Benzophenone, reaction

The reactions involving either benzophenone hydrazone or w-hexylamine have been studied by reaction calorimetry. The benzophenone hydrazone reaction presents zero order kinetics, while the hexylamine reaction is first order in the aryl halide and zero order in the amine. Under synthetically relevant conditions, at 90°C, the rate of the hexylamine reaction is about 30-fold higher than the rate of the benzophenone reaction. 

Figure 26.1 represents the heat profile of the benzophenone hydrazone and hexylamine reactions. At the same conditions, at 90°C, the reaction involving hexylamine is considerably faster. The heat profile of the hexylamine reaction at 70°C shows how the reaction has positive order kinetics, while the benzophenone reaction shows overall zero order kinetics. 

We can see from Figure 26.3 that a complex arises at the beginning, showing peaks in both the phosphoras and fluorine NMR it is the same previously observed during the benzophenone reaction when the hexylamine reaction starts, and its product begins to form, this complex disappears and a single peak in the P is visible, referring to the Pd(BINAP)2. 

Such normal free-radical substitution processes might be geometrically directed to otherwise unremarkable positions in substrates, as the benzophenone reactions had been. Consequently, in our first example, we found that intramolecular chlorination could be directed by attachment of a PhICl2 group to the steroid [156], i.e., compound 82 directed chlorination exclusively to C-14 (83), while 84 directed halogenation exclusively to C-9 (85). As shown in Scheme 1.1, an intramolecular hydrogen abstraction by... 

Another curiois the rearrangement followed by cycli-zation of the azide derived from the dichloride of benzophenone (reaction 97). An example of ring opening of a triazole leading to an amidine is reaction (98)... 

We saw before that H202 reacts stoichiometrically with fuchsone leading selectively to HQ and benzophenone (reaction 2). How does this reaction work ... 

Water 10% by volume of the solvent b NaOH 0.1% by weight of benzophenone Reaction conditions same as in Fig. 1. 

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