Aromatics benzoylation indium metal

Table 3.13 Benzoylation of aromatics with BC in the presence of indium metal...

Bieber reported that the reaction of bromoacetates is greatly enhanced by catalytic amounts of benzoyl peroxide or peracids and gives satisfactory yields with aromatic aldehydes. A radical chain mechanism, initiated by electron abstraction from the organometallic Reformatsky reagent, is proposed (Scheme 8.27).233 However, an alternative process of reacting aldehydes with 2,3-dichloro-l-propene and indium in water followed by ozonolysis provided the Reformatsky product in practical yields.234 An electrochemical Reformatsky reaction in an aqueous medium and in the absence of metal mediator has also been reported.235... 

The preparation and use of indium trichloride, gallium trichloride, and zinc chloride supported on MCM-41 as Lewis acids in the Friedel-Crafts acylation of aromatics with acyl chlorides was investigated. The support itself shows no catalytic activity in the benzoylation of benzene with BC, whereas the highest activity is showed by the supported indium trichloride. The order for acylation activity of the supported metal chloride (indium trichloride > gallium trichloride zinc chloride) is quite similar to that of the redox potential of the metals [E , +/, (-0.34 V) > E°Ga /Ga ( 0.53 V) > E 2n +/zn ( 0.74 V)] and confirms a possible relationship between the redox potential and the catalytic activity of the supported metal chloride. The reaction can be efficiently applied to a variety of aromatic compounds, including toluene, para-xylene, mesitylene, anisole, and 2-MN (70%-90% yield), confirming the moisture insensitivity of the catalyst. ... 

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