growing need for energy (energy efficiency, climate change) force us to take advantage from available knowledge to develop new chemical strategies. Substitution of chlorine in end products in compounds where “chlorine is used in the making” means that we avoid electrolysis as primary energetic source; this makes chemistry “without chlorine” considerably more difficult and illustrates why it has not found favor in the past. The rationale behind this Special Topic issue is to seek useful and industrially relevant examples for alternatives to chlorine in synthesis, so as to facilitate the development of industrially relevant and implementable breakthrough technologies.
*Pure Appl. Chem. 84, 411–860 (2012). A collection of invited papers for the IUPAC project 2008-016-1-300 “Chlorine-free Synthesis for Green Chemistry”.