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The reaction of benzoyl peroxide with trimethylphenyltin: a polar mechanism of formation of trimethyltin benzoate
Cl JoumaIofiQr;pu2ometdlicChemis&, 1~5(19’77)Cl-C5 Lausanne A E%iuted in The Netherlands
0. EZse+er Seqiioia SA,
Preliminary
Communication
THi2 REACTION A POLAR
SEIZI
OF
BENZOYL
MECHANISM
FORMATIO??
and Jt2?-ICHI
KOZUKA
Department
OF
PEROXIDE
of Applied
University,
WITH OF
TRIME2HYLTIN
BENZOATE
NAKAGAMI
Chemistry,
Sugimotocho,
TRI_KKTHYLPHENYLTIN:
Faculty
Sumiyoshi,
of Engineering,
Osaka
Osaka
City
558, Japan
(Received March 15th, 19771 Summary The mechanism by thermal
of the reaction
decomposition
trimethylphenyltin
of benzoyl
was
investigated.
from
the peroxide,
which
was derived
shown
to give the benzoate.
Razuvaev of benzoyl
pathway l-e.,
et al. have
peroxide
trimethyltin
reported
Homolytic
of the decomposition dioxide was
with
(eq. 1,2).1'3
Although
undoubtedly
of radical
was no definite
was
decomposition gives
was
the major
products
Accordingly,
obtained,
the formation
attack
evidence
on tin for this
0
4
(Ph!!Of2
E-
PhCO*
G
Me3SnPh
-
2 Ph!O .
Ii
Me2SnOCPh
of
acid,
the tin compound
of the other
in terms
there
of benzoic
of trimethylphenyltin
fission
benzoate
in the presence
that the thermal
in view
explained
trimethyltin
Reaction
and hydrocarbons.
of the benzoate
gives
peroxide
in the presence
benzoate.
carbon
which
+ Ph-
(2)
c2 this
mechanism, tin-carbon
bond
has
cleavage
there
However, of
reaction
by
are
of
other
of
the
carboxy
inversion
the
Another
possible
nylation the
reaction
peroxide
gives
Kinetics peroxide the
Kate
by
results
or
given
mode
suggests
both
of
was
phenyltin.
benzoic
acid
whether
the
measured observed The
Trapping
of
the
presence
ds
5
could
give
protodestan-
acid, 6#7
since
8 compound
catalyzes
benzoic the
to
in the
acid
may
mechanism
obtain
the prove
of
a better
under-
by
the
the
or
benzoyl
absence
of
in th.e absence under
addition
and
peroxide
accelerated results
of
peroxide
were
additive.
The
1.
decomposition
inhibition
not
the
were
tin
formation
oxygen,
is the
thermolysis. the
the
peroxide
benzoic
decomposition
the
of
of
concentration.
rule
all out
by tin
of
an
conditions
styrene,
acceleration
at
the
additive
used.
which
Inhi-
in turn
the
decomposition
The
rate
addition
of
of
the
are decom-
trimethyl-
corn-pound catalyzed
decompo-
peroxide.
Dicyclohexylcarbodiimide
which
with
in order
of
benzoyl
peroxide,
investigated
unimoleculer
These
of
have
the
in
the
with
position
upon
of
process
compound
for
carbonyl
diacyl
polar
not.
in Table
observed
detectable
of
formation
for
rigorously %as
the
whether
We
iodometry
are
The
to
example
th_is reaction.
constants
measured
sition
answer
benzoate
of
tin acid
possibility.
standing
bition
this
decomposition
other
not
the
should
trimethyltin
was
of
mechanisms
decomposition
tin
acid-catalyzed
an
4
attack.
possible
Thus,
coordination
benzoate.
considered.as
radical
trimethyltin-benzoate.
by way
been
produced added
DCC
produced
in the although formation
(DCC)
in the
reaction.
or
benzoic
the
affect
presence
the
of
a slight of
was
carbon
employed
to destroy
In order
to determine
anhydride
decomposition,
these
compounds.
acceleration dioxide
by was
and
dicyclohexylurea
the
kinetics
No DCC
was
measured
the
major
effect
were was
found. with
or
without
c3 Table
Rate
1
for
constants
peroxide
the
M)
(0.01
at
decomposition
‘cyclohexane
6.62
+ 0.59
PhCH=CH2
0.1
3.19
f 0.13
Me3SnPh
0.1
4.94
2 0.42
4.06
+ 0.23
a)
CHCl3-cyclohexane
-1
k x 10'sec
mole/l
none
cyciohexane cyclohexane
benzoyl
80°C
Additive
Solvent
of
none
CHC13 -cyclohexane
Me3SnPh
0.1
4.34
+ 0.29
CHC13-cyclohexane
DCCb)
0.02=)
5.92
+ 0.28
CHC13 -cyclohexane
PhCOOCOPh
CI-1
4.92
f 9.30
DC@)
o-02=)
3.43
f 0.33
CHCl
3
-cyclohexane
'a) Itl. v/v with the
b)
mixture*
higher
Dhcyclohexylcarbodi~ide,
concentrations
limited
could
solubility
of
the
DCC
(under
conditions
analysis
shown
not
be
c)
performed d)
additive.
Pxperimenfs
hecause
of
N,N'-Dicyclohexyl-
urea.
addition
of
product
interception amount
of
addition
of the
of the
of
the
DCC.*
by
of
was
trimethyltin
trimethytin amounts
* 29
of
% And
DCC,
not
by
to the
out
the
used
for
examine
the
the possible 9
carbodiimide.
influenced
rule and
those
at
both
all
the
hy
The
the
possibilities
interception
of
the
benzoyloxy
DCC.
of benzoyl
trimethylphenyltin
hexylurea
results
decomposition
Thermolysis of
was
to
in order
radical
dioxide These
catalyzed
radical
in Table.2)
benzoyioxy
carbon
similar
found
with as
or
was
(0.62
CDCl,)
(5.21
28
obtained
respectively.
CO2
were
DCC
determined
ppm,
ppm)
carried
addition
when
dichloromethane
% of
was
without
a product
benzoate
signal
peroxide
was
by
in
Present.
to
that
presence
presence
DicycloThe of of
nitromethane
in the
the
DCC-
integration
relative and
of
out
the the
(4.20
and
yield PMR known ppm)
absence
of
-.
cd added
after
evaporation
shown
in Table
2.
The results seem to-support Conclusive
indicate
obtained a polar
was
PhCOOH
reaction.
rather
was formed acid
.PhlO_
of benzoic
Trimethyltin
.
decomposition
presence
2 PhCOOH
(3)
8 Me3SnOCPh
of benzoyl
peroxide
at 80°C,
Me3SnOCOPh,
in the
18 hrma) Yield
4.4
CHC13-cyclohexaneC)
0.0
13.4
(2)
CHC13-cyclohexane-
1.0
0.0
(2)
10 ml of solvent. of runs averaged,
(%)")
and the tin cornPound (2 aunol) in
5) Parenthetical error:
at 80°C
in 47 % yield.
0.0
(1 mmol)
(4)
in a separate
(10 ml) was heated
cyclohaxane
a) The Peroxide
+ PhH
and trimethylphenyl-
was obtained
DCC mmol
results
by protodestannylation
(1 mmol)
of trimethylphenyltin
Solvent
No t_ri-
These
mixture.
(4) was confirmed
acid
benzoate
of DCC-
(eq. 3,4).
RR
in reaction
solvent _. process. ._
than radical
in the product
in chloroform-cyclohexane
Thermal
are
and in the-mixed
protodestannylation
shown
A mixture
for 16 hr.
The results
.by the addition
by benzoic
t Me3SnPh
(2 mmol)
2
found
homolysisL2
The process
Table
mechanism
that the tin benzoate
of trimethylphenyltin
tin
in cyclohexane
was obtained
benzoate
(PhO) 2
.sblve~~t-..
of the reaction
within
numbers
1.1 8.
indicate
numbers
c) 1:1 v/v mixture.
REFERHNCES 1
G- A. -Razuvaev, 0. S. D'yachkovskaya, Shchepetkova,
..
.-.
evidence
methyltin
_.
Doklady
Akaa.
Nauk
N. S. Vyazankin
SSSR.,
137
and 0. A.
(1961) 618_
c5 :
2
-3
4
NW S. Vyftzankin and 0. S. D'yachkovskaya,
-G. A: Bazuvaev, -0bshch.
Whim._, 32
arid Sons, New York,
5. T. Kashiwagi
and S. Oae,
6
R. Sasin
7
J. Nasielsky,
0. Buch&n,
xaetal. Chem.,
19
and G. S. Sasin,
C- G. Swain, 80
9
and 0. A, Schepetokova,
Tetrahedron, 18 (1962) 667. . See for example, W. P. Neumann, Wiley
The Organic
Chemistry
of Tin,
1967, p 39.
Tetrahedron, J- Org.
26
Chem.,
M. Grosjean
(1970) 3631. 20
(1955) 770.
and M. Jaquet,
J. Organo-
(1969) 353.
L, S. Schaad
and A. J. Kresge,
J. Amer.
Chem.
Sot.,
(1958) 5313.
G. Rrunton, 98
Zh.
(1562) 2161.
G-~~A..Razuv.aev, N. S. Vyazankin _
John
8
‘..
J. F. Taylor
(1976) 4879.
and K.
U.
Ingold,
J. Amer.
Chem.
Sot.?,,
0. EZse+er Seqiioia SA,
Preliminary
Communication
THi2 REACTION A POLAR
SEIZI
OF
BENZOYL
MECHANISM
FORMATIO??
and Jt2?-ICHI
KOZUKA
Department
OF
PEROXIDE
of Applied
University,
WITH OF
TRIME2HYLTIN
BENZOATE
NAKAGAMI
Chemistry,
Sugimotocho,
TRI_KKTHYLPHENYLTIN:
Faculty
Sumiyoshi,
of Engineering,
Osaka
Osaka
City
558, Japan
(Received March 15th, 19771 Summary The mechanism by thermal
of the reaction
decomposition
trimethylphenyltin
of benzoyl
was
investigated.
from
the peroxide,
which
was derived
shown
to give the benzoate.
Razuvaev of benzoyl
pathway l-e.,
et al. have
peroxide
trimethyltin
reported
Homolytic
of the decomposition dioxide was
with
(eq. 1,2).1'3
Although
undoubtedly
of radical
was no definite
was
decomposition gives
was
the major
products
Accordingly,
obtained,
the formation
attack
evidence
on tin for this
0
4
(Ph!!Of2
E-
PhCO*
G
Me3SnPh
-
2 Ph!O .
Ii
Me2SnOCPh
of
acid,
the tin compound
of the other
in terms
there
of benzoic
of trimethylphenyltin
fission
benzoate
in the presence
that the thermal
in view
explained
trimethyltin
Reaction
and hydrocarbons.
of the benzoate
gives
peroxide
in the presence
benzoate.
carbon
which
+ Ph-
(2)
c2 this
mechanism, tin-carbon
bond
has
cleavage
there
However, of
reaction
by
are
of
other
of
the
carboxy
inversion
the
Another
possible
nylation the
reaction
peroxide
gives
Kinetics peroxide the
Kate
by
results
or
given
mode
suggests
both
of
was
phenyltin.
benzoic
acid
whether
the
measured observed The
Trapping
of
the
presence
ds
5
could
give
protodestan-
acid, 6#7
since
8 compound
catalyzes
benzoic the
to
in the
acid
may
mechanism
obtain
the prove
of
a better
under-
by
the
the
or
benzoyl
absence
of
in th.e absence under
addition
and
peroxide
accelerated results
of
peroxide
were
additive.
The
1.
decomposition
inhibition
not
the
were
tin
formation
oxygen,
is the
thermolysis. the
the
peroxide
benzoic
decomposition
the
of
of
concentration.
rule
all out
by tin
of
an
conditions
styrene,
acceleration
at
the
additive
used.
which
Inhi-
in turn
the
decomposition
The
rate
addition
of
of
the
are decom-
trimethyl-
corn-pound catalyzed
decompo-
peroxide.
Dicyclohexylcarbodiimide
which
with
in order
of
benzoyl
peroxide,
investigated
unimoleculer
These
of
have
the
in
the
with
position
upon
of
process
compound
for
carbonyl
diacyl
polar
not.
in Table
observed
detectable
of
formation
for
rigorously %as
the
whether
We
iodometry
are
The
to
example
th_is reaction.
constants
measured
sition
answer
benzoate
of
tin acid
possibility.
standing
bition
this
decomposition
other
not
the
should
trimethyltin
was
of
mechanisms
decomposition
tin
acid-catalyzed
an
4
attack.
possible
Thus,
coordination
benzoate.
considered.as
radical
trimethyltin-benzoate.
by way
been
produced added
DCC
produced
in the although formation
(DCC)
in the
reaction.
or
benzoic
the
affect
presence
the
of
a slight of
was
carbon
employed
to destroy
In order
to determine
anhydride
decomposition,
these
compounds.
acceleration dioxide
by was
and
dicyclohexylurea
the
kinetics
No DCC
was
measured
the
major
effect
were was
found. with
or
without
c3 Table
Rate
1
for
constants
peroxide
the
M)
(0.01
at
decomposition
‘cyclohexane
6.62
+ 0.59
PhCH=CH2
0.1
3.19
f 0.13
Me3SnPh
0.1
4.94
2 0.42
4.06
+ 0.23
a)
CHCl3-cyclohexane
-1
k x 10'sec
mole/l
none
cyciohexane cyclohexane
benzoyl
80°C
Additive
Solvent
of
none
CHC13 -cyclohexane
Me3SnPh
0.1
4.34
+ 0.29
CHC13-cyclohexane
DCCb)
0.02=)
5.92
+ 0.28
CHC13 -cyclohexane
PhCOOCOPh
CI-1
4.92
f 9.30
DC@)
o-02=)
3.43
f 0.33
CHCl
3
-cyclohexane
'a) Itl. v/v with the
b)
mixture*
higher
Dhcyclohexylcarbodi~ide,
concentrations
limited
could
solubility
of
the
DCC
(under
conditions
analysis
shown
not
be
c)
performed d)
additive.
Pxperimenfs
hecause
of
N,N'-Dicyclohexyl-
urea.
addition
of
product
interception amount
of
addition
of the
of the
of
the
DCC.*
by
of
was
trimethyltin
trimethytin amounts
* 29
of
% And
DCC,
not
by
to the
out
the
used
for
examine
the
the possible 9
carbodiimide.
influenced
rule and
those
at
both
all
the
hy
The
the
possibilities
interception
of
the
benzoyloxy
DCC.
of benzoyl
trimethylphenyltin
hexylurea
results
decomposition
Thermolysis of
was
to
in order
radical
dioxide These
catalyzed
radical
in Table.2)
benzoyioxy
carbon
similar
found
with as
or
was
(0.62
CDCl,)
(5.21
28
obtained
respectively.
CO2
were
DCC
determined
ppm,
ppm)
carried
addition
when
dichloromethane
% of
was
without
a product
benzoate
signal
peroxide
was
by
in
Present.
to
that
presence
presence
DicycloThe of of
nitromethane
in the
the
DCC-
integration
relative and
of
out
the the
(4.20
and
yield PMR known ppm)
absence
of
-.
cd added
after
evaporation
shown
in Table
2.
The results seem to-support Conclusive
indicate
obtained a polar
was
PhCOOH
reaction.
rather
was formed acid
.PhlO_
of benzoic
Trimethyltin
.
decomposition
presence
2 PhCOOH
(3)
8 Me3SnOCPh
of benzoyl
peroxide
at 80°C,
Me3SnOCOPh,
in the
18 hrma) Yield
4.4
CHC13-cyclohexaneC)
0.0
13.4
(2)
CHC13-cyclohexane-
1.0
0.0
(2)
10 ml of solvent. of runs averaged,
(%)")
and the tin cornPound (2 aunol) in
5) Parenthetical error:
at 80°C
in 47 % yield.
0.0
(1 mmol)
(4)
in a separate
(10 ml) was heated
cyclohaxane
a) The Peroxide
+ PhH
and trimethylphenyl-
was obtained
DCC mmol
results
by protodestannylation
(1 mmol)
of trimethylphenyltin
Solvent
No t_ri-
These
mixture.
(4) was confirmed
acid
benzoate
of DCC-
(eq. 3,4).
RR
in reaction
solvent _. process. ._
than radical
in the product
in chloroform-cyclohexane
Thermal
are
and in the-mixed
protodestannylation
shown
A mixture
for 16 hr.
The results
.by the addition
by benzoic
t Me3SnPh
(2 mmol)
2
found
homolysisL2
The process
Table
mechanism
that the tin benzoate
of trimethylphenyltin
tin
in cyclohexane
was obtained
benzoate
(PhO) 2
.sblve~~t-..
of the reaction
within
numbers
1.1 8.
indicate
numbers
c) 1:1 v/v mixture.
REFERHNCES 1
G- A. -Razuvaev, 0. S. D'yachkovskaya, Shchepetkova,
..
.-.
evidence
methyltin
_.
Doklady
Akaa.
Nauk
N. S. Vyazankin
SSSR.,
137
and 0. A.
(1961) 618_
c5 :
2
-3
4
NW S. Vyftzankin and 0. S. D'yachkovskaya,
-G. A: Bazuvaev, -0bshch.
Whim._, 32
arid Sons, New York,
5. T. Kashiwagi
and S. Oae,
6
R. Sasin
7
J. Nasielsky,
0. Buch&n,
xaetal. Chem.,
19
and G. S. Sasin,
C- G. Swain, 80
9
and 0. A, Schepetokova,
Tetrahedron, 18 (1962) 667. . See for example, W. P. Neumann, Wiley
The Organic
Chemistry
of Tin,
1967, p 39.
Tetrahedron, J- Org.
26
Chem.,
M. Grosjean
(1970) 3631. 20
(1955) 770.
and M. Jaquet,
J. Organo-
(1969) 353.
L, S. Schaad
and A. J. Kresge,
J. Amer.
Chem.
Sot.,
(1958) 5313.
G. Rrunton, 98
Zh.
(1562) 2161.
G-~~A..Razuv.aev, N. S. Vyazankin _
John
8
‘..
J. F. Taylor
(1976) 4879.
and K.
U.
Ingold,
J. Amer.
Chem.
Sot.?,,