- Email: [email protected]
difluoride
445
SHORT
COMMUNICATION
FLUORINATION
WITH
PREPARATION
MARK0
ZUPAN
“J .Stefan”
of
limited
of
their
for
the
Dimroth
The
acid.
The
oxide
and aqueous
method
methylene fluorination. solution
The
of
The fluorinating
developed using
X-@-l
: H,
*Presented
part
at
September
address:
Cambridge,
available
Dept.
’
the
of of
the is
Garvey
with
the
of
method
161 et al .,
46 o/c HF
reaction
in
in acetic
of
mercuric in
is then
used
electrolysis
of
directly
for
an acetonitrile
methyl
iodide
in makes
the
this
Chem., 023139,
reaction
potential
[la. for
X-@-IF2
European
[9!
the
synthesis
m-Cl,
of
agent
various in
aryliodine/l
methylene
+ Xe
p-Cl,
Symposium
m-NO2
on Fluorine
Chemistry,
1974.
Massachusetts
much difficulty
particular
first
methyliodine/lIl/difluoride of
as fluorinating
p-OCH8,
5th
one of
solution
involves
method
difluoride
HF CH2C12
are The
a one-step
groups
the aryliodine/lIl/dichloride
chloride
of
readily
m-OCH8,
in
A viemore,
synthesis an excess
2
methods
is treated
several received
iodobenzene.
with
a similiar
phenyliodine/lll/
from
because
i fl uorides.
modified
with
[81
and
using
attention
possibly
[77] involves acid
procedure
xenon
+ XeF
the
methylene
reported
agent
difluorides,
XPresent
third
bonds
Three
compound
Carpenter The
difluoride
We
L-55! or
silver/l/fluoride
recent
xenon
and storage.
hydrofluoric
chloride.
agents,
of aryliodine/lll/d
aryliodoso
of
double
aryIiodine/lII/difluorides
as fluorinating
ap’propriate
Chemistry,
has received
corresponding
Bockemuller
the
of
Yugoslavia
to olefinic
preparation
which
X
Department
agent
preparation
and
POLLAKX
Ljubljana,
chlorine
attention
in
interest
of
and
Liubljana,
g-41.
involved
DIFLUORIDE,
ALFRED
as a halogenating
workers
more
of
of
addition
dichloride
and
Institute
University
The
XENON
OF ARYLIODINE/III/DIFLUORIDE” ___-. ~~~
Massachusetts U .S .A.
Institute
of
Technology,
chloride
II/
446 solution
in
reaction
with
of
the
m-nitro,
preserce
three
solubility
of
anhydrous
hydrogen
p-methoxiiodobenzene hours
were
and separation
needed.
from
fluoride
was completed
the
The
most
room
promising,
seems
products,
at
in 4.5 min., due
temperature.
The
while
case
to
in
its
the
stability,
to be m-chlarophenyliodine/lll/
difluoride. The
quantity
benzene
was
of
active
converted
aryliodine/lIl/difluorides formation
of
The
was
established
by reaction
with
by iodometry.
95 % of
We
synthesised
tested
all
1,1-diphenylethene,
which
iodo-
resulted
in
1,’ -difluoro-1,2_diphenylethone.
Q2c =
CH2
on the
HF
+ X-&IF,
substituted
studies
fluorine
to aryliodine/lII/difluoride.
’
0-CF2-CH2-6
d’fl I uorides
aryIiodine/lII;’
reaction
EXPERIMENTAL
CH2C12
mechanism
of
offer
fluorination
the
possibility
with
these
of
future
reagents.
SECTION
I .r.
spectra
were
and
‘9F
n.m.r.
spectra
recorded
and
CCl3F
as internal
spectrometer.
T.I
by using
standards.
.c.
a Perkin
Elmer
by a Jeol-JNM-PS-100 Mass
separation
from
spectra
was carried
137
CC14
were
taken
on
Merck
out
spectrometer, solution
‘H
with
by a CEC
TMS
21-110
Fertigplatten
SiO2.
Materials Substituted
iodobenzenes
ominoderivotes known
methods
photosynthetic
n 3:
chloride
was purified Purum
Substituted 1 .1 ml)
the
reaction
at
for
of
room
its
difluoride than
molecular
sieves.
was dissolved
in
over
was
99.5
by
prepared
%.
anhydrous
HF
stirring
pure turned
seconds
the
colourless
solution
After
45
min.
p-OCH3
Hydrogen
fluoride
under (for
reaction
or
(l-3
was
XeF2
(1.1
mmo’)
dark
green
3 hr.
appeared
methylene
mmols)
for
The
After
gas was
derivate)
to be complete.
into
was added.
and xenon
m-NO2
chloride
introduced
gas evo-
solution
was used
olefins.
1. I-difluoro-1,2-diphenylethane To
a solution
fluoride,
1 mmol
of of
the
temperature.
After
2 hr.
ml),
washed
and
solvent
preparative
was t.I .c.
previously
prepared
1 .I-diphenylethene
chloride
(15
the
evaporated and
by
Methylene
difluorides iodobenzene
of
Xenon
from corresponding
was prepared
was better
temperature,
and
methods
used.
and
fluorinotion
use.
substituted
hod ceased
by known
1,1-diphenylethene
purity
and stored
was
mixture
evolved. lution
[12]
use. before
and
iodobenzene/lll/ mmol
(5
a few
[l’]
quality
prepared
before
ond distilled
methods
of
Fluka
were
ond distilled
reaction
(10
ml of
in vacua.
1 .l-difluoro-’
substituted
was added mixture 5% The
iodobenzene/lll/
under
stirring
was diluted
aqueous crude
with
NaHC03), product
.2_diphenylethone
at
methylene dried
(No2SO4)
wos separated wos
di-
room
isolated
by
in a yield
447 of
60-70%.
After
6!?~-6~C,
lit.
d 7.2
lOH,
(m,
Determination To ride,
that
and
active of
KI
water)
and
the. mixture
We
in
thank
Professor
Novo
mesto,
D.F.Banks,
are
diluted
and
in
1 litre
HCI
(1
:1)
by
of
The
reaction
of active
fluorine.
for
and
XeF2
Kidric
of
Na2S203
and
66 -
E.Miller,
(1966),
J.Amer.Chem.Soc.,
F.R.Stermitz,
P.S.Ramey,
72 -
(1931),
522,
O.Dimroth,
W.Bockemuller,
Ber.,
-64
(1931),
516.
9
J.A.Gibson,
for
temperature
The
results
facilities.
The
“Krka”
showed
Pharmaceutical
(1950),
64 -
H.Schmidt,
room
J.Org.Chem.,
L.F.Halley,
370.
J.Amer.Chem.Soc.,
Ber.,
8
at N).
243.
W.Bockemuller,
W.Carpenter,
N2
(0.025
J.Marsel
Foundation
I I/ difluo-
was added.
in an atmosphere
titrated
difluorides
mixture
O.Dimroth,
7
Hz)
acknowledged.
Chem.Rev.,
Jr.,
at
J=15
of a 1 :4
G.C.Gidley,
B.S.Garvey,
melted
-CH2-,
iodobenzene/l
D.D.Tanner,
6
crystals
2H,
substituted
dissolved
J .Slivnik Boris
(t,
iodobenzene/lll/
prepared
1 mmol
of, the
D.H.R.Barton, S.J.Cristol,
was
white
3.3
substituted
KI
the dark
included
assistance
in
1 ml of
iodine
the
6
PhCF2-).
previously (99
pentane, (CC14)
(t,
fluorine
the
solution
Liberated
from n.m.r.
6 - 96.75
was stirred
6 hr.
financial co.,
Ph)
of
50 ml of
mixture for
mp 66’C,
a solution
methanol
crystallisotion
iI.
-33
C.F.Allen,
(1968),
78 -
(1956),4939.
38.
J.Amer.Chem.Soc.,
-59 (1937),
1827. J.Org.Chem., H.Meinert,
-31
Angew.Chem.,
A.F.Janzen,
M.Zupan,
11
S.Williamson,
Inorg.Syn.,
12
J.H.Mathews,
J.Amer.Chem.Soc.,
13
J .E.Dubois,
A.F
2688. -72
J.Chem.Soc.,
10
A.Pollak,
(1966),
in
.Hegarty,
press -11
(1960),
Chem.Comm.,
Tetrahedron (1968),
109. 1973,
739.
Lett.
147. -48
E.D.Bergmann,
(1926), J .Org
562. .Chem.,
-37
(1972)
2218.
SHORT
COMMUNICATION
FLUORINATION
WITH
PREPARATION
MARK0
ZUPAN
“J .Stefan”
of
limited
of
their
for
the
Dimroth
The
acid.
The
oxide
and aqueous
method
methylene fluorination. solution
The
of
The fluorinating
developed using
X-@-l
: H,
*Presented
part
at
September
address:
Cambridge,
available
Dept.
’
the
of of
the is
Garvey
with
the
of
method
161 et al .,
46 o/c HF
reaction
in
in acetic
of
mercuric in
is then
used
electrolysis
of
directly
for
an acetonitrile
methyl
iodide
in makes
the
this
Chem., 023139,
reaction
potential
[la. for
X-@-IF2
European
[9!
the
synthesis
m-Cl,
of
agent
various in
aryliodine/l
methylene
+ Xe
p-Cl,
Symposium
m-NO2
on Fluorine
Chemistry,
1974.
Massachusetts
much difficulty
particular
first
methyliodine/lIl/difluoride of
as fluorinating
p-OCH8,
5th
one of
solution
involves
method
difluoride
HF CH2C12
are The
a one-step
groups
the aryliodine/lIl/dichloride
chloride
of
readily
m-OCH8,
in
A viemore,
synthesis an excess
2
methods
is treated
several received
iodobenzene.
with
a similiar
phenyliodine/lll/
from
because
i fl uorides.
modified
with
[81
and
using
attention
possibly
[77] involves acid
procedure
xenon
+ XeF
the
methylene
reported
agent
difluorides,
XPresent
third
bonds
Three
compound
Carpenter The
difluoride
We
L-55! or
silver/l/fluoride
recent
xenon
and storage.
hydrofluoric
chloride.
agents,
of aryliodine/lll/d
aryliodoso
of
double
aryIiodine/lII/difluorides
as fluorinating
ap’propriate
Chemistry,
has received
corresponding
Bockemuller
the
of
Yugoslavia
to olefinic
preparation
which
X
Department
agent
preparation
and
POLLAKX
Ljubljana,
chlorine
attention
in
interest
of
and
Liubljana,
g-41.
involved
DIFLUORIDE,
ALFRED
as a halogenating
workers
more
of
of
addition
dichloride
and
Institute
University
The
XENON
OF ARYLIODINE/III/DIFLUORIDE” ___-. ~~~
Massachusetts U .S .A.
Institute
of
Technology,
chloride
II/
446 solution
in
reaction
with
of
the
m-nitro,
preserce
three
solubility
of
anhydrous
hydrogen
p-methoxiiodobenzene hours
were
and separation
needed.
from
fluoride
was completed
the
The
most
room
promising,
seems
products,
at
in 4.5 min., due
temperature.
The
while
case
to
in
its
the
stability,
to be m-chlarophenyliodine/lll/
difluoride. The
quantity
benzene
was
of
active
converted
aryliodine/lIl/difluorides formation
of
The
was
established
by reaction
with
by iodometry.
95 % of
We
synthesised
tested
all
1,1-diphenylethene,
which
iodo-
resulted
in
1,’ -difluoro-1,2_diphenylethone.
Q2c =
CH2
on the
HF
+ X-&IF,
substituted
studies
fluorine
to aryliodine/lII/difluoride.
’
0-CF2-CH2-6
d’fl I uorides
aryIiodine/lII;’
reaction
EXPERIMENTAL
CH2C12
mechanism
of
offer
fluorination
the
possibility
with
these
of
future
reagents.
SECTION
I .r.
spectra
were
and
‘9F
n.m.r.
spectra
recorded
and
CCl3F
as internal
spectrometer.
T.I
by using
standards.
.c.
a Perkin
Elmer
by a Jeol-JNM-PS-100 Mass
separation
from
spectra
was carried
137
CC14
were
taken
on
Merck
out
spectrometer, solution
‘H
with
by a CEC
TMS
21-110
Fertigplatten
SiO2.
Materials Substituted
iodobenzenes
ominoderivotes known
methods
photosynthetic
n 3:
chloride
was purified Purum
Substituted 1 .1 ml)
the
reaction
at
for
of
room
its
difluoride than
molecular
sieves.
was dissolved
in
over
was
99.5
by
prepared
%.
anhydrous
HF
stirring
pure turned
seconds
the
colourless
solution
After
45
min.
p-OCH3
Hydrogen
fluoride
under (for
reaction
or
(l-3
was
XeF2
(1.1
mmo’)
dark
green
3 hr.
appeared
methylene
mmols)
for
The
After
gas was
derivate)
to be complete.
into
was added.
and xenon
m-NO2
chloride
introduced
gas evo-
solution
was used
olefins.
1. I-difluoro-1,2-diphenylethane To
a solution
fluoride,
1 mmol
of of
the
temperature.
After
2 hr.
ml),
washed
and
solvent
preparative
was t.I .c.
previously
prepared
1 .I-diphenylethene
chloride
(15
the
evaporated and
by
Methylene
difluorides iodobenzene
of
Xenon
from corresponding
was prepared
was better
temperature,
and
methods
used.
and
fluorinotion
use.
substituted
hod ceased
by known
1,1-diphenylethene
purity
and stored
was
mixture
evolved. lution
[12]
use. before
and
iodobenzene/lll/ mmol
(5
a few
[l’]
quality
prepared
before
ond distilled
methods
of
Fluka
were
ond distilled
reaction
(10
ml of
in vacua.
1 .l-difluoro-’
substituted
was added mixture 5% The
iodobenzene/lll/
under
stirring
was diluted
aqueous crude
with
NaHC03), product
.2_diphenylethone
at
methylene dried
(No2SO4)
wos separated wos
di-
room
isolated
by
in a yield
447 of
60-70%.
After
6!?~-6~C,
lit.
d 7.2
lOH,
(m,
Determination To ride,
that
and
active of
KI
water)
and
the. mixture
We
in
thank
Professor
Novo
mesto,
D.F.Banks,
are
diluted
and
in
1 litre
HCI
(1
:1)
by
of
The
reaction
of active
fluorine.
for
and
XeF2
Kidric
of
Na2S203
and
66 -
E.Miller,
(1966),
J.Amer.Chem.Soc.,
F.R.Stermitz,
P.S.Ramey,
72 -
(1931),
522,
O.Dimroth,
W.Bockemuller,
Ber.,
-64
(1931),
516.
9
J.A.Gibson,
for
temperature
The
results
facilities.
The
“Krka”
showed
Pharmaceutical
(1950),
64 -
H.Schmidt,
room
J.Org.Chem.,
L.F.Halley,
370.
J.Amer.Chem.Soc.,
Ber.,
8
at N).
243.
W.Bockemuller,
W.Carpenter,
N2
(0.025
J.Marsel
Foundation
I I/ difluo-
was added.
in an atmosphere
titrated
difluorides
mixture
O.Dimroth,
7
Hz)
acknowledged.
Chem.Rev.,
Jr.,
at
J=15
of a 1 :4
G.C.Gidley,
B.S.Garvey,
melted
-CH2-,
iodobenzene/l
D.D.Tanner,
6
crystals
2H,
substituted
dissolved
J .Slivnik Boris
(t,
iodobenzene/lll/
prepared
1 mmol
of, the
D.H.R.Barton, S.J.Cristol,
was
white
3.3
substituted
KI
the dark
included
assistance
in
1 ml of
iodine
the
6
PhCF2-).
previously (99
pentane, (CC14)
(t,
fluorine
the
solution
Liberated
from n.m.r.
6 - 96.75
was stirred
6 hr.
financial co.,
Ph)
of
50 ml of
mixture for
mp 66’C,
a solution
methanol
crystallisotion
iI.
-33
C.F.Allen,
(1968),
78 -
(1956),4939.
38.
J.Amer.Chem.Soc.,
-59 (1937),
1827. J.Org.Chem., H.Meinert,
-31
Angew.Chem.,
A.F.Janzen,
M.Zupan,
11
S.Williamson,
Inorg.Syn.,
12
J.H.Mathews,
J.Amer.Chem.Soc.,
13
J .E.Dubois,
A.F
2688. -72
J.Chem.Soc.,
10
A.Pollak,
(1966),
in
.Hegarty,
press -11
(1960),
Chem.Comm.,
Tetrahedron (1968),
109. 1973,
739.
Lett.
147. -48
E.D.Bergmann,
(1926), J .Org
562. .Chem.,
-37
(1972)
2218.