Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15118 - 15127
Опубликована: Июль 10, 2023
Precise
control
in
reaction
selectivity
is
the
goal
modern
organic
synthesis,
and
it
has
been
widely
studied
throughout
synthetic
community.
In
comparison,
of
divergent
reactivity
a
given
reagent
under
different
conditions
relatively
less
explored
aspect
chemical
selectivity.
We
herein
report
an
unusual
between
polycyclic
aromatic
hydrocarbons
periodic
acid
H5IO6
(1),
where
product
outcome
dictated
by
choice
conditions.
That
is,
reactions
solution-based
condition
give
preferentially
C-H
iodination
products,
while
solvent-free
mechanochemical
provide
oxidation
quinone
products.
Control
experiments
further
indicated
that
not
intermediate
toward
vice
versa.
Mechanistic
studies
unveiled
situ
crystalline-to-crystalline
phase
change
2
during
ball-milling
treatment,
we
assigned
as
polymeric
hydrogen-bond
network
1.
believe
this
crystalline
shields
more
embedded
electrophilic
I═O
group
1
from
bias
pathway
(with
I═O)
solid
state.
Collectively,
work
demonstrates
mechanochemistry
can
be
employed
to
completely
switch
unmask
hidden
reagents.
To
address
the
growing
demand
for
more
sustainable
and
greener
chemistry,
mechanochemical
methodologies
are
emerging
as
key
players.
However,
to
date
there
has
been
little
data
highlighting
benefits
of
these
rising
technologies
with
regard
process
scale-up
activities
or
implementation
in
commercial
production
scale.
Herein,
we
report
first
application
bead-mill
technology
(Dyno®-mill)
synthesis
Acetaminophen,
known
under
brand
name
Paracetamol.
Using
Beckmann
rearrangement,
optimized
solvent-free
methodology
delivered
a
final
product
on
scale
several
tens
grams.
In
comparison
current
solvent-based
process,
proposed
achieves
higher
yield
while
also
allowing
removal
solvents
chemical
reaction,
hereby
reducing
one
extensive
drivers
waste
generation.
The
approach
was
compared
using
combination
green
metrics
EcoScale
score.
paracetamol
scores
highest
all
over
currently
used
solution-based
processes.
Faraday Discussions,
Год журнала:
2022,
Номер
241, С. 9 - 62
Опубликована: Ноя. 28, 2022
The
paper
presents
a
view
on
the
achievements,
challenges
and
prospects
of
mechanochemistry.
extensive
reference
list
can
serve
as
good
entry
point
to
plethora
mechanochemical
literature.
International Journal of Molecular Sciences,
Год журнала:
2024,
Номер
25(10), С. 5504 - 5504
Опубликована: Май 18, 2024
Molecularly
imprinted
polymers
(MIPs)
are
established
artificial
molecular
recognition
platforms
with
tailored
selectivity
towards
a
target
molecule,
whose
synthesis
and
functionality
highly
influenced
by
the
nature
of
solvent
employed
in
their
synthesis.
Steps
"greenification"
imprinting
technology
(MIT)
has
already
been
initiated
elaboration
green
MIT
principles;
developing
MIPs
solvent-free
environment
may
not
only
offer
an
eco-friendly
alternative,
but
could
also
significantly
influence
affinity
expected
resulting
binding
sites.
In
current
study
first
mechanochemical
via
liquid-assisted
grinding
(LAG)
is
reported.
The
successful
polymer
was
functionally
demonstrated
measuring
its
template
rebinding
capacity
process
comparison
ones
obtained
conventional,
non-covalent
liquid
media.
results
similar
capacities
molecule
superior
chemoselectivity
compared
to
solution-based
MIP
method.
adoption
chemistry
principles
all
inherent
advantages
be
able
alleviate
potential
environmental
health
concerns
associated
analytical
(e.g.,
selective
adsorbents)
biomedical
drug
carriers
or
reservoirs)
applications,
might
conceptual
change
technology.
Green Chemistry,
Год журнала:
2023,
Номер
25(7), С. 2853 - 2862
Опубликована: Янв. 1, 2023
A
novel
accelerated
aging
cross
dehydrogenative
coupling
of
glycine
esters/amides
and
various
nucleophiles
under
metal-free
solvent-minimal
conditions
was
developed,
providing
a
sustainable
strategy
to
the
synthesis
1,4-DHP
α-substituted
derivatives.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2023,
Номер
11(24), С. 9047 - 9056
Опубликована: Июнь 5, 2023
A
simple
and
single-step
synthetic
protocol
is
reported
here
for
synthesizing
medicinally
important
amide
compounds
such
as
acetanilide
(N-phenylacetamide)
its
derivatives
(including
paracetamol
phenacetin).
Compared
to
the
existing
reports
used
a
amidation
that
requires
multiple
reagents,
herein,
waste-derived
iron
nanoparticles
(FeOx-NPs)
isolated
from
"free-of-cost
available
dust/powder"
were
same
reaction
without
using
any
external
reagents
high
pressure,
resulting
in
cost-effective
viable
procedure.
The
Soxhlet-purified
dust
subjected
high-temperature
heating
at
∼800
°C
muffle
furnace
achieve
heterogeneously
active
form
(Fe3O4-type
moieties
on
surface).
as-prepared
catalyst
has
been
synthesize
17
including
two
essential
antipyretic
drugs,
phenacetin,
gram
scale,
one
industrially
dye/pigment
precursor
(2-nitroacetanilide).
Based
X-ray
photoelectron
spectroscopy
vibrating
sample
magnetometry
results,
possible
mechanism
proposed.
sustainability
associated
with
whole
process
direct
formation
magnetically
separable
metal
solvent-free
conditions,
which
provides
way
utilize
large-scale
industrial
waste,
thus
directly
reducing
some
environmental
stress.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Июнь 30, 2023
Organomagnesium
halides
(Grignard
reagents)
are
essential
carbanionic
building
blocks
widely
used
in
carbon-carbon
and
carbon-heteroatom
bond-forming
reactions
with
various
electrophiles.
In
the
Barbier
variant
of
Grignard
synthesis,
generation
air-
moisture-sensitive
reagents
occurs
concurrently
their
reaction
an
electrophile.
Although
operationally
simpler,
classic
approach
suffers
from
low
yields
due
to
multiple
side
reactions,
thereby
limiting
scope
its
application.
Here,
we
report
a
mechanochemical
adaptation
Mg-mediated
reaction,
which
overcomes
these
limitations
facilitates
coupling
versatile
organic
(e.g.,
allylic,
vinylic,
aromatic,
aliphatic)
diverse
range
electrophilic
substrates
aromatic
aldehydes,
ketones,
esters,
amides,
O-benzoyl
hydroxylamine,
chlorosilane,
borate
ester)
assemble
C-C,
C-N,
C-Si,
C-B
bonds.
The
has
advantage
being
essentially
solvent-free,
simple,
immune
air,
surprisingly
tolerant
water
some
weak
Brønsted
acids.
Notably,
solid
ammonium
chloride
was
found
improve
ketones.
Mechanistic
studies
have
clarified
role
mechanochemistry
process,
indicating
transient
organometallics
facilitated
by
improved
mass
transfer
activation
surface
magnesium
metal.
Open Research Europe,
Год журнала:
2025,
Номер
5, С. 73 - 73
Опубликована: Март 20, 2025
Mechanochemistry
is
several
thousand
years
old,
but
it
has
been
overlooked
in
favour
of
solution-based
chemistry
for
long
time
and
its
methods
have
only
recently
emerged
as
a
key
technology
advancing
green
sustainable
chemistry,
offering
solvent-free
(or
low-solvent)
alternative
to
traditional
chemical
processes.
Successfully
used
metallurgical
industry,
mechanical
alloying
paved
the
way
use
mechanochemistry
other
industrial
sectors
(e.g.,
waste
treatment
soil
decontamination),
with
potential
applications
also
preparing
pharmaceuticals,
transforming
biomass,
recycling
degrading
polymers,
just
cite
some.
Overall,
seems
provide
an
interesting
pathway
decarbonizing
industry.
Several
initiatives
subsequently
blossomed
under
combined
efforts
scientists
belonging
International
Mechanochemical
Association
(IMA):
approval
COST
Action
CA18112
MechSustInd
consequent
building
collaborative
networks
favoured
funding
EU
Horizon
IMPACTIVE
project,
establishment
EuChemS
Working
Party
on
Mechanochemistry,
organization
Round
Robin
project
mechanochemical
transformations
IUPAC
terminology
symbolisms.
All
these
are
actively
promoting
by
addressing
challenges
field
fostering
collaboration
across
academia
These
place
Europe
at
forefront
innovation,
pushing
forward
environmentally
friendly
processes
while
development
standardised
applications.
