The
hydrodeoxygenation
of
amide
to
amine
is
one
the
most
important
synthetic
approaches
in
chemical
engineering.
However,
low
reactivity
and
poor
selectivity
remain
big
challenges
for
catalytic
amides.
Here,
Ru-VOx/TiO2
catalysts
with
different
V/Ru
atomic
ratios
were
prepared
sequential
impregnation
method.
physicochemical
properties
characterized
by
using
XRD,
Raman,
TEM,
CO
chemisorption,
NH3-TPD,
H2-TPR,
XPS,
Formamide-DRIFTS.
hydrogenation
butyramide
as
a
model
reaction
was
used
evaluate
performance.
conversion
butylamine
varied
ratio
volcano-type
relationship,
2V-4Ru/TiO2
catalyst
(V/Ru
=
1)
presented
best
performance
(96%
82%
selectivity)
at
423
K
5
MPa
H2.
also
reused
five
successive
times
without
an
obvious
decline
either
activity
or
selectivity,
showing
excellent
stability.
Based
on
characterization
evaluation
results,
interaction
between
Ru
nanoparticles
(∼2
nm)
VOx
species
promoter
generated
abundant
Ru-VOx
boundary
V4+
adjacent
oxygen
vacancies
(Ru-Vo-V4+).
As
1,
catalyst,
monolayer
dispersed
species,
maximum
showed
amine.
minimized
surface
acidity
suppressed
secondary
side
reaction.
Moreover,
evaluations
various
amides
including
aliphatic
primary
cyclic
90–99%
78–99%
corresponding
amines,
suggesting
wide
applicability
catalyst.
study
provides
highly
efficient
strategy
improve
optimizing
metal
oxide
promoters.
Applied Organometallic Chemistry,
Journal Year:
2022,
Volume and Issue:
37(2)
Published: Dec. 7, 2022
Vanadium
coordination
compounds,
[VO
2
L]·(CH
3
OH)
(
1a
and
1b
),
were
prepared
from
the
reaction
of
tridentate
hydrazone
ligand,
[HL=(
E
)‐4‐amino‐N′‐(1‐(pyridin‐2‐ylethylidene)benzohydrazide]
with
NH
4
VO
V
O
5
,
respectively.
These
compounds
characterized
by
various
analytical
methods,
structures
determined
single
crystal
X‐ray
analysis
which
indicated
that
they
have
same
composition
but
crystallized
in
different
unit
cells
can
be
considered
as
polymorphs.
The
silica‐supported
catalyst
Si‐VO
L
)
was
obtained
immobilization
1
on
surface
silica
using
propionyl
chloride‐functionalized
gel.
thermal
gravimetric
(TGA),
energy‐dispersive
spectroscopy
(EDX),
Fourier‐transform
infrared
(FT‐IR)
spectroscopy,
diffuse‐reflectance
(DRS),
photoelectron
(XPS),
scanning
electron
microscopy
(SEM),
diffraction
(XRD)
employed
heterogeneous
oxidation
styrene
derivatives,
aqueous
H
used
green
oxidant.
recovered
several
times,
methods.
results
its
high
stability.
effects
parameters
such
temperature,
ratio
reagents,
nature
solvent
selectivity
activity
investigated.
both
steric
electronic
substituents
phenyl
ring
affect
products.
Electron
withdrawing
groups
decrease
substrate
donating
increase
activity.
Applied Catalysis A General,
Journal Year:
2024,
Volume and Issue:
676, P. 119602 - 119602
Published: Feb. 7, 2024
The
development
of
catalysts
for
simultaneous
hydrodeoxygenation
(HDO)
and
hydrodenitrogenation
(HDN)
is
relevant
the
production
renewable
fuels.
In
this
work,
activity
CeO2-ZrO2
supported
Pt,
Co,
PtCo,
Cu,
PtCu,
Ni,
PtNi,
Ru
RuNi
was
studied
in
hydrotreatment
n-hexadecanamide
at
300
°C
80
bar
H2.
bimetallic
differed
from
corresponding
monometallic
terms
selectivity.
PtCu
less
active
than
Pt
catalyst,
as
addition
Cu
suppressed
hydrogenolysis
reactions.
PtCo
showed
a
similar
but
remarkably
different
selectivity,
with
favoring
n-hexadecane
n-pentadecane.
PtNi
exhibited
higher
nitrogen
removal
an
improved
selectivity
n-pentadecane
compared
to
catalysts,
emphasizing
potential
containing
Ni
noble
metal.
Furthermore,
formation
C32
compounds
limited
on
RuNi.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
12(5)
Published: March 28, 2023
Abstract
Amines
are
one
of
the
most
important
functional
groups
in
organic
synthesis,
particularly
scaffolds
constituting
active
ingredients
natural
products,
pharmaceutical
molecules,
and
agrochemicals.
Among
various
transformations
to
access
amines,
amide
reduction
has
been
considered
as
facile
efficient
strategy,
but
it
is
also
problematic,
often
requiring
use
highly
reactive
stoichiometric
reductants,
such
lithium
aluminum
hydride,
well
rare
transition
metal
catalysts,
or
both,
harsh
reaction
conditions.
This
review
covers
recent
advances
catalytic
amides
amines
without
need
for
thus
overcoming
problems.
Catalysis Science & Technology,
Journal Year:
2023,
Volume and Issue:
14(2), P. 431 - 448
Published: Dec. 15, 2023
The
Lewis
acid
properties
of
the
support
influence
activity
and
selectivity
supported
Pt
catalysts
in
hydrodeoxygenation
hydrodenitrogenation
n
-hexadecanamide
to
-paraffins.
Catalysis Science & Technology,
Journal Year:
2023,
Volume and Issue:
14(1), P. 90 - 97
Published: Dec. 4, 2023
A
heterogeneous
Pt–MoO
x
/TiO
2
catalyst
for
the
hydrogenation
of
several
2°
and
3°
amide
as
well
imide
under
milder
conditions
is
described.
The
catalytic
reactivity
proposed
to
originate
from
synergistic
effect
between
surface
active
species.
ChemistrySelect,
Journal Year:
2022,
Volume and Issue:
7(37)
Published: Oct. 4, 2022
Abstract
The
chemoselective
reduction
of
amides
is
important
in
the
synthesis
fine
chemicals
and
inter‐mediates.
However,
highly
stable
amide
bond
due
to
orbital
overlap
between
nitrogen
lone
pair
antibonding
carbonyl
group
poses
a
significant
limitation
developing
suitable
heterogeneous
catalysts.
In
this
work,
we
have
developed
efficient
robust
Ru‐(0.2)Mo/TiO
2
catalyst
for
primary
amides.
As
consequence,
afforded
83.1
%
conversion
with
80
selectivity
amine
after
reaction
12
h
HDO
cyclohexanecarboxamide
at
160
°C.
Moreover,
also
presented
excellent
reusability
substrate
diversity.
characterizations
revealed
that
Ru
promoted
Mo
6+
5+
0
,
resultant
low‐coordinated
responsible
selective
activation
C=O
amide,
while
RuMo
alloy
hydrogen.
