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Issue 14, 2006
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Aromatic chlorination of ω-phenylalkylamines and ω-phenylalkylamides in carbon tetrachloride and α,α,α-trifluorotoluene

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Abstract

The aromatic halogenation of simple alkylbenzenes with chlorine proceeds smoothly in acetic acid but is much less efficient in less polar solvents. By contrast chlorination of ω-phenylalkylamines, such as 3-phenylpropylamine, occurs readily in either acetic acid, carbon tetrachloride or α,α,α-trifluorotoluene, and in the latter solvents gives high proportions of ortho-chlorinated products. These effects are attributable to the involvement of N-chloroamines as reaction intermediates, with intramolecular delivery of the chlorine electrophile. ω-Phenylalkylamides, such as 3-phenylpropionamide, also easily undergo aromatic chlorination in carbon tetrachloride and α,α,α-trifluorotoluene. These reactions generally show a first-order dependence on the substrate concentration, but not on the amount of chlorine. With carbon tetrachloride, very similar reaction rates are observed with chlorine concentrations ranging from 0.1–1.5 M. In α,α,α-trifluorotoluene, the rates reach a plateau at a chlorine concentration of approximately 0.2 M. These features indicate that the reactions proceed via the formation of intermediates which evidence suggests may be the corresponding O-chloroimidates. Irrespective of the mechanistic details, the reactions are remarkably rapid, being faster than analogous reactions in acetic acid and three to four orders of magnitude more rapid than reactions of simple alkylbenzenes in carbon tetrachloride. Therefore, chlorination of the amines and amides may be accomplished without the need for highly polar solvents, added catalysts or large excesses of chlorine, which are often employed for electrophilic aromatic substitutions. Although the use of carbon tetrachloride is becoming increasingly impractical due to environmental concerns, the trifluorotoluene is a suitable alternative.

Graphical abstract: Aromatic chlorination of ω-phenylalkylamines and ω-phenylalkylamides in carbon tetrachloride and α,α,α-trifluorotoluene

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Publication details

The article was received on 06 Apr 2006, accepted on 25 May 2006 and first published on 08 Jun 2006


Article type: Paper
DOI: 10.1039/B605010G
Citation: Org. Biomol. Chem., 2006,4, 2716-2723

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    Aromatic chlorination of ω-phenylalkylamines and ω-phenylalkylamides in carbon tetrachloride and α,α,α-trifluorotoluene

    J. L. O'Connell, J. S. Simpson, P. G. Dumanski, G. W. Simpson and C. J. Easton, Org. Biomol. Chem., 2006, 4, 2716
    DOI: 10.1039/B605010G

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