Allyl experimental protocol

Benzyl and allyl bromides could not be studied using the normal experimental protocol. The reaction was too fast to adequately monitor by simply sampling at different time intervals. On the other hand, GLC response calibration of benzyl bromide gave inconsistent results [177]. We used a variation of the technique, in which several reactions—one for each point to be plotted— were set up. They were loaded with a previously prepared mixture of bromides/ internal standard. A substoichiometric amount of active zinc, different for each reaction, was then injected. The reactions went to completion within minutes. Direct analysis of the unreacted bromides by NMR provided, if not... 

When the commodity chemical propylene oxide is heated to high temperature in the gas phase in a shock tube, unimolecular rearrangement reactions occur that generate the CsHgO isomers allyl alcohol, methyl vinyl edier, propanal, and acetone (Figure 15.9). Dubnikova and Lifshitz carried out a series of calculations to determine the mechanistic pathway(s) for each isomerization, with comparison of activation parameters to those determined from Arrhenius fits to experimental rate data to validate the theoretical protocol. 

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