Here,
we
present
the
first
mechanochemical
Fries
rearrangement
for
industrially
important
synthesis
of
para
hydroxyacetophenone,
inside
a
ball
mill
and
twin-screw
extruder.
Our
approach
leads
to
quantitive
conversion
in
as
little
90
minutes.
Furthermore,
utilisation
liquid-assisted
grinding
can
shift
isomer
ratio
resulting
an
excess
desired
product.
The
multigram
scale-up
via
continuous
extrusion
process
similar
results
only
three
minutes
residence
time
while
completely
avoiding
solvents.
temperature
75-100
°C
even
further
be
reduced
by
combining
at
50°C
with
subsequent
ageing
step.
Crystal Growth & Design,
Journal Year:
2022,
Volume and Issue:
22(9), P. 5726 - 5754
Published: Aug. 21, 2022
Mechanochemistry
by
ball
milling
is
garnering
significant
attention
as
an
efficient
and
versatile
means
of
chemical
synthesis
which
minimizes
the
need
for
solvents
reduces
amount
energy
required
to
conduct
many
molecular
transformations.
Understanding
reactions
often
requires
monitoring
reaction
solid
forms,
with
little
or
ideally
no
disruption
process.
Herein,
we
provide
a
broad
but
succinct
summary
how
different
ex
situ
more
recently
developed
in
techniques
have
been
applied
monitor
mechanochemical
reactions,
revealing
pathways
mechanisms
driving
solid-state
materials
transformations
milling.
The
rapidly
evolving
field
has
already
revolutionized
our
understanding
complex
self-assembled
phases
intermediates
catalytic
other
types
through
multitude
reported
investigating
are
touched
upon
this
summary,
promise
dramatically
increase
pace
development
chemistry.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(27), P. 7475 - 7481
Published: Jan. 1, 2023
We
demonstrate
the
use
of
a
metal
surface
to
directly
catalyse
copper-catalysed
alkyne-azide
click-coupling
(CuAAC)
reactions
under
conditions
Resonant
Acoustic
Mixing
(RAM)
-
recently
introduced
and
scalable
mechanochemical
methodology
that
uniquely
eliminates
need
for
bulk
solvent,
as
well
milling
media.
By
using
simple
copper
coil
catalyst,
this
work
shows
direct
mechanocatalysis
can
occur
in
an
impact-free
environment,
relying
solely
on
high-speed
mixing
reagents
against
surface,
without
specially
designed
containers
introducing
experimental
setup
enables
real-time
Raman
spectroscopy
monitoring
RAM
processes,
we
0th-order
reaction
kinetics
several
selected
CuAAC
reactions,
supporting
surface-based
catalysis.
The
herein
presented
RAM-based
is
simple,
effective
one-pot,
two-step
synthesis
triazoles
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
59(8), P. 1010 - 1013
Published: Dec. 12, 2022
Resonant
acoustic
mixing
(RAM)
enables
mechanoredox
catalysis
with
BaTiO3
as
the
piezoelectric
catalyst
on
model
diazonium
coupling
reactions.
RAM
proceeds
without
formal
grinding
or
impact
media,
is
faster
than
analogous
ball-milling
strategy,
and
readily
scalable.
X-ray
diffraction
spectroscopy
indicate
that
reusability
of
a
under
might
be
limited
by
boration.
Journal of Advanced Ceramics,
Journal Year:
2023,
Volume and Issue:
12(10), P. 1833 - 1843
Published: July 26, 2023
In
recent
years,
more
and
metal
oxides
have
been
finding
critical
tribo-catalytic
applications.
Presently,
we
explored
the
conversion
of
H2O
CO2
using
Co3O4
nanoparticles
obtained
some
surprising
results.
an
as-received
150
mL
glass
reactor
enclosed
with
10
H2O,
0.10
g
nanoparticles,
1
atm
CO2,
a
Teflon
magnetic
rotary
disk,
observed
production
as
much
57.41
µmol/L
H2,
0.15
CH4,
0.21
CO
after
5
h
stirring.
Metallic
coatings
Cu,
Ni,
SUS316,
Ti,
Nb,
Mo,
W
were
further
introduced
on
bottoms
separately.
For
those
reduction
was
dramatically
enhanced
C2+
products
C2H6
C2H4
observed.
Especially
for
Ti
coating,
amounts
H2
CH4
increased
by
2
26
times
from
bottom,
respectively,
very
impressive.
proven
chemically
stable
under
stirring
in
water,
hydroxyl
radicals
superoxide
detected
through
fluorescence
spectroscopy
electron
paramagnetic
resonance
analyses.
These
findings
not
only
reveal
outstanding
capability
to
generate
multicarbon
tribo-catalysis
but
also
highlight
promising
potential
whole
harness
mechanical
energy
addressing
shortages
environmental
pollution.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(65)
Published: July 28, 2023
Here
we
describe
the
development
of
a
sustainable
and
cost-effective
approach
for
catalytic
cross-coupling
reactions
in
mechanochemistry.
It
is
found
that
substrate's
impact
with
vessel
wall
alone
sufficient
to
initiate
reaction,
thus
indicating
milling
balls
function
primarily
as
mixing
agent
direct
mechanocatalytic
Suzuki
coupling.
The
absence
can
be
offset
by
adjusting
rheology
using
liquid-assisted
grinding
(LAG).
LAG
sweet
spot
0.25
μL
mg-1
confirmed
both
resonance
acoustic
mixers
(RAMs)
ball-free
mixer
mills,
higher
than
presence
balls.
RAMs
exhibit
excellent
performance
achieving
yields
90
%
after
60
min
complete
conversion
min.
longevity
significantly
improved
RAM,
allowing
at
least
20
without
deterioration.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2023,
Volume and Issue:
11(13), P. 5175 - 5183
Published: March 21, 2023
We
report
the
scale-up
of
a
batch
solid
synthesis
zeolitic
imidazolate
framework-8
(ZIF-8)
for
reactive
extrusion.
The
crystalline
product
forms
in
extruder
directly
under
mixture
2-methylimidazole
and
basic
zinc
carbonate
presence
catalytic
amount
liquid.
process
parameters
such
as
temperature,
liquid
type,
feeding
rate,
linker
excess
were
optimized
using
setup
specifically
designed
situ
Raman
spectroscopy.
Highly
ZIF-8
with
Brunauer–Emmett–Teller
(BET)
surface
area
1816
m2
g–1
was
quantitatively
prepared
at
mild
temperature
ethanol
small
linker.
Finally,
we
developed
simple
comprehensive
approach
to
evaluating
environmental
friendliness
scalability
metal–organic
framework
(MOF)
syntheses
view
their
large-scale
production.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2024,
Volume and Issue:
12(9), P. 3565 - 3574
Published: Feb. 16, 2024
Diverse
methods
have
been
reported
for
the
synthesis
of
acyl
fluorides;
however,
an
environmentally
benign
method
fluorides
remains
underdeveloped.
In
this
study,
we
developed
solvent-free
mechanochemical
deoxyfluorination
carboxylic
acids
to
mediated
by
1,1,2,2-tetrafluoroethyl-N,N-dimethylamine
(TFEDMA)
using
a
ball
mill.
This
facilitated
high
product
yields
in
short
reaction
times
even
sterically
challenged
acids.
We
also
realized
coupling
and
amines
as
well
TFEDMA-mediated
direct
with
via
sequential
one-pot
deoxyfluorination/coupling
pathway.
Furthermore,
protocol
was
expanded
include
peptide
synthesis.
The
efficiency
protocol,
terms
speed,
characteristics,
favorable
E-factor,
aligns
requirements
current
environmental
policies.
RSC Mechanochemistry,
Journal Year:
2024,
Volume and Issue:
1(1), P. 50 - 62
Published: Jan. 1, 2024
Resonant
acoustic
mixing
(RAM)
is
shown
to
be
an
effective
mechanochemical
method
for
producing
halogen-bonded
cocrystals,
characterized
here
by
X-ray
diffraction
and
solid-state
NMR.
An
elusive
stoichiomorph
unobtainable
milling
found
via
RAM.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(14), P. 8341 - 8347
Published: Jan. 1, 2024
Resonant
Acoustic
Mixing
(RAM)
allows
High
Throughput
Experimentation
(HTE)
using
commercially
available
96-well
plates
as
exemplified
by
the
nickel
catalyzed
C–N
cross
coupling
of
aryl
halides
with
different
amine
and
anilines.
