Hetero- and homolytic rearrangements in the chemical reactions of 3,3,3-trichloro-2-methylpropene

Summary

• 1. A study was made of the addition of hydrogen bromide to 3,3,3-trichloro-2-methylpropene in presence of benzoyl peroxide. The results show that in this reaction the isorherization of the radical (III) into the radical (IV) occurs:

  $$\begin{array}{*{20}c} {CCl_3 ---\dot C---CH_2 X} \\ | \\ {CH_3 } \\ \end{array} \begin{array}{*{20}c} { \to \dot CCl_2 ---CCl---CH_2 X,} \\ | \\ \begin{gathered} CH_3 \hfill \\ \begin{array}{*{20}c} {(III)} & {(IV)} \\ \end{array} \hfill \\ \end{gathered} \\ \end{array} $$

  in which X=Br or Cl.

• 2. A study was made of the electrophilic addition of chlorine to 3,3,3-trichloro-2-methylpropene in a medium of acetic acid. It was found that the direction of addition was contrary to Markovnikov's rule and was determined by the orienting effect of the trichloromethyl group.

• 3. 3,3,3-Trichloro-2-methylpropene reacts with benzene and toluene, and with the nucleophilic reagents sodiomalonic ester and diethylamine, with accompanying allyl rearrangement.