Alkyl chloroformates are esters of chloroformic acid that are used for the production of pesticidal, fungicidal, and herbicidal products. Specifically, alkyl chloroformates are useful in the preparation of herbicidal sulfonamides (EP0209230), fungicidal carbamates (US3562290A), and for the manufacture of carbamic acid pesticidal compositions (US4607051A).<br/>This undergraduate project analyzes in detail, the solvent mechanisms of propyl-, 3-chloropropyl-, butyl-, and 3-chlorobutyl- chloroformate esters. All reactions follow pseudo first-order kinetics. Using the two-term Grunwald-Winstein linear free energy relationship, we will show that the esters portray a duality of mechanistic pathways that is directly dependent on the solvents ability to hydrogen-bond. In the polar aqueous-organic solvents, ethanol, methanol, acetone, and 2,2,2-trifluroethanol-ethanol, the bimolecular addition-elimination process dominates, whereas, in the highly ionizing aqueous 1,1,1,3,3,3-hexafluro-2-propanol and 2,2,2-trifluroethanol mixtures, an ionizing S<sub>N</sub>1 process is clearly evident.<br/>

Understanding the solvent reactions of some common chloroformic acid esters with herbicidal properties

255th National Meeting (2018)

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