Aluminum chloride Beckmann rearrangement

While metallocenes are usually acetylated with acid halides, acid anhydrides, or carboxylic acids, a number of other acylating agents have been reported. The reaction of ferrocene with various isocyanates and aluminum chlorides leads to N-substituted ferrocenecarboxamides (IX) (89). Use of ruthenocene in place of ferrocene leads to analogous results (88). The preparation of V-phenyl-ferrocenecarboxamide from phenyl isocyanate in this manner has been used as a proof of structure for the product obtained from the Beckmann rearrangement of benzoylferrocene oxime (124). 

Dimethylaniline has been prepared by reduction of the corresponding nitro compound, either chemically or catalyti-cally. It has been prepared from 3,4-dimethylphenol by heating with ammonia, ammonium bromide, and zinc bromide from w-toluidine hydrochloride by alkylation with methanol at high temperatures from anhydro-4-amino-2-methylbenzyl alcohol by dry distillation from calcium hydroxide from 2-methyl-S-aminobenzyl alcohol by reduction with sodium from 2-methyl-5-nitrobenzyl chloride and 2-methyl-S-nitrobenzyl acetate by catalytic reduction from o-xylene by direct amination with hy-droxylamine hydrochloride in the presence of aluminum chloride and from 3,4-dimethylacetophenone by the Beckmann rearrangement of the oxime.i" The present method has been published. ... 

Beckmann rearrangement of phthalimide derivative (46) is induced by aluminum chloride in benzene and terminated by electrophilic aromatic substitution, as shown in equation 21) ... 

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