90
T. Ishida et al. / Applied Catalysis A: General 425–426 (2012) 85–90
line in Scheme 4) did not enhance the hydration, giving benzoni-
trile as a major product. On the other hand, Au/Al2O3 and Au/CeO2
would enhance the hydration of benzonitrile or the direct oxi-
dation of hemiaminal to produce benzamide as a major product
(dashed line in Scheme 4). According to the fact that benzonitrile, N-
benzylidenebenzylamine, and 2,4,6-triphenyl-1,3,5-triazine were
obtained as by-products over Au/Al2O3 and Au/CeO2, the one-pot
ammoxidation followed by the hydration is more likely. In our
experiments, the ammoxidation was carried out under the pres-
surized NH3 in organic solvents in contrast to the direct amidation
of alcohols in aqueous solution of NH3 in the presence of inorganic
base [15]. These conditions facilitated preferentially the dehydra-
tion of hemiaminal to form imine which was easily oxidized to
nitrile.
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We have found that MnO2, Co3O4, and NiO were catalyti-
cally active for the ammoxidation of primary alcohols including
unactivated alcohols to produce nitriles. In particular, MnO2 exhib-
ited remarkably high catalytic activity and excellent selectivity to
nitriles. The MnO2 catalyst could be reused at least for three times.
We have also found that Au NPs deposited on MnO2 promoted the
hydration of benzonitrile to form benzamide without further addi-
tion of water. Some other supported Au catalysts were also active
for the ammoxidation of benzyl alcohol to produce benzonitrile and
benzamide, presenting a new type of catalysis by Au NPs.
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This work was financially supported by JST-CREST and a Grant-
in-Aid for Young Scientists (B) (No. 21750160) from the Ministry of
Education, Culture, Sports, Science, and Technology, Japan.
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