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New hydrophobic host molecules containing multiple redox-active centres
Tetrahedron Printed in
Letters,Vol.29,No.l9,pp Great Britain
NEW
2349-2352,1988
HYDROPHOBIC MULTIPLE
HOST
0040-4039/88 $3.00 Pergamon Press plc
MOLECULES
RBDOX-ACTIVE
+ .OO
CONTAINING
CENTRES
Paul D. Beer* and E. Louise Tite Department of Chemistry. University of Birmingham, P.O. Box 363, Birmingham BIS 2TT.
Abstract The
synthesis
nnd twelve ferrocene
Although
there
a redox-active
latter
molecules and
hydrophobic containing
in close
of redox stems
host
molecule (6).
of type
proximity
interest
in the design
to a crown
into hydrophobic
ether’-3 host
the idea of investigating guest
(4) that
that
I.g,9
current
centres
organic
analogue
It is well known products
from
an included
host molecules (4) and (6) containing respectively four
macrocyclic hydrophobic centres is described.
is considerable
centre
the incorporation
moiety
of two novel redox-active
reactions
A simple
substrate.
contains
adaptation
paper
ferrocenyl
of resorcinol
or cryptand
molecules
been
catalytic
reports groups
with aldehydes
and
interactions
a novel
acidic
by using
molecules site,
repor(ed.S-7
the preparation
under
of this methodology
of receptor
coordination
have
the potential
This
four
and synthesis
containing
few examples Interest
between
of
in these
the redox-active
of a new &ox-active
twelve
conditions
ferrocenyl
can
group
lead
to macrocyclic
a metallocenecarboxaldehyde
leads to
R= CH, ,C,H,
(1) respective
two step
(2) in the presence organic
solvents
preparations
tentatively
assigned
of (3) in dry tetrahydrofuran solid.
m.p.
>250
of (4) and
of hydrochloric
(10%
overall
acid and
(6).
as the phenolic
followed
The
ethanol
by column
reaction gave
macrocycle chromatographic
yield for the two steps).
2349
of ferrocenecarboxaldehyde
initially (3).
a black
precipitate,
Subsequent separation
gave
(1) and insoluble
benzoylation
resorcinol
in all common of a suspension
(4) as an orange
crystalline
2350
Ii
Ii CHO
t Fe
(4) An analogous m.p.
>25O’C
procedure
(10% overall
using ferrocenecarbonyl yield).
chloride
(5) gave (6) as an orange-red
crystalline
solid
2351
(6) Elemental spectroscopy
analyses, confirmed
CDC13 at ambient possesses shows
temperature
two electron
reveals
of the respective These
four
interesting
which
reversible ferrocenyl
two types
exciting
= 2057,
(6) m/z 29211 and
It is noteworthy of ferrocene
Preliminary
oxidation
waves
groups
electrochemical at 19.575
V and
that
IH
the IH
and
lSC
n.m.r.
n.m.r.
spectrum
of (4) in
suggesting
the solution
structure
of (4)
experiments
(acetonitrile,
S.C.E.)
on (4)
+0.665
V corresponding
to the oxidation
moieties.
electrochemical
may exhibit
[(4) m/z
structures.*O*ll
a C2 axis of syrnmetry.lO~II
two,
species
mass spectrometry the proposed
observations
indicate
the future
new electronic,
optical,
catalytic
possibility and
physical
for preparing properties.
mixed-valence
2352
Acknowlednements We thank the SERC for a CASE award to E.L.T.,
for use of the high field n.m.r.
service at the
University of Warwick and The Research Corporation Trust, L and D Blond for additional financial support.
References I.
(a) P.D. Beer, J. Chem. Sot. Chem. Commun. 1985, 111.5. (b) T. Saji. Chem. Lett. 1986, 275. Czech and A. Ratajczak. Pol. J. Chem. 1980, s, Chem. 1986, m, 1983, &
ClO.
767.
(c) B.
(d) P.D. Beer and A.D. Keefe, J. Organometal.
(e) S. Akabori, Y. Habata, Y. Sakamoto, M. Sato and S. Ebine, Bull. Sot. Jpn.
537.
2. R.E. Wolf and S.R. Cooper, J. Am. Chem. Sot. 1984, &)$, 4646. Sot. Chem. Commun. 1986, 220. Trans 1 1986. 2069.
(b) L. Echegoyen,
D.A. Gustowski,
(c) K. Maruyama, H. Sohmiya and H. Tsukube, J. Chem. Sot. Perkin
(d) F. Diet& G. Giener and
Merz, Synthesis 1986, 626.
A.
3. A. Kaifer, D.A. Gustowski. L. Echegoyen. V.J. Gatto, R.A. Schultz, T.P. Cleary. C.R. Morgan, D.M. Goli. A.M. Rios and C.W. Gokel, J. Am. Chem. Sot. 1985, 107, 1958. 4. (a) P.D. Beer, A.D. Keefe, C.G. Crane, A.R. Whyman, J. Organometal. P.D. Beer, CD.
Bush and T.A. Hamor, J. Organometal.
Chem. 1986. 314, C9.
Chem. 1988, m,
(b)
133.
5. A. Veno, F. Monivaki, T. Osa, F. Hamadal and K. Murai, Chem. Pharm. Bull. 1986, 3,
438.
6. I. Tabushi. N. Shimizu, K. Yamamura. J. Am. Chem. Sot. 1977, B. 7100. 7. P.D. Beer, A.D. Keefe, J. Inclusion Phenom. 1987, 2, 499. 8. A.G.S. Hogberg, J. Org. Chem. 1980, g.
4498.
9. A.G.S. Hogberg, J. Am. Chem. Sot. 1980, 102, 6046. IO. The result
of a single crystal
X-ray
analysis of (4)
is
in accordance with the proposed structure.
P.D. Beer, E.L. Tite. A.M.Z. Slawin and D.J. Williams, to be reported elsewhere. 11.
‘H NMR (CDCl3) for (4) 3.93 (24H. g)), 4.05 (4H g), 4.12 (4H g), 4.23 (4H, g)). 5.65 (4H. s). 6.64 (2H. s). 6.73 (ZH, s), 6.75 (2H. s), 7.20-7.25 (8H, m). 7.42-7.58 (16H m), 7.82-7.99 (16H, m). KBr disc = 1735 cm-l.
Cy2&@1gFeq
requires found
(Received
in
C, 72.4, H 4.3 C, 72.3, H 4.5
UK 23 March
1988)
I’ (C = 0)
Letters,Vol.29,No.l9,pp Great Britain
NEW
2349-2352,1988
HYDROPHOBIC MULTIPLE
HOST
0040-4039/88 $3.00 Pergamon Press plc
MOLECULES
RBDOX-ACTIVE
+ .OO
CONTAINING
CENTRES
Paul D. Beer* and E. Louise Tite Department of Chemistry. University of Birmingham, P.O. Box 363, Birmingham BIS 2TT.
Abstract The
synthesis
nnd twelve ferrocene
Although
there
a redox-active
latter
molecules and
hydrophobic containing
in close
of redox stems
host
molecule (6).
of type
proximity
interest
in the design
to a crown
into hydrophobic
ether’-3 host
the idea of investigating guest
(4) that
that
I.g,9
current
centres
organic
analogue
It is well known products
from
an included
host molecules (4) and (6) containing respectively four
macrocyclic hydrophobic centres is described.
is considerable
centre
the incorporation
moiety
of two novel redox-active
reactions
A simple
substrate.
contains
adaptation
paper
ferrocenyl
of resorcinol
or cryptand
molecules
been
catalytic
reports groups
with aldehydes
and
interactions
a novel
acidic
by using
molecules site,
repor(ed.S-7
the preparation
under
of this methodology
of receptor
coordination
have
the potential
This
four
and synthesis
containing
few examples Interest
between
of
in these
the redox-active
of a new &ox-active
twelve
conditions
ferrocenyl
can
group
lead
to macrocyclic
a metallocenecarboxaldehyde
leads to
R= CH, ,C,H,
(1) respective
two step
(2) in the presence organic
solvents
preparations
tentatively
assigned
of (3) in dry tetrahydrofuran solid.
m.p.
>250
of (4) and
of hydrochloric
(10%
overall
acid and
(6).
as the phenolic
followed
The
ethanol
by column
reaction gave
macrocycle chromatographic
yield for the two steps).
2349
of ferrocenecarboxaldehyde
initially (3).
a black
precipitate,
Subsequent separation
gave
(1) and insoluble
benzoylation
resorcinol
in all common of a suspension
(4) as an orange
crystalline
2350
Ii
Ii CHO
t Fe
(4) An analogous m.p.
>25O’C
procedure
(10% overall
using ferrocenecarbonyl yield).
chloride
(5) gave (6) as an orange-red
crystalline
solid
2351
(6) Elemental spectroscopy
analyses, confirmed
CDC13 at ambient possesses shows
temperature
two electron
reveals
of the respective These
four
interesting
which
reversible ferrocenyl
two types
exciting
= 2057,
(6) m/z 29211 and
It is noteworthy of ferrocene
Preliminary
oxidation
waves
groups
electrochemical at 19.575
V and
that
IH
the IH
and
lSC
n.m.r.
n.m.r.
spectrum
of (4) in
suggesting
the solution
structure
of (4)
experiments
(acetonitrile,
S.C.E.)
on (4)
+0.665
V corresponding
to the oxidation
moieties.
electrochemical
may exhibit
[(4) m/z
structures.*O*ll
a C2 axis of syrnmetry.lO~II
two,
species
mass spectrometry the proposed
observations
indicate
the future
new electronic,
optical,
catalytic
possibility and
physical
for preparing properties.
mixed-valence
2352
Acknowlednements We thank the SERC for a CASE award to E.L.T.,
for use of the high field n.m.r.
service at the
University of Warwick and The Research Corporation Trust, L and D Blond for additional financial support.
References I.
(a) P.D. Beer, J. Chem. Sot. Chem. Commun. 1985, 111.5. (b) T. Saji. Chem. Lett. 1986, 275. Czech and A. Ratajczak. Pol. J. Chem. 1980, s, Chem. 1986, m, 1983, &
ClO.
767.
(c) B.
(d) P.D. Beer and A.D. Keefe, J. Organometal.
(e) S. Akabori, Y. Habata, Y. Sakamoto, M. Sato and S. Ebine, Bull. Sot. Jpn.
537.
2. R.E. Wolf and S.R. Cooper, J. Am. Chem. Sot. 1984, &)$, 4646. Sot. Chem. Commun. 1986, 220. Trans 1 1986. 2069.
(b) L. Echegoyen,
D.A. Gustowski,
(c) K. Maruyama, H. Sohmiya and H. Tsukube, J. Chem. Sot. Perkin
(d) F. Diet& G. Giener and
Merz, Synthesis 1986, 626.
A.
3. A. Kaifer, D.A. Gustowski. L. Echegoyen. V.J. Gatto, R.A. Schultz, T.P. Cleary. C.R. Morgan, D.M. Goli. A.M. Rios and C.W. Gokel, J. Am. Chem. Sot. 1985, 107, 1958. 4. (a) P.D. Beer, A.D. Keefe, C.G. Crane, A.R. Whyman, J. Organometal. P.D. Beer, CD.
Bush and T.A. Hamor, J. Organometal.
Chem. 1986. 314, C9.
Chem. 1988, m,
(b)
133.
5. A. Veno, F. Monivaki, T. Osa, F. Hamadal and K. Murai, Chem. Pharm. Bull. 1986, 3,
438.
6. I. Tabushi. N. Shimizu, K. Yamamura. J. Am. Chem. Sot. 1977, B. 7100. 7. P.D. Beer, A.D. Keefe, J. Inclusion Phenom. 1987, 2, 499. 8. A.G.S. Hogberg, J. Org. Chem. 1980, g.
4498.
9. A.G.S. Hogberg, J. Am. Chem. Sot. 1980, 102, 6046. IO. The result
of a single crystal
X-ray
analysis of (4)
is
in accordance with the proposed structure.
P.D. Beer, E.L. Tite. A.M.Z. Slawin and D.J. Williams, to be reported elsewhere. 11.
‘H NMR (CDCl3) for (4) 3.93 (24H. g)), 4.05 (4H g), 4.12 (4H g), 4.23 (4H, g)). 5.65 (4H. s). 6.64 (2H. s). 6.73 (ZH, s), 6.75 (2H. s), 7.20-7.25 (8H, m). 7.42-7.58 (16H m), 7.82-7.99 (16H, m). KBr disc = 1735 cm-l.
Cy2&@1gFeq
requires found
(Received
in
C, 72.4, H 4.3 C, 72.3, H 4.5
UK 23 March
1988)
I’ (C = 0)