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Hetero[17]annulene Dioxides and [16]Annulene Dioxide Prepared by Using Furan as Building Blocks.

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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
-
All of the heteroannulenes thus obtained were clearly dia-
with a benefit r.f t h e Setter electron doncr qroup ( i d t i ) .
tropic, Since the chemical shifts of those outer protons
This consideration leads to a conclusion that the twisted
A_ , 4
_ and 2-
were downfield shifted and of those inner protons were up-
perimeters of
field shifted, as compared with the atroprc model, dihydro-
currents.
118lannulene dioxide L (X= -CH2-CI12 -in &) 12' [see Table T I ] .
to the excessive bridging groups.
do not Guench the diamagnetic ring
The lack of diatropicity in 9
- is >resumably due
The relative magnitudes of these changes rn both directions
Isomerization i-5 occurred by heating or most sinply by acid
l A 6 = H-11 - H-10) clearly show the diamagnetic ring current
catalysis (CF3COOD, 'li-N?lR spectroscopy) .
--
Back-isomeriza-
.iecrensed ln the order5->4>1
- [ A d = 4.36, 3.51 and 1.54 ppm in
tion via protonated species g+-=+
w a s unsuccessful.
-5 . 2 and 2, respectively]. confirming
-
this respect, thlall7lannulene system cannot form a chemical
that diatropicity de-
creased with the decreasing availability of a pair of
electrons on the heteroatom.
more planar conformation than
It appeared t h a t z a d o p t s
5
by putting the heteroatom
compared with that
5 and
of didehydrothia[171 a n n ~ l e n e s ' ~ ~ ,
despite of twisted perimeters of
-
2 and 4.
Thia[l7lannulene
9 sustains no ring current, in spite of its planarrty'51.
The value obtained from
2
in 11Slannulenone dioxide161 a s a model of the H+ punping
cycle of bacteriorhodopsin[
.
The structure of - was confirmed by 'Hf 1s more pronounced as
( A 6 = 4.36 ppn) 1s considerably
large, when one reminds that the corresponding value A ?
obtained from lH-azail7lannulene S i 3 ] (X= WHI 1s 5 ppm
In
cycle, made up of four sequential ste?s, as it was realized
a
towards outside of the ring.
The diatropic character of
_ -
data [see, Fig. 11.
and 13C-NMR spectral
The observed very lob field resonances
of the inner protons (2H. t17.18 ppm) and the high field
Yesonances of the outer protons (10H. 64.40- 4.93ppm) confirmed t h a t6 is strongly paratropic.
Although the high-
temperature 'H-NMR spectrum (lSODC, in DMF-d7) showed broadeninijs.
the spectrum was essentially unaffected.
The
-
observed conformational rigidity of d m a k e s a marked contrast with the mobile character of isomeric [16lannulene dioxide
-
'I,
in which averaging of the chemical shifts of
the central trans-double bond dces occur
even at -6O'C
due
to the structural equivalence of the interconvertlng forms.
Electronic spectrum of g w a s closely similar i n broader
bands appearing hnax
at 278 and 530 nm to that of Llblann-
ulene itself, indicating that&
-
Table 11.
483
-
-
NMR Spectral Data of 3 , 4 and 2 ( 6 values. i n
CDC13 at 100MHz. TMS as internal standard)
is a 1 6 n bond alternant
485
-
system
w,,
Finally, it can be mentioned that furan ring can serve as a
H-
7.48d
Jg ,9=12
H- 9
7.2-7.3m
acetylenic bond-for
H-10
3.3aq
J9,10=12
J10.11'16
twisted heteroannulenes as well as of [4n+2]- and (4nlannu-
nice building block-even
more suitable in some cases than
the ring current determinations of
lenes.
H-7)5 17.18
4
( J =16 H )
1
6 17.5
AA=IH -H
)
11 10
=4.36 ppm
A6'IHl1-Hlo)
=3.51 ppm
S 5 = IHl1-Hlo)
16=(H9 -HlO)
=3.82-3.92 ppn
dZ'(H9
:.*= ( H
9 -50)
=1.14-1.24 w p m
= 3.20 ppm
- 484 -
=1.54 ppm
5 5.0
17.0
45
Fig. 1 'H-NMR Spectrum of [16]annulene dioxide
CDC13 at 30'C (100 MHz)
-
486
-
a in
40
References
X r c h bie Adcition anionischer Kucleop3ile X- an das 3 r b i n -
[l] W. Wagemann,
!:ohlenstoffaton
M. Iyoda, H.M. Deqer, 3. Sombroek, and
E. Vogel, Anqew. Chem. 90 ( 1 9 7 8 ) 9 8 8 : Angew. Chem.
internat.
Engl.
_
_ _ _Ed.
__
_ 17 ( 1 9 7 8 ) 956.
[ Z ] H. Ogawa, C. Fukuda, T. Imoto, I. Miyamoto, Y. Taniguchi,
T. Koya, and Y. Nogami, Tetrahedron Lett. 23 ( 1 9 8 3 ) 1 0 4 5 .
13] a ) C.
b)
:5.
S c ! > r b 3 e r , E r e and A p p l . Chem.
Rtitteie, G. ~
3
(1975)
=
kationincher Carbin-Komplexc [ (CC) I.;C\TLt2]BP4
Cr, !;I) gelingt es, zahlreiche A2inocarben-Komplexe des
zu synthetlsleren, die auf dim l e r k o m -
Typs (cO),!~:[C(lZ3,,)X]
iichen direkten ‘Weg oit nicht zuzjnglich sin6 / 2 , 3 / .
Werden die gleicnen Carbln-Koaplexe aber mit starY reduzie-
925:
~ and~ G. 1Schroder,
,
Chem. Ber.
(n
111
11978) 04.
J.M. Brown and F. Sondheimer, Anqew. Chem. 86 ( 1 9 7 4 )
3 4 6 : Angew. Chem. internat. Ed. Engl. 13 ( 1 9 7 4 ) 3 3 7 .
( 5 1 T.N. Cresp and M.V. Sargent, J. Chem. SOC. Perkin I 1973
141
1786.
I. Mlyamoto, H. Kato and
Y. Taniguchi, Angew. Chem.
(1983) 2 4 4 ; Angew. Chem.
internat. Ed. Enql. 22 ( 1 9 8 3 ) 253;. Angew. Chem. S u e p l .
renden Nuclecphilen wie den anionischen Organylverbindungen
der 5. Hauptgruppe umgesetzt, konnen zum Teil viillig andere
Fleaktionsprodukte isoliert werden: Durch reduktive Cg4CR--iierknupfung zweier Carbin-Fragmente entstehen die p-Bis(arninocarben)-Komplexe [(C0)5CrCNEt2]2
/5/.
/4/ und [(CO)5WCNEt,],
[ 6 1 ti. Ogawa, T. Inoue, T. Imoto.
1983,
.-
243-253.
Bei der Verwendung sehr stark reduzierender Nucleophile kann
diese reduktive Dimerlsierung zur dominierenden Konkurrenzreaktion gegenuber der Addition des Nucleophils an das Car-
Stoeckenius, R.H. Rozler, and A . Bogomolni, Biochim.
aiophys. Acta 5C! ( 1 9 7 9 ) 2 1 5 ; references cited therein.
( 7 1 W.
181 Reexperiments of our previous report [ti.
and I. Tabushi. Tetrahedron Lett.
t ion.
1973
Oqawa, M . Kubo
in prepara-
3611,
bin-Kohlenstoffatom wcrden. So erhalt man z.B.
(1) mit
setzung von [(C0);WCNEtz]SF4
phid als Hauptprodukt eben den Biscarben-Komplex [(CO) 5YCNBt2],
(2).
Daneben lassen sich bei dleser Reaktion auch die
einkernigen Honocarben-Komplexe
Received June 16,
1981,
revised February 2 8 ,
1983 / Z 418 S /
bei der Um-
Kaliummethylphenylphos-
(2)
(CO)iWIC(Nst,)P~ePh]
trans-(MePhFH)(CO)CWIC(NEt,)PPieFh]
(4) isolieren
Die trans-Pnosphan-’Wolfram-Verbindung
und
/>/.
5 zeichnet sick1 nun
durch die bemerkenswerte Xigenschaft a m , sich beim 3rw5rrnen
in Losung unter Abspaltung von HI’KePh spontan zun neuartigen
cyclischeii Carben-Komplex
-
407
-
-
( ~ c ) ~ C(NEt2)i;Fiei’h]
il[
(5)
489
umzuiagern.
-
Konplex 2 , dessen Struktur spe!<troskopisch, elementaranaly-
Dieses Manuskript ist
zu zitieren als
Angew. Chem. Suppl.
This manuscript is
to be cited as
Angew. Chem. Suppl.
1983,488-500
7983,488- 500
0 Verlag Chemle GrnbH. D-6940 Weinheim. 1983
0721 42271831050504888 42.5010
tisch sowie rontgenographisch bewiesen wurde, ist unseres
Wissens eine der wenigen Verbindungen, in denen ein CarbenLiqand Bestandteil eines dreiqliedrigen Metallacycl2s I S L , der
noch eln weiteres Hauptgruppenelement-Heteroatom enthiilt.
A e soedtroskoyischen Jater, v o n Verbinduce 2 lassen sich
dur.cr! die .)i-HaGtn-Funktion des Aninc(31.osCr.~no)carben-,,igan.’en er’rlaren.
Das 18-Spektrum von
C!12C12:
2214
1 8 6 5 cm-l,
irnst Otto Flscher *, Rudolf Reitmeier und Klaus Ackermann
em-’,
5
1st mit seinen vier Absorptionen (in
s ; 1923 cm-’, vs ;
1917 cm-’, sh ;
s ) im CO-Bereich den eines cis-Tetracarbonyl-
(ph0sphan)carben-Komplexes sehr ahnlich /6/.
Der Fhosphan-
Ligand bewirkt durch sein groRes 6-Donor/T-Akzeptorvermogen
eine starke Verschiebung (ca. 70-60 cm-l gegenuber der entsprechenden Pentacarbonylstruktur / 5 / )
der CO-Banden zu nied-
rigeren Wellenzahlen. Die Lage der C(Carben)-N-Streckschwingung bei 1 5 7 9 cm-’ (KBr-Frebiing) deutet auf partieile %-Bindungsanteile hin.
Dementsprechend findet man im ‘TI-NMR-Spektrum von
* Prof. Dr.
k,.
0. lischer, Dip1.-Chem. R. Reitmeier.
5
erwar-
tungsgemaB eine Aufspaltung der Quartetts und Tripletts der
Dr. K. Ackermann, Anorganisch-Chemisches Institut der
infolge gehinderter Rotation nichtaquivalenten N-Ethyl-Proto-
Technischen Universitxt Munchen, Liohtenbergstr. 4.
nen (13 bzw. 25 Hz). Aucb die Methylprotonen des Phosphino-
D-8046 Garching
Substituenten erscheinen aufgrund einer Phosphor-WasserstoffKopplung uber zwei Bindungen als Dublett (Kcpplungskonstante:
8
112).
Das Signal der Fhenylgruppe am Phosphor wird als
Pseu.io-DJS?ett i r n ,.iblichen3ereich beobachtet.
-
400 -
-
490
-
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