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A new reversible synthesis of vinyl phosphates from mercurials
Tetrahedron Letters No.45, pp. 3995-3998, Printed in Great Britain.
A
NEW
REVERSIBLE
1965.
Pergamon Prem
SYNTHESIS
PHOSPHATES
FROM
Philip
Chevron
5.
OF
Ltd.
VINYL
MERCURIALS
Mogec
Chemical Company
Ortho Division Richmond, California
(Received 2 August 1965)
Halomercuri-aldehydes aqueous mercurotion
of vinyl
and ketones ore easily prepared in high yield by
acetates (I).
,OAc Hg(OAc)*
5
+ CH2 = C
[AcOHgFH$H]
+ AcOH
‘H KCI 0 ClHgCH$H
We report that the dry mercuriols non-hydroxylic
solvents to produce vinyl
+ CIHgCHz
-
!JCl
0 (C2H5O)3P
+ BrHgCH2;
phosphates with
liberation
phosphites in
of free mercury.
0
0 (C2H5O)3P
react smoothly with trialkyl
CH3
-
(QHsO)$
CHC13
OCH
0 t (QH5O)2POC
= CH2 + Hg’ + C2H5Cl
= CH2 + Hg’ + QH5Bt iH3
Of related phosphates, providing
interest
is the observation
a cyclic process of intrinsic
3995
of mercurial value.
regeneration
from vinyl
This is o useful extension
of
3996
No.45
the Nesmeyanov
nercuriol
synthesis as vinyl phosphates are often much more accessible
0
0
(C”30)2b”CH (vlathe
= CH2 + Hg(OAc)2
Perkov reaction)
simple alkyl
KCI ___c_
-!=+
than the corresponding
vinyl acetates(2).
and aryl substituted vinyl esters, however,
methyl p,p-dichlorovinyl electronegative
phosphate (DDVP)
groups will,
ClHgCH2;
H
It may be limited to
as we were unable to convert di-
to its related
mercurial.
of course, reduce the nucleophilicity
Halogens and other of the vinyl group toward
Hg (11). In many cases, the simple Perkov route to vinyl phosphates would be the method of choice however,
over the mercurial has heretofore
and difficult
chemical
route.
The specific
required the use of anhydrous chloroacetaldehyde, to acquire (3).
city of chloromercuriacetaldehyde,
With
normal precautions
large quantities
made in a few hours from readily
available
think in terms of a halomercuri
likely
Ouel lette(4)
While
however,
the details
to phosphite attack
against the presumed toxivinyl phosphates can be
on solvolyrir
group with phosphite attack
to the Perkov reaction,
mechanism is operating. is sympathetic
leaving
of dialkyl
of RHgX tempts one to
at the carbonyl
makes it more likely
of the Perkov are still in flux,
at the halogen’atom
(5, 6).
s+
0 + CIHgCH2;
R’ b
(RO)gP
OJ (RO)37Cl
H;
CH;=‘?
...C,..*Hg...;;2& transition
/
state
d ’
R’ -
(R0)3POC=
1st ion-pair
CH2 + Hg’
Cl@ 2nd ion-pair J ‘:
R’
RCI + (RO)2P 0 i: = CH2
center.
that a similar the current thinking
We suggest the following
in its grosser aspects:
(R0)3P
a hazardous
vinyl acetate.
The recent work of Jensen and
Its obvious relation
case of unsubstituted vinyl phosphates,
as
No.45
3997
It will be interesting reaction)
to see if those cases which yield phosphonates (Arburov iodoacetone,
rather than vinyl phosphates, e.g., Unlike
mercurial.
the simple Perkov reaction,
being separated by a Hg’ atom. C- versus O-attack
In borderline
will do so with the corresponding
the first ion-pair
is necessarily
“non-intimate”,
cases, this may exert a significant
on the chlorophosphonium
influence
on
cation.
EXPERIMENTAL Triethyl in chlorobenzene
phosphite was refluxed
for I .2 hours.
and washed with benzene. 99-105’/20-25 (30%)
was identical
stretching dimethyl
bromomercuriacetone separation
of triethyl
of finely
product.
(I645 cm-l) as in an available
A strong vinyl authentic
sample of
phosphite was added dropwise to a stirred slurry of The bulk of the mercurial
divided
20 minutes at 60” is insufficient.
The infrared
The bottoms plus column runback
peaks to the overhead
mercury.
5l.Y/O.l
spectrum is identical
entered solution with con-
After 20 minutes of reflux,
During solvent stripping,
boiling sharply at 50.5-
vinyl phosphate, b.p.
The NMR spectrum is also fully consistent with structure.
in chloroform.
and the slurry filtered.
mercury was separated as a gray solid
P, 17.19; found: P, 16.75.
appears at the same frequency vinyl phosphate.
of chloromercuriacetaldehyde
gave a 60% yield of diethyl
in all major infrared
An equivalent
comitant
The finely divided
Distillation
mm..; calcd.:
with an equivalent
more mercury separated,
Final distillation mm. in 72%yield;
Celite
was added
indicating
that
gave diethyl
isopropenyl phosphate
calcd.:
P, 15.94; found: P, 15.25.
with that of an authentic
sample prepared
from triethyl
phosphite and chloroacetone. Dimethyl water acidified
vinyl phosphate was shaken with an equivalent
with acetic
acid.
After 30 minutes, the solution was clarified
and excess aqueous potassium chloride crystalline
solid in 68% yield.
ocetaldehyde
of mercuric
was added.
It is identical
prepared from vinyl acetate
(I).
The mercurial
with an authentic
acetate
in
with carbon
separated rapidly
as a
sample of chloromercuri-
3998
No.45
REFERENCE8
(1)
A.N. N~emeyanov. 1-P. Lnteenko, 8.8.8.X.
(2)
A ride
Otdel Khim. Nauk,
variety
and Z.Y. Tamanova,
601 (Ipug);
of a-haloketonee
to the correeponding
vinyl
and aldehydee
phoephatee
Isveet.
Chem. Abet.
are available
in high yield
Akad. Nauk.
44,7225~(1950).
is
and convereion
experimentally
limple. (3)
Chloroacetaldehyde market beaanee
(4)
F B. Jensen referencea
(5)
A.J.
(6)
B. Hoffvn
can no longer of
l
evere
end B.J.
be purchaeed.
probleme
Ouellette,
in etorage
It wae removed
from the
stability.
J, Am, Chem. 80~. 2,
363(1963),
cited therein.
Epesiale
and L.B.
and E.J.
Smith,
Diehr,
J. Am. Chem. 80c.
Tetrahedron
Lettere
84,
1868 (1962).
No. 13, 383 (1962).
and
A
NEW
REVERSIBLE
1965.
Pergamon Prem
SYNTHESIS
PHOSPHATES
FROM
Philip
Chevron
5.
OF
Ltd.
VINYL
MERCURIALS
Mogec
Chemical Company
Ortho Division Richmond, California
(Received 2 August 1965)
Halomercuri-aldehydes aqueous mercurotion
of vinyl
and ketones ore easily prepared in high yield by
acetates (I).
,OAc Hg(OAc)*
5
+ CH2 = C
[AcOHgFH$H]
+ AcOH
‘H KCI 0 ClHgCH$H
We report that the dry mercuriols non-hydroxylic
solvents to produce vinyl
+ CIHgCHz
-
!JCl
0 (C2H5O)3P
+ BrHgCH2;
phosphates with
liberation
phosphites in
of free mercury.
0
0 (C2H5O)3P
react smoothly with trialkyl
CH3
-
(QHsO)$
CHC13
OCH
0 t (QH5O)2POC
= CH2 + Hg’ + C2H5Cl
= CH2 + Hg’ + QH5Bt iH3
Of related phosphates, providing
interest
is the observation
a cyclic process of intrinsic
3995
of mercurial value.
regeneration
from vinyl
This is o useful extension
of
3996
No.45
the Nesmeyanov
nercuriol
synthesis as vinyl phosphates are often much more accessible
0
0
(C”30)2b”CH (vlathe
= CH2 + Hg(OAc)2
Perkov reaction)
simple alkyl
KCI ___c_
-!=+
than the corresponding
vinyl acetates(2).
and aryl substituted vinyl esters, however,
methyl p,p-dichlorovinyl electronegative
phosphate (DDVP)
groups will,
ClHgCH2;
H
It may be limited to
as we were unable to convert di-
to its related
mercurial.
of course, reduce the nucleophilicity
Halogens and other of the vinyl group toward
Hg (11). In many cases, the simple Perkov route to vinyl phosphates would be the method of choice however,
over the mercurial has heretofore
and difficult
chemical
route.
The specific
required the use of anhydrous chloroacetaldehyde, to acquire (3).
city of chloromercuriacetaldehyde,
With
normal precautions
large quantities
made in a few hours from readily
available
think in terms of a halomercuri
likely
Ouel lette(4)
While
however,
the details
to phosphite attack
against the presumed toxivinyl phosphates can be
on solvolyrir
group with phosphite attack
to the Perkov reaction,
mechanism is operating. is sympathetic
leaving
of dialkyl
of RHgX tempts one to
at the carbonyl
makes it more likely
of the Perkov are still in flux,
at the halogen’atom
(5, 6).
s+
0 + CIHgCH2;
R’ b
(RO)gP
OJ (RO)37Cl
H;
CH;=‘?
...C,..*Hg...;;2& transition
/
state
d ’
R’ -
(R0)3POC=
1st ion-pair
CH2 + Hg’
Cl@ 2nd ion-pair J ‘:
R’
RCI + (RO)2P 0 i: = CH2
center.
that a similar the current thinking
We suggest the following
in its grosser aspects:
(R0)3P
a hazardous
vinyl acetate.
The recent work of Jensen and
Its obvious relation
case of unsubstituted vinyl phosphates,
as
No.45
3997
It will be interesting reaction)
to see if those cases which yield phosphonates (Arburov iodoacetone,
rather than vinyl phosphates, e.g., Unlike
mercurial.
the simple Perkov reaction,
being separated by a Hg’ atom. C- versus O-attack
In borderline
will do so with the corresponding
the first ion-pair
is necessarily
“non-intimate”,
cases, this may exert a significant
on the chlorophosphonium
influence
on
cation.
EXPERIMENTAL Triethyl in chlorobenzene
phosphite was refluxed
for I .2 hours.
and washed with benzene. 99-105’/20-25 (30%)
was identical
stretching dimethyl
bromomercuriacetone separation
of triethyl
of finely
product.
(I645 cm-l) as in an available
A strong vinyl authentic
sample of
phosphite was added dropwise to a stirred slurry of The bulk of the mercurial
divided
20 minutes at 60” is insufficient.
The infrared
The bottoms plus column runback
peaks to the overhead
mercury.
5l.Y/O.l
spectrum is identical
entered solution with con-
After 20 minutes of reflux,
During solvent stripping,
boiling sharply at 50.5-
vinyl phosphate, b.p.
The NMR spectrum is also fully consistent with structure.
in chloroform.
and the slurry filtered.
mercury was separated as a gray solid
P, 17.19; found: P, 16.75.
appears at the same frequency vinyl phosphate.
of chloromercuriacetaldehyde
gave a 60% yield of diethyl
in all major infrared
An equivalent
comitant
The finely divided
Distillation
mm..; calcd.:
with an equivalent
more mercury separated,
Final distillation mm. in 72%yield;
Celite
was added
indicating
that
gave diethyl
isopropenyl phosphate
calcd.:
P, 15.94; found: P, 15.25.
with that of an authentic
sample prepared
from triethyl
phosphite and chloroacetone. Dimethyl water acidified
vinyl phosphate was shaken with an equivalent
with acetic
acid.
After 30 minutes, the solution was clarified
and excess aqueous potassium chloride crystalline
solid in 68% yield.
ocetaldehyde
of mercuric
was added.
It is identical
prepared from vinyl acetate
(I).
The mercurial
with an authentic
acetate
in
with carbon
separated rapidly
as a
sample of chloromercuri-
3998
No.45
REFERENCE8
(1)
A.N. N~emeyanov. 1-P. Lnteenko, 8.8.8.X.
(2)
A ride
Otdel Khim. Nauk,
variety
and Z.Y. Tamanova,
601 (Ipug);
of a-haloketonee
to the correeponding
vinyl
and aldehydee
phoephatee
Isveet.
Chem. Abet.
are available
in high yield
Akad. Nauk.
44,7225~(1950).
is
and convereion
experimentally
limple. (3)
Chloroacetaldehyde market beaanee
(4)
F B. Jensen referencea
(5)
A.J.
(6)
B. Hoffvn
can no longer of
l
evere
end B.J.
be purchaeed.
probleme
Ouellette,
in etorage
It wae removed
from the
stability.
J, Am, Chem. 80~. 2,
363(1963),
cited therein.
Epesiale
and L.B.
and E.J.
Smith,
Diehr,
J. Am. Chem. 80c.
Tetrahedron
Lettere
84,
1868 (1962).
No. 13, 383 (1962).
and