Direct Acetoxylation of Anilides Using Ion-supported [Bis(trifluoroacetoxy)iodo] benzene

doi:10.7503/cjcu20120852

Abstract

Abstract:

1-[4-Iodobenzamidoethyl]-3-methylimidazolium tetrafluoroborate was prepared by the reaction of 1-methylimidazole with N-(2-chloroethyl)-4-iodobenzamide, then anion exchange with NaBF₄ was performed in aqueous solution. The imidazolium tetrafluoroborates was oxidized to a novel ion-supported[bis(trifluoroacetoxy)iodo]benzene(BTI) reagent(solid) {1-[4-bis(trifluoroacetoxy) iodobenzamidoethyl]-3-methylimidazolium tetrafluoroborate} with amide linkage in a mixture of hydrogen peroxide and trifluoroacetic anhydride. The new reagent exhibited good stability in air or high humid atmosphere over several days.Direct acetoxylation of acetanilide using ion-supported(diacetoxyiodo)benzene(DIB) reagent and three ion-supported BTI reagents was studied. Due to low oxidation capacity of the ion-supported DIB reagent and low yields of its relative product, two ion-supported BTI reagents with amide linkage failed to carry out the acetoxylation reaction. However, 1-[4-bis(trifluoroacetoxy)iodobenzyl]-3-methylimidazolium tetrafluoroborat was an ideal oxidant. Treatment of various anilides with 1.1 mol of 1-[4-bis(trifluoroacetoxy)iodobenzyl]-3-methylimidazolium tetrafluoroborat and 1.0 mol of BF₃稯Et₂ in AcOH at room temperature afforded the corresponding para-acetoxylated products with high regioselectivity. After the acetoxylation, the reagent was transformed into ion-supported iodobenzene, which could be recovered and regenerated easily without lost of acetoxylation activity.

Key words: Task-specific ionic liquid, [Bis(trifluoroacetoxy)iodo]benzene, 1-Methylimidazole, Acylamide, Acetoxylation

CLC Number:

O621.25\++6.6

TrendMD:

ZHANG Ji-Zhen, ZHANG Mao-Lin, ZHAO De-Jian, WANG Ya-Zhen, JIA Hong-Bin. Direct Acetoxylation of Anilides Using Ion-supported [Bis(trifluoroacetoxy)iodo] benzene[J]. Chem. J. Chinese Universities, 2013, 34(4): 863.

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