Effects of Hydrogen Bonding Solvation by Diverse Fluorinated Bulky Alcohols on the Reaction Rate and Selectivity in Crown Ether Mediated Nucleophilic Fluorination in an Aprotic Solvent
ACS Organic & Inorganic Au,
Journal Year:
2024,
Volume and Issue:
5(1), P. 69 - 83
Published: Nov. 28, 2024
Solvent
effects
play
a
critical
role
in
ionic
chemical
reactions
and
have
been
research
topic
for
long
time.
The
solvent
molecules
the
first
solvation
shell
of
solute
are
most
important
solvating
species.
Consequently,
manipulation
structure
this
can
be
used
to
control
reactivity
selectivity
reactions.
In
work,
we
report
extensive
experimental
insightful
computational
studies
adding
diverse
fluorinated
bulky
alcohols
with
different
abilities
fluorination
reaction
alkyl
bromides
potassium
fluoride
promoted
by
18-crown-6.
We
found
that
stoichiometric
amount
these
acetonitrile
solution
has
an
effect
on
kinetics
selectivity.
effective
alcohol
was
2-trifluoromethyl-2-propanol
(TBOH-F3),
use
3
equiv
fluorinate
primary
bromide
led
78%
yield
just
6
h
time
at
mild
temperature
82
°C,
8%
E2
yield.
more
challenging
secondary
substrate
obtained
44%
56%
18
More
six
or
fluorine
atoms
resulted
relatively
acidic
alcohols,
leading
large
amounts
corresponding
ethers
as
side
products.
widely
hexafluoroisopropanol
(HFIP)
least
one
monofluorination,
indicating
both
acidity
bulkiness
features
promoting
using
KF
salt.
Nevertheless,
ether
HFIP
easily
formed
substrate,
generating
highly
product.
Theoretical
calculations
predict
ΔG
‡
close
agreement
experiments
explain
higher
induced
relation
crown
alone.
Language: Английский
Theoretical Study of CH4 and CO2 Separation by IRMOFs
Ana Luiza Andrade Mizuno,
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Edna da Silva Machado,
No information about this author
João B. L. Martins
No information about this author
et al.
ACS Omega,
Journal Year:
2024,
Volume and Issue:
9(37), P. 38686 - 38695
Published: Sept. 4, 2024
Porous
materials
such
as
isoreticular
metal-organic
frameworks
(IRMOFs)
can
be
applied
in
several
areas
that
explore
the
physical
adsorption.
An
area
has
gained
prominence
is
fuel
gas
storage,
it
provides
storage
of
a
large
amount
at
low
pressure
and
purification
combustible
due
to
selectivity
different
chemical
environments
its
pores.
IRMOFs
represent
an
ideal
study
group
their
wide
range
pore
sizes
resulting
from
use
organic
ligands.
In
this
context,
exploring
adsorb
more
efficiently
stands
out,
mainly
for
optimizing
ligand,
pressure,
temperature.
This
work
focused
on
adsorption
separation
CH
Language: Английский