ORGANIC
LETTERS
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Vol. XX, No. XX
000–000
Direct Oxidative Conversion of
Methylarenes into Aromatic Nitriles
Daisuke Tsuchiya, Yuhsuke Kawagoe, Katsuhiko Moriyama, and Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku,
Chiba 263-8522, Japan
Received July 8, 2013
ABSTRACT
A variety of methylarenes were successfully converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with
NBS or DBDMH in the presence of a catalytic amount of AIBN or BPO, followed by the reaction with molecular iodine in aq NH3 in a one-pot
procedure. The present reaction is a useful and practical transition-metal-free method for the preparation of aromatic nitriles from methylarenes.
Study of the practical transition-metal free methods for
the preparation of aromatic nitriles is very important since
they are precursors for the preparation of amides, esters,
primary amines, carboxylic acids, aldehydes, ketones, and
nitrogen-containing heterocycles, such as tetrazoles and
oxazoles.1 They have also great importance in the synthesis
of agrochemicals, therapeutic drugs, functional materials,
natural products, dyes, and pigments.1,2 Today, the most
conventional methods for the preparation of aromatic
nitriles are the dehydration of primary aromatic amides3,4
with SOCl2, TsCl/Py, P2O5, POCl3, COCl2, (EtO)3P/I2,
Ph3P/CCl4, or (COCl)2/DMSO and the Sandmeyer reac-
tion of aromatic diazonium ion with toxic CuCN.4,5
Recently, the direct transformation of aromatic bromides
into the corresponding aromatic nitriles was actively stu-
died with CuCN in N,N-dimethylformamide (DMF)
at 153 °C (the Rosenmundꢀvon Braun reaction),6a and
related reactions with palladium and metal cyanide were
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r
10.1021/ol401906q
XXXX American Chemical Society