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Synthesis of [18]Annulene Dioxide An Oxygen-bridged [18] Ц Annulene Possessing Equivalent Kekul Structures.

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to be cited as
Angew. Chem. Suppl.
1983,471-479
zu zitieren als
Angew. Chem. Suppl.
1983,471 -479
Q Veilag Chernse GmbH. D-6940Weinhem, 1983
S 02 5010
0721-4227/83/0505-0471
Synthesis
of (181Annulene Dioxide: An Oxy~en-bridgedL181-
Annulene Possessrng Equivalent KekulL Structures
I
Haru
Ogawa',
Naomi Sadakarr, Tail1 Imoto, Izuml
Miyamoto,
Hidefumi Kato and Ydlchi Taniguchi
Llu
[18]Annulene trioxrde
first
rule
oxygen-bridged
1 'la'
was characterized as
L18lannulene satisfying the
Fig.
the
dehydration
of
yield (35)).
3
the
outer protons and on its closely similar electronic spec-
2L1b1.
Our
-
isolated,
cyclo-olefin, such as
1,albeit
and
it was separated from an
intense
chloro-
green band by chromatography on S i 0 2 !n-hexane)
phyll-like
rum of
* Prof. Dr. H. Ogawa,
1
-
3
The 13C-NMR spcct-
(CDC13) exhibited five resonance lines ! F l q .
spectrum of 2
- (CDC13, 100 MHz,
'H-NMR
cates
Fiq.
3)
as is implied by the centrosymmetrical forniulation
-
triplet
at
extremly high field (6 -5.89 ppml, while
I. Niyamoto, Dr. H. Kato and Prof. Dr. Y. Taniguchl
Department of General Chemistry, National Kurume
signals
of
the
3c.
The signal of the 2 inner protors appeared as a
12 outer protons
were
found
communication
-
-
3.
indicates
2
that
Inspection
has a
pseudo-hexagonal
geometry,
successive
sp2
placed
both ends of the longer axis of the
at
carbon
units, and two
as indicated I n Fig. 1.
the
twu oxygen
cavity,
103 9
furan
in
three
rings
are
molecule,
A "snag-frt" accomodation of
and two hydrogen atoms is possible In the
putting all of the outer and inner protons coplaTwo equivalent KekulL
narly with the molecular plane.
structures
2 can be written for 3 , as for benzene,
La,
as a consequence of the two oxygen bridges.
expected
to
Thus,
be a resonance-stabilized bridged
2
is
Fig. 2
13C-NMR spectrum o i Ll8lannulene dioxide 3
in C D C l j
annulene,
whose properties are to be fully investigated by synthesis.
Double
Wittig reaction of furan-2.5-dialdehyde
trimethylene-bis-triphenylphosphonium
excess)
dilution
-
of the molecular model
each side of the hexagon is constructed with
which
1181 -
concerns with "one pot synthesis" of
annulene dioxide
473
in
dry
DMF at 85'
condition
lead
bromide
(LiOMe as
to
3
[
base)
presumably
6
-
2
(15%
under
via
"f
Hb 1000
with
high
thermal
I///
!I
W m 0
r- m o
H,
In ln4
Fig. 3
-
472
-
I
I
'H-NMR spectrum of Il8lannulene dioxide 3
In CDC13 (100 MHz)
-
474
-
the
downfield
Technrcal College, Kurume 830 !Japan)
471
2)
indi-
clearly that there are only four different nagnetic
sites,
Sadakari, Prof. D r . T. ImotO
Faculty of Pharmaceutical Sciences, Kyushu Universlty
62, Fukuoka 812 (Japan)
N.
-
lower
present
The
2
-
in
could be obtained as a sole annulere to be
[m.p. 2 3 5 " , green plates (n-hexanel 1.
I
-
2
Huckel
bclsed on the very lowfield proton resonances of
crum with that of ll8lar.nulene itself
Scale drawing from the CPK model
1
(9.13 - 10.001.
Thus, the aromatic character of
3
is
confirmed
by the exsistence of a strong diamagnetic
current.
The 'H-NMR spectrum was found to be essentially
Table 1 . Electronic Spectral Data
I.
unaffected by further heating (up to 150' in DMF-d
The difference of chemical shifts of the inner protons1H 1
and
outer protons (H
in
I
is the highest value yet
recorded
and didehydroll8lannulene series[41.
the
Hzl
is
[18lannulene 2
-
(Jtrans=
13.5 Hzl, the JCis value (J . = 10.8 Hzl of 3 is different
cis
from that of 2 1J . = 8.0 H z l , indicating that the H\C=COH
cis
valence bond angles 8 and $ o f 2 should be larger than
hmax
(3.891
______
350
(4.70) 323
(4.801
335
365
valence angle dependence of the vicinal coupling constants
559
11.851
of the cis double bond"].
569
595
In
accordance with
electronic
tially
2
[Fig. 4 and Table 1 1 was
in shape to those of
as
trisrnethan0[18lannulene"~,
annulene
dioxide
trioxide J
based on
the
theoretical prediction[6',
spectrum of
similar
2,
and
an
the
essen-
[18lannulene 2
well as to those of
and
1181-
unsymmetrical I18lannulene
which is constructed with the same building
-
3
, but possesses a different array
in
the
blocks
with
oxygen
bridges [i.e., two furan rings and 10 sp2 carbons,
for the structure
tion,
4,see
Table 1 1 .
absorption maxima
correlations each
other
annulenes make
as shown in
475
good
see the
Table 1
405
426
_____
675
692
708
752
11.701
(2.001
(1.901
(1.901
764
779
810
12.101
12.001
(1.501
(4.841
345
382
403
(3.531
(3.78)
14.241
438
460
14.~11 423
14.62)_ 442
(4.11)
(3.35)
503
520
527
-
(1.711
460
12.011 (1.95) 439
12.141
12.101
536
546
560
570
>84
600
607
619
626
632
641
659
671
704
716
(2.191
12.88)
(2.52
(2.201
12.101
(2.17)
(2.53)
12.82)
12.801
13.1Cl
(2.731
(3.081
-
effectively
to
14.631
336
345
393
413
(1.801
(1.80)
603
(1.851
616
(1.851
____
622
(1.601
636
(1 851
-
I
logc
(5.461
13.511
_(3.741
To a first approxima-
of these
-
247
(3.871
273
(4.261 284
(4.90)
379
(5.501 332
411
(3.951 370
--__
419
(3.85)
~
_ 391
(4.451
13.901
fully symmetrical Dsh structure
-
log & hmax
(3.691
(3.35)
13.44) 278
Amax
220
139
(4.30) 309
456
463
those of
log E
4131
3
-
l[la.91
-
loge
While the magnitude
vicinal coupling constant of 3
- 1Jtrans= 13.5
coincided with that of
2[61
hmax
if3',
[18lannulene Ll2], bridged f18lannulene dioxide
of
(Ama, in nm)
ring
a
rigid
introduced in
and planar
477
3
(5.661
13.401
(4.86)
(3.731
498
5 ~ 2
12.01)
12.323
533
12.181
544
12.05)
564
573
58)
602
12.46)
(1.15)
(1.95)
(L.10)
13.361
(4.34) 636
(1.661
(0.96)
12.531
-
as to keep the 1 8 X perimeter
centrosymmetrical conformation,
wherein X-delocalization occurs extensively with no bondlength alternation.
Thus,
2
is a good model to show the
significance of equivalent Kekuli. structures for the stabilization of 14nt21annulenes.
Indeed,
3
can be stored
at room temperature for a long time without decomposition.
References and Note:
[11 a) G. M. Badger, J. A. Elix, and G. E. Lewis, Austral.
J. _
Chem.
_
_
19 (19661 1221. bl G. M. Badger, '"Aromatic
Character and Aromaticity", Cambridge University
103; for the electronic spectrum of
P.
cl B. Briat, D. A. Schooley, R. Xecords, E.
Bunnenberg, and C. D]erassi,
t
100
GOO
h -
500
SOD
700
[2] J.
Electronic spectrum of I18lannulene dloxlde
in n-hexane
lines indicated in Table 1 1 .
annulene dioxides
4 and 2 .
i
-
89
Gllles, J. F. M. 0th. F. Sondheimer, E.
119711 2177: The A6 of
2
P.
[la]-
These bathochromic shifts can
since
considerable bathochromlc shifts were observed in
4
through the entire wavelength bands even by the non-planar
Taniguchi, T. Koga and Y. Nogami, Tetrahedron Lett.,
(1983) in press.
[4] M. Nakagawa, Pure and A e p l . Chem.
44
11975) 885.
A6 in tetra-t-butyl didehydroI18 Iannulene=14.90 ppm.
[51 H. Giinther, "NMR Spectroscopy", John Wiley and Sons.
1980, P. 110 (Translated by R.
W.
Gleasonl.
[ 6 ] H. R. Blattmann, E. Heilbronner, and G. WagniGre,
At
present
we conclude that oxygen bridges are
-
476
-
Woo,
is 12.13ppm.
[ 3 ] H. Ogawa, C. Fukuda, T. Imoto, I . Mlyamoto, Y.
1 to
ascribable to the removal of one oxygen bridge,
the
M.
J. Chem. SOC. 1Bl
There are steady bathochro-
mic shifts by passing from il8lannulene trioxlde
be
J. Amer. Chem. SOC.
(19671 7 0 6 2 .
ZOO
€19.4
- see
1,
1969,
also
most
Amer. Chem. SOC. 90 (19681 4786.
-
478
-
&
171 W. Wagemann, M. Iyoda, H. M. Deger, J. Sombroek, and
other hand, knowledges collected from heteroIl71annulenes[31
90
indicated that dratroplcrty of the heteroannulenes is sensi-
E. vogel, Angew. Chem.
Int. Ed. Engl.
(1978) 988; Angew. Chem.
11 (1978) 956.
tive to the structures, and small structural perturbation
[8] Reported electronic spectral data of
- are
1
rmcomplete,
may be sufficient to destroy the n-bond delocalization.
since those of the absorptlon maxima longer than 4 2 6 nm
are lacking in the references la and lc.
Received February 11, 1 9 8 3 / Z 277 S /
-
The double Wittig reaction of dialdehyde 1"' with bisphosphonium salt
& (X=
as a sole isomer.
0) in Dt4F at 6O0C [LiOMe as base1 gave
_S
-
In contrast, similar reaction of L w i t h
2b (X= S ) gave three annulenes.
I
These were separated by
chromatography (Si02. n-hexane), and characterized as f1616, di-trans
thia[l7]annulene
annulene dioxide P
-
5 and
-
mono-
-
trans thia(l7lannulene Q [for the physical data, see Table
~
11.
-
479 -
-
Dieses Manuskript ist
zu zitieren als
Angew. Chern. Suppl.
This manuscript is
to be cited as
Angew. Chern. Suppl.
1983,480-487
1983,480-487
0 Verlag Chernie GmbH. D-6940Weinhem. 1983
07214227/83/0505JJ4808
02 5010
-
Selected Physical Data of Compound
2
,
A, 2
,
A
the oxall7iannulene A : mp 236O (EtOX); yield 8.0%; M S :
252(M+); l3C-NXR (CDC13, TMS int. 6) 94.8, 95.7, 108.5,
110.1, 111.7, 113.8, 115.8, 123.0, 127.7, 141.0
m,'~
uvLn-hexane): imax = 236nm ( E = 22500), 242 (22400), 287sh
(348001, 298 (43500). 309 (46500), 384 ( 7 8 0 0 ) , 401 (11300)
and 426 (115001
Hetero [17lannulene Dioxides and I16IAnnulene Dioxide
Prepared by Using Furan as Building Blocks
By Haru Ogawa
Table 1.
and
481
, Chiyukl Fukuda. Taiji Imoto. I z w i Xiyaxoto,
Xidefumr Xato and Yoichi Taniguchi
Recent investigations of bridged [18lannulene~'l'~~
have
di-trans thia[l7]annulene 2
- : np 176 (EtOH); yield 2.0%;
MS: m/n 268 (M+); "C-NMR
(CDCl3, TMS int. 6 ) : 108.5, 109.2,
109.6, 112.0, 112.9, 113.9, 116.4, 116.6, 121.0, 123.3,
126.3, 148.2, 152.8. 161.1; UV fn-hexane): Amax = Z2Onm
(6 = 7000), 241 (8000), 321 (21500), 331 (23100), 394
(1670). 413 (2200), and 436 (2400)
demonstrated that aromatic s-delocalization is not hampered
even by the lack of planarity.
In order to examine
whether such behaviour arises also in isoelectronic hetero[17lannulenes, we prepared oxa[l7lannulene 2 and two stereoisomeric thiaIl7lannulenes 2 and
5.
Yodel considerations
indicate that these a r e not capable of attainlng planarity,
but they are forced to have twisted conformations.
*
On the
mono-trans thiall7lannulene
: mp 221' (EtOH); yield
2.2%; MS: d x 268 (M'I;
13C-NMR (CDCl3, TMS int. 6): 109.6.
110.2, 114.4, 115.9, 122.9, 123.4, 124.2, 127.3, 152.8.
161.0; UV (n-hexane): Amax =243nm ( E = 15000). 331 (42700),
316.5 (36600). 390 (36601, 415 (5600). and 439 (6600)
the 116lannulene dioxide
-
:
mp 182-184' (EtOH); yield 2.0%,
MS: ~ /236
s (M+); 13C-NMR (CDCl3. TMS int. 6 ) : 109.2,
112.9, 116.9, 120.9, 125.7, 135.4, 155.7; UV (n-hexane):
Amax = 278 na ( E = 724001, 331 (4500). 530 (270)
Prof. Dr. H. Ogawa, C. Fukuda, Prof. Dr. T. Imoto
Faculty of Pharmaceutical Sciences, Kyushu University
62 Fukuoka 812 (Japan)
I. Miyamoto. Dr. H. Kato, Prof. Dr. Y. Taniguchi
Department of General Chemistry, National Kurume
Technical College, Komorino, Kurume (Japan)
-
480 -
-
482
-
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equivalence, structure, synthesis, dioxide, annulene, bridge, possessive, kekul, oxygen
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