Nucleophilic Cl^– Reagents

Mechanism + Description

Typically S_N2 with displacement of another halogen (Iodide) or leaving group (sulphonate, nitro), etc. Also via reaction of Cl^– with other electrophiles, like diazonium salts. Chlroride anions can add to radical iminium cations as well.

General comments

Normally, simple bromide salts like Na/K/Li Chloride, or tetralkyl ammonium or phosphonium chlorides like nBu4NCl, are used. Hydrogen chloride is typically used for deoxychlorination, but can be used to add HCl to unsaturated C-C bonds and epoxides, etc. The Sandmeyer reaction can be used to make aryl chlorides from anilines.

Key references

Liu, Y.; Xu, Y.; Jung, S. H.; Chae, J. A Facile and Green Protocol for Nucleophilic Substitution Reactions of Sulfonate Esters by Recyclable Ionic Liquids [bmim][X]. Synlett. 2012, 23, 2663-2666.

Kim, D. W.; Song, C. S.; Chi, D. Y. Significantly Enhanced Reactivities of the NucleophilicSubstitution Reactions in Ionic Liquid. J. Org. Chem. 2003, 68(11), 4281-4185.

Kim, D. W.; Song, C. S.; Chi, D. Y. Significantly Enhanced Reactivities of the Nucleophilic Substitution Reactions in Ionic Liquid. J. Org. Chem. 2003, 68(11), 4281-4285.

Fortt, R.; Wootton, R. C. R.; De Mello, A. J. Continuous-Flow Generation of Anhydrous Diazonium Species:  Monolithic Microfluidic Reactors for the Chemistry of Unstable Intermediates. Org. Process Res. Dev. 2003, 7(5), 762–768.

Relevant scale up example

Org. Process Res. Dev. 2010, 14, 562–567.
Experimental
26 kg scale