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New decarboxylation syntheses of polyfluorophenylorganometallic compounds
Journal of Fluorine Chemistry, 8 (1976) 545 ~ 548 0 Elsevier Sequoia S.A., Lausanne - Printed in the Netherlands Received:
545
July 20, 1976
PRELIMINARY NOTE
New Decarboxylation
Syntheses
of Polyfluorophenylorganometallic
Compounds
G. B. DEACON, G. J. FARQUHARSON, and R. J. PHILLIPS
Chemistry
Department,Monash
Syntheses reactions
University,
of organometallic
Clayton,Victoria
compounds
by thermal decarboxylation
are currently limited to derivatives
[3], nickel
[4], tin [l ,5],
fluorocarbon
compounds
and are known [l-4,6] decarboxylation successful compounds, elimination
for all the above elements
syntheses
application
to a Group 3B derivative*),
whilst
nitrogen several
(Table 1) were prepared by decomposition pyridine
germanium was obtained
for l-10
hr.,
* Decarboxylation conditions
of the method
tin.
We now report (the first
some fluorocarbon
bond).
(1 atm.) for 1 hr. gave tris-
of the appropriate
compounds polyfluoro-
and pentafluorophenyltriphenyland decomposition
in the same solvent.
(3 hr.) of Details
are given in Table 1.
of thallic
carboxylates
has been observed,
has no preparative
tin
(the first use of an
polyfluorophenyltin
by ‘in situ’ formation
pentafluorobenzoatotiphenylgermanium(IV) of the reactions
to
of pentafluorobenzoatobispentafluorophenyl-
[8] at ~a. 280-300’under
in boiling
except
in the formation of a germanium-carbon
pentafluorophenylthallium,
benzoates
Group 1B
Applications
of trispentafluorophenylthallium
and pentafluorophenyltriphenylgermanium reaction
[l].
have been important in development
Thermal decomposition thallium(II1)
of Group 28 [1,2],
and arsenic
lead [l ,6],
3168 (Australia)
consequences
under mass spectrometric
but is caused [7].
by electron
impact and
H20
H20
’
b -
c
’
+ p-HC6F4SnPh3
Ph3GeC6F5
’
c
p-(Ph3Sn)2C6F4
Ph3Sn-pEtOC6F4
c
a
25
15
81
47
65
40
Yield (%) to)
116 - 117
90 - 93
236
63
84 - 85
258 - 263
m.p.
pure.
those
114 - 116
4
d
!I
86
260 - 265
1it.m.p.
a From treatment of the product with 1,4-dioxan. Infrared, NMR, and mass spectra in agreement with authentic sample prepared by the reported method [9]. b Prepared from triphenyltin hydroxide and the appropriate acid in methanol, and obtained analytically 2 Satisfactory analyses obtained. d New compound. 5 Identified by NMR and mass spectrometry.
Ph3GeBr+Ag02CC6Fg
p-(Ph3Sn02C)2C6Fq.
Ph3SnO2C-p-EtOC6F4.
Ph3SnC6F5
Ph3Sn02CC6F5.H20
’
(C F ) Tl.diox 6 53
and -germanium
(c,F~)~TI~~CC~F~
Reactions
-tin,
Product
by Decarboxylation
of Polyfluorophenyl-thallium,
Reactant
Compounds
Syntheses
TABLE 1
of an
[lOI
DOI
[ 91
[Ref.]
547
(1)
Ph3SnO2CR E-(Ph3Sn02C)2C6F4
AgBri+
Detection
of a near quantitative
precluded
the possibility
rearrangement
[Ph3Ge02CC6F51*
that the organothallium
[9] complex
the compounds
acetone/petrol)
evaporation
were isolated
of the residue
chromatography
to dryness,
(5)
by dissolution
In other cases
by preparative
obtained
as the air-
and washing
t.1. c.
on evaporation obtained
of the
the complex
[reactions
(2) -
(eluted with of the pyridine.
in low yield
(Table 1) on
of the crude product from (3), may be formed by slight
(6) of the major product e-(Ph3Sn)2C6F4
These results decarboxylation
indicate
reactions
of thallium,
G.B.Deacon,
on the t.1.c.
plates.
Ph3SnOH +E-HC6 F4SnPh3
e-(Ph3Sn)2C6F4+H20’
references
(1)
was formed by
isolated
(diox = 1,4-dioxan)
Triphenyl-2,3,5,6-tetrafluorophenyltin,
P.Sartori
compound
was conveniently
with petrol to remove perfluoropolyphenyls.
derivatives
in reaction
(4)
2 (C, F5) 3Tl + Tl (02CC6F5J 3
(C6F5J3Tl.diox
crude product in dioxan,
hydrolysis
Ph3GeC6F5+C02
(5).
Trispentafluorophenylthallium
(4)],
(3)
yield of carbon dioxide
3(C6F5J2T102CC6F5w
stable
(2)
e-(Ph3Sn)2C6F4+2C02
-
Ph3GeBr+Ag02CC6F5--*
(R=C6F5 ore-EtOC6F4)
Ph3SnR+ CO2
l
considerably
increased
in organometallic germanium,
(6)
potential
synthesis.
for
Extensions
to other
and tin are being investigated.
Organomet.Chem.Rev.
(A), 5 (1970) 355, and
therein. and H.Adelt,
J.Fluorine
Chem.,
P. Sartori and H. J. Frohn, Chem. Ber., R.H.Mobbs, A. Caimcross,
and D.E.M.Walton, J. R.Roland,
3 (1973/1974)
275:
107 (1974) 1195: M.W.Buxton,
J.Fluorine
R. M. Henderson,
Chem .Sot. , 92 (1970) 3187: C.M.Mitchell
Chem.,
1 (1971/1972)
and W.A. Sheppard, and F.G.A.Stone,
179. J.Amer.
Chem.
P.O.Okulevich, Commun. , (1970) 1263: V.R.Polishchuk, . L.A.Fedorov, L.S.German, and I.L.Knunyants, Tetrahedron Lett., (1970) 3933.
548
4
P.G.Cookson
and G.B.
5
R.A.Cummins,
P.Dunn,
6
P.G.Cookson,
G.B.Deacon,
7
A.T.T.Hsieh,
A.G.
8
G.B.Deacon,
Aust. J.Chem.,
9
G.B.Deacon
and D.G.Vince,
J.Chem.,
10 S.G.Cohen
27 (1974)
Deacon,
Aust.J.Ciiem.,
and D.Oldfield, P.W.Felder
25 (1972)
Aust.J.Chem.,
2095.
24 (1971)
and G.J.Farquharson,
2257.
Aust.
1895. Lee,
and A.G.Massey,
and P.L.Sears, 20 (1967)
J.Org.Chem., 459.
Aust.J.Chem., Adv.
37 (1972) 2637.
Fluorine
28 (1975) Chem.,
1931.
6 (1970)
83.
545
July 20, 1976
PRELIMINARY NOTE
New Decarboxylation
Syntheses
of Polyfluorophenylorganometallic
Compounds
G. B. DEACON, G. J. FARQUHARSON, and R. J. PHILLIPS
Chemistry
Department,Monash
Syntheses reactions
University,
of organometallic
Clayton,Victoria
compounds
by thermal decarboxylation
are currently limited to derivatives
[3], nickel
[4], tin [l ,5],
fluorocarbon
compounds
and are known [l-4,6] decarboxylation successful compounds, elimination
for all the above elements
syntheses
application
to a Group 3B derivative*),
whilst
nitrogen several
(Table 1) were prepared by decomposition pyridine
germanium was obtained
for l-10
hr.,
* Decarboxylation conditions
of the method
tin.
We now report (the first
some fluorocarbon
bond).
(1 atm.) for 1 hr. gave tris-
of the appropriate
compounds polyfluoro-
and pentafluorophenyltriphenyland decomposition
in the same solvent.
(3 hr.) of Details
are given in Table 1.
of thallic
carboxylates
has been observed,
has no preparative
tin
(the first use of an
polyfluorophenyltin
by ‘in situ’ formation
pentafluorobenzoatotiphenylgermanium(IV) of the reactions
to
of pentafluorobenzoatobispentafluorophenyl-
[8] at ~a. 280-300’under
in boiling
except
in the formation of a germanium-carbon
pentafluorophenylthallium,
benzoates
Group 1B
Applications
of trispentafluorophenylthallium
and pentafluorophenyltriphenylgermanium reaction
[l].
have been important in development
Thermal decomposition thallium(II1)
of Group 28 [1,2],
and arsenic
lead [l ,6],
3168 (Australia)
consequences
under mass spectrometric
but is caused [7].
by electron
impact and
H20
H20
’
b -
c
’
+ p-HC6F4SnPh3
Ph3GeC6F5
’
c
p-(Ph3Sn)2C6F4
Ph3Sn-pEtOC6F4
c
a
25
15
81
47
65
40
Yield (%) to)
116 - 117
90 - 93
236
63
84 - 85
258 - 263
m.p.
pure.
those
114 - 116
4
d
!I
86
260 - 265
1it.m.p.
a From treatment of the product with 1,4-dioxan. Infrared, NMR, and mass spectra in agreement with authentic sample prepared by the reported method [9]. b Prepared from triphenyltin hydroxide and the appropriate acid in methanol, and obtained analytically 2 Satisfactory analyses obtained. d New compound. 5 Identified by NMR and mass spectrometry.
Ph3GeBr+Ag02CC6Fg
p-(Ph3Sn02C)2C6Fq.
Ph3SnO2C-p-EtOC6F4.
Ph3SnC6F5
Ph3Sn02CC6F5.H20
’
(C F ) Tl.diox 6 53
and -germanium
(c,F~)~TI~~CC~F~
Reactions
-tin,
Product
by Decarboxylation
of Polyfluorophenyl-thallium,
Reactant
Compounds
Syntheses
TABLE 1
of an
[lOI
DOI
[ 91
[Ref.]
547
(1)
Ph3SnO2CR E-(Ph3Sn02C)2C6F4
AgBri+
Detection
of a near quantitative
precluded
the possibility
rearrangement
[Ph3Ge02CC6F51*
that the organothallium
[9] complex
the compounds
acetone/petrol)
evaporation
were isolated
of the residue
chromatography
to dryness,
(5)
by dissolution
In other cases
by preparative
obtained
as the air-
and washing
t.1. c.
on evaporation obtained
of the
the complex
[reactions
(2) -
(eluted with of the pyridine.
in low yield
(Table 1) on
of the crude product from (3), may be formed by slight
(6) of the major product e-(Ph3Sn)2C6F4
These results decarboxylation
indicate
reactions
of thallium,
G.B.Deacon,
on the t.1.c.
plates.
Ph3SnOH +E-HC6 F4SnPh3
e-(Ph3Sn)2C6F4+H20’
references
(1)
was formed by
isolated
(diox = 1,4-dioxan)
Triphenyl-2,3,5,6-tetrafluorophenyltin,
P.Sartori
compound
was conveniently
with petrol to remove perfluoropolyphenyls.
derivatives
in reaction
(4)
2 (C, F5) 3Tl + Tl (02CC6F5J 3
(C6F5J3Tl.diox
crude product in dioxan,
hydrolysis
Ph3GeC6F5+C02
(5).
Trispentafluorophenylthallium
(4)],
(3)
yield of carbon dioxide
3(C6F5J2T102CC6F5w
stable
(2)
e-(Ph3Sn)2C6F4+2C02
-
Ph3GeBr+Ag02CC6F5--*
(R=C6F5 ore-EtOC6F4)
Ph3SnR+ CO2
l
considerably
increased
in organometallic germanium,
(6)
potential
synthesis.
for
Extensions
to other
and tin are being investigated.
Organomet.Chem.Rev.
(A), 5 (1970) 355, and
therein. and H.Adelt,
J.Fluorine
Chem.,
P. Sartori and H. J. Frohn, Chem. Ber., R.H.Mobbs, A. Caimcross,
and D.E.M.Walton, J. R.Roland,
3 (1973/1974)
275:
107 (1974) 1195: M.W.Buxton,
J.Fluorine
R. M. Henderson,
Chem .Sot. , 92 (1970) 3187: C.M.Mitchell
Chem.,
1 (1971/1972)
and W.A. Sheppard, and F.G.A.Stone,
179. J.Amer.
Chem.
P.O.Okulevich, Commun. , (1970) 1263: V.R.Polishchuk, . L.A.Fedorov, L.S.German, and I.L.Knunyants, Tetrahedron Lett., (1970) 3933.
548
4
P.G.Cookson
and G.B.
5
R.A.Cummins,
P.Dunn,
6
P.G.Cookson,
G.B.Deacon,
7
A.T.T.Hsieh,
A.G.
8
G.B.Deacon,
Aust. J.Chem.,
9
G.B.Deacon
and D.G.Vince,
J.Chem.,
10 S.G.Cohen
27 (1974)
Deacon,
Aust.J.Ciiem.,
and D.Oldfield, P.W.Felder
25 (1972)
Aust.J.Chem.,
2095.
24 (1971)
and G.J.Farquharson,
2257.
Aust.
1895. Lee,
and A.G.Massey,
and P.L.Sears, 20 (1967)
J.Org.Chem., 459.
Aust.J.Chem., Adv.
37 (1972) 2637.
Fluorine
28 (1975) Chem.,
1931.
6 (1970)
83.