A Novel and Efficient Ceric Ammonium Nitrate Catalyzed Oxidative Nuclear Chlorination of Activated Aromatic Compounds by Acetyl Chloride

Abstract

C e r i c A m m o n i u m N i t r a t e C a t a l y z e d O x i d a t i v e N u c l e a r C h l o r i n a t i o n SubhasAbstract: A mild and efficient oxidative chlorination of activated aromatic compounds have been achieved in excellent yields using acetyl chloride in the presence of a catalytic amount of ceric ammonium nitrate at room temperature. However, chlorination failed to occur with deactivated aromatic rings.

Cerium(IV) Ammonium Nitrate as a Catalyst in Organic Synthesis

“…As an extension of the work described in ref , the same authors reported the ortho -chlorination of a number of cyclic and acyclic ketones by acetyl chloride and CAN (Scheme ) …”

“…In the presence of CAN, acetyl chloride, which is a wellknown acetylating agent and had never been previously reported to chlorinate aromatic compounds, was found to be an effective reagent for the chlorination of activated aromatic compounds. 82 Thus, stoichiometric amounts of acetyl chloride reacted with activated aryl compounds bearing methyl, methoxy, and N,N-disubstituted amino groups in the presence of 10 mol % of CAN to give monochlorinated compounds in very good yields (Scheme 61). As expected, aniline and phenol gave the acetylated products, while acetanilide furnished the chlorinated product.…”

Understanding Reactivity Patterns of the Dialkylaniline Radical Cation

“…Although amine radical cations are well-known, nucleophilic substitution reactions involving these species have attracted little attention. Chlorination of DMA using acetyl chloride and catalyzed by ceric ammonium nitrate was reported recently, and this reaction might have involved DMA •+ . Mechanistic details, however, are not discussed in the paper.…”

Ceric ammonium nitrate catalyzed mild and efficient α-chlorination of ketones by acetyl chloride

“…When 2-hydroxy acetophenone was subjected to the reaction condition, instead of chlorination, acetylation on hydroxyl group occurred exclusively as expected. 12 Aldehydes gave an inseparable mixture of compounds under the reaction condition. The spectral data of all the products were compared with those of authentic samples.…”