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Attempted Synthesis of anti-1 6 8 13-Bismethano[14]annulene.

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spectrum (CDC13) shows a broad multiplet (2.45-2.8 T) and
a singlet (2.9 T) for the 20 phenyl protons, and a singlet
(8.29 T) due to the two methyl groups. In CsD6 the CH3 signal
appears at appreciably higher field (8.84 T), and the phenyl
protons give two complex multiplets (2.3-2.6 7 ; 2.6-3.0 T;
ratio of areas 8 : 12) which can be clearly differentiated. The
diamagnetic shift of the CH3 signal of ( 4 ) , which is remarkable in view of T C H ~for ( I ) , may perhaps indicate a
considerable anisotropy effect for the phenyl substituents.
The strongest peak in the mass spectrum[41 is that of the
molecule ion at mje = 434.
The ultraviolet spectrum of ( 4 ) , which shows only slight
structure, is little influenced by the polarity of the solvent:
(acetonitrile) = 334 m p (E = 26500), 300 (26200), and
237 (15800); Amax (cyclohexane) = 336 m!l (E = 23800),
298 (26000). As in the case of the vinylogous 7,8,9,10-tetraphenylsesquifulvalene 161 electrophilic aLtack in CF3COOH
by the proton takes place exclusively at position 1, giving
compound (3), X a = CF3COOo (NMR analysis).
The calicene derivative ( 4 ) is thermally quite stable, but, like
( I ) 171, reacts rapidly with oxygen, giving the allene ketone (6)
whose structure is proved by, inter olio, ultraviolet, infrared,
N M R , and mass spectra: Amax (CHjCN) = 420 m p (E =
2000), 308 (shoulder, 14200), 258 (shoulder, 34800), and
246 (37200); vc=c at 1927 cm-1; vc=c at 1684 cm-1;
2.6-2.1 T (m), 7.84 T (s), and 8.11 T (s) (CC14; ratio of areas
20: 3 : 3). The strongest peaks in the mass spectrum 141 a those
of the molecule ion of ( 6 ) (m/e = 450), of (6)-tolan (272),
and of tolan (178).
Received: April 2 1 ~ 1 ,1966
IZ 211 IE]
German version: Angcw. Chem. 78, 642 (1966)
[!] Laboratoire dc Chimie organique de i'UiiiversitC de Lausannc
(Sw i tzer laud).
[2] H . Pri/i:boch and U . Fisclier, Aii~e..b.Chc-n. 77, 621 (1965);
Angew. Chem. internat. Edit. 4,598 (1965).
[3] A. S. Ken& and P .T . 1::0, J. Amer. chem. SOC. 87, 4162
(1965); I Y . M . Jams and X. S. Pj.r0/7, ibid. 87, I608 (1965);
M . Uciio, 1. Mio.afc/, and Y . Kitn/icrrer, Tctrahzdran Letter; i965,
2967; E. D . Berguiniin and 1. A-rnmf, Chcm. Corn:nm. 21, 512
(1965).
[4] We t h a n k Dr. /I. A c l r e n b c d (Uni\;xit;it Freiburg) Tor tk.e
mass-spectrometric measureaents.
[S] H . Priiizbncli, D. S i p , and U . F i s c l i r r , Angcw. Chcm. 77,
258 (1965); Angew. Chr:n. Internat. Edit. 4 , 242 (1955).
[6] H . Pritr-hoch, D . Seip, L.. / ( l i ~ f / i ~ .and CY. Foirst, Li3bigs
A n n . Chcm., i n press.
[7] H . Priri.:bnr/r and 17.
Fisrlier, Chimia 20, 156 (1966).
Attempted Synthesis of
anti-l,6 :8,13-Bismethano[14lannulene
By Prof. Dr. E. Vogel, Dr. M. Biskup, cand. chem. A. Vogel,
cand. chem. U. Haberland, and Dipl.-Chem. J. Eimer
Institut fur Organische Cheniie, Universitiit Koln (Germany)
2,7,15,16-Tetrahydro-trons-l5,16-dimethylpyrene
(f) can be
readily deh!drogenated
to 15,16-dihydro-trons-15,16-dimethylpyrene (2), a [14]annulene uitli aromatic properties [il.
Whereas (2) has an almost planar c 1 4 perimeter, planarity
of the outer cI4 skeleton of the analogous onfi-1,6:8,13-bismethano[l4]annulene (3) could be achieved only at the cost
of appreciable bond-angle deformation, mainly of the
C-CH2-C angles. Compound (3) might thus be a n olefinic
pendant to compound (2).
We describe below the synthesis of 7,14-dihydro-nnri-8,13bismethano[l4]annulene ( S ) , corresponding to ( I ) , and some
of its reactions.
1,4,5,8,9,10-Hexahydroanthracene (4) 121 served as starting
material. It was prepared by reduction of 9,lO-dihydroanthracene with lithium in methylamine 131. Addition of a
C1,CI
(4)
(5)
CIAC1
(7)
(9)
cyclopropane ring to the skeleton of ( 4 ) by means of dichlorocarbene [41 (obtained by thermal decomposition of
sodium trichloroacetate in 1,2-dimethoxyethane151) led,
when the components were used in molar ratio 1:4, t o the
diadduct (5) (40 %), m.p. 262-263 "C, whose N M R spectrum
showed a weakly split singlet at T = 4.6, a multiplet at T =
7.65, and a sharp singlet at 7 = 7.75 (proton ratio 4: 12). I n
favor of carbene addition in the anti-position is the finding
that the resonances of the four middle CH2 protons always
appear as a singlet in the N M R spectra of compound (5) and
the products (6) and (8) obtained therefrom (occurrence of a
symmetry center) [61. Compound (5) is converted by lithium
and t-butyl alcohol in tetrahydrofuran into the hydrocarbon
( 6 ) (90 %), m.p. 29 OC,which takes up two mo!es of bromine
in methylene dichloride at -75'C with formation of (7)
(84 %), m.p. 129-130 "C (dccomp.) (probably a mixture of
isomers). When the tetrabromide is treated with methanolic
m.p. 147-14SoC, is
KOH, the hexaene (8) (50-55
formed directly with loss of four moles of HBr and opening
of the three-membered ring. The structure of this hydrocarbon follows from its N M R spectrum: it consists of an
A A ' X X system at TA = 3.6 and TX = 4.0, a broad singlet
at T 7s 6.6, and a n AB system at TA = 7.27 and TB = 8.54
(J = 11.5 cps) (8:4:4). The ultraviolet spectrum contains
maxima at ?. =-= 221 nip (E = 41500) and 258 m p (8400) in
cyclohexane.
In remarkable contrast to the ready dehydrogenation of ( I ) ,
attempts to convert (8) into ( 3 ) by use of noble-metal dehydrogenation catalysts or 2,3-dichloro-5,6-dicyano-1,4benzoquinone were unsuccessful. Selenium dioxide in
dioxane / water oxidizes (8) at the allylic CH? groups of the
pcripheral ring, giving a mixture consisting in the main of a
monohydroxy, a monooxo, and a hydroxyoxo compound.
The colorless monoketone, m.p. 165-166 "C [ultraviolet
spectrum: maxima at 213 (F ~=30500), 217 (31000), and 268
nip (11900), with a shoulder at 315 my (4500), in cyclohexane], gives an N M R spectrum containing two complex
groups of signals at T = 3.2 and 7 = 3.7, a broad singlet at
7 = 6.4, and an AB system at TA
7.26 and TB =: 8.55 with
J =: 12.5 cps (6:2:2:4); it thus has structure (9). This compound is a potential hydroxy derivative of the [14]annulene
( 3 ) ; with potassium t-butoxide in dimethyl sulfoxide or
tetrahydrofuran it gives intensely reddish-violet solutions,
which are still under study.
z),
7
Further oxidation, by chromium trioxide in pyridine, of the
hydroxyketone obtained from (8) leads to a diketone, m.p.
Augen.. Clzeni. iiiteriicit. Edit. ,' Vol. 5 (1966)
/ No. 6
603
299-300°C [ultraviolet spectrum: A,,
= 252 (E = 25500)
and 292 m p (9200), in dioxane]; its N M R spectrum has only
an AABB' system, centered at T = 3.05, and an AB system
at TA = 6.87 and TB = 8.43 (J = 13.5 cps) (8:4), so that
structure (10) must be ascribed to it. Since this product is
Cl"C1
A
(11)
(10)
0
colorless, and, as far as established, has no pronounced
oxidizing capacity, it cannot be regarded as a quinone, in
contrast to the yellow 15,16-dihydro-trans- 15.16-dimethyl2,7-pyrenedione (11) [81. The main reason for this difference
between (11) and (10) is doubtless to be sought in the
steric hindrance to conjugation present in the latter.
Received: M a y 16th, 1966
[Z 236 lE]
German version: Angew. Chem. 78, 642 (1966)
[ I ] V. Boekelheide and J . B. Phillips, Proc. nat. Acad. Sci. U.S.A.
51, 550 (1964).
[2] J. Runge, Z. Chem. 2, 374 (1962); A . J . Birch, P . Fitton,
D . C. C. Smith, D . E. Steere, and A . R . Stelfos, J. chem. SOC.
(London) 1963, 2209.
[3] Reduction of 9,lO-dihydroanthracene to (4) has meanwhile
also been studied by Prof. R . G. Harvey, University of Chicago
(personal communication).
[4] Reaction of (4) with methylene diiodide (molar ratio 1:3)
and a zinc-copper couple in a Simmons-Smith reaction gives a
complex mixture of cyclopropanation products, from which the
rnonoadduct, 1,4,5,8,9,10-hexahydro-4a,9a-methanoanthracene
(25 %), mp. 55-56 "C, can be isolated.
[5] W . M . Wagner, H . Kloosterziel, and S. van der Ven, Recueil
Trav. chim. Pays-Bas 80, 740 (1961).
[6] The dipole moment of (5) is less than 0.3 D.
[7] P . Bruck, D.Thompson, and S. Winstein, Chem. and l n d .
1960, 405.
[S] V . Boekelheide and J . B. Phillips, J. Amer. chem. SOC.85,
1545 (1963); F. Gerson, E. Heilhronner. and V . Boekelheirle,
Helv. chim. Acta 47, 1123 (1964).
Tricyclo[4.3.1.0196]deca-2,4,7-triene,
an Acidic Alicyclic Hydrocarbon
By Dr. W. Grimme, M. Kaufhold, U. Dettmeier, and
Prof. E. Vogel
Institut fur Organische Chemie, Universitat Koln (Germany)
The existence and aromatic character of the neutral or
positively charged lox-electron systems 1,6-methanocycloand bicyclo[5.4.l]dodecapentaenylium
decapentaene (1)
cation (2) I21 suggested a n attempt at synthesis of the bicyclo[4.3.l]decatrienyl anion (11) [31, the negatively charged
analogue of compound ( I ) and cation (2). If the anion is
stable it should be produced by sufficiently strong bases from
tricyclo[4.3.1.0~~6]deca-2,4,7-triene
(9), which can be regarded as the stabilization product of 1,6-methano-1,3,5,7cyclononatetraene (lo).
For the preparation of the hydrocarbon (9) we started from
4,7-dihydro-2-indanone ethylene ketal ( 3 ) [41. This takes up
dichlorocarbene (generated from chloroform and potassium
t-butoxide) preferentially at the nucleophilic central double
bond, whereby the product ( 4 ) , m.p. 97-98"C, is formed
(30 %). This can be nearly quantitatively reduced by sodium
in liquid ammonia to compound ( 5 ) , b.p. 71-72°C/0.4 mrn,
n20 - 1.5085. Compound (5) is converted into the ketone (6)
,
[56%; m.p. 99-100°C;
N M R spectrum: A2B2 system
centered at T = 4.0 (4); doublet at T = 7.48 (4); and AB
system at T = 8.6 and 9.9 (2) with J = 5 cps], by reaction
with bromine (0 "C, CHZCI~),dehydrohalogenation of the
dibromide with ethanolic NaOCzHS, and hydrolysis of the
diene ketal produced by HCI in tetrahydrofuran, yields being
increased if the intermediates are not isolated. The ketone is
then converted into the oxime, m.p. 77-78 "C (80 %), which
is reduced by LiAIH4 to the corresponding amine (according
to the N M R spectrum a mixture of the two stereoisomers)
which is exhaustively methylated by methyl iodide and
potassium carbonate in methanol; the yield of quaternary
ammonium iodide calculated on (7) is 39 %. Hofmann
degradation of the base (8) prepared from the iodide with
silver oxide yields, finally, a 57 % yield of the norcaradiene
hydrocarbon (9), free from isomers, as R colorless liquid, b.p.
65-66 "C/14 mm, n: = 1.5470. The N M R spectrum of the
hydrocarbon shows a multiplet at T = 3.6-4.4 (51, a double
triplet at T = 4.8 (l), a quintuplet at T = 7.4 (2), and an AB
system at T = 8.6 and 10.0 (2) with .I = 3.0 cps. The ultravioletspectrum (in cyclohexane) has a double maximum at A =
260 m p ( E --= 3100) and 270 m p ( E
3100), in excellent
agreement with that of tricyclo[4.3.1.01,6] deca-2,4-diene [51.
Catalytic hydrogenation (PtO2 in ethyl acetate) gives mainly
tricyclo[4.3.1.01~6]decane151; the compound adds maleic
anhydride even in the cold (m.p. of adduct 105-106'C).
i
Compound (9) is not sufficiently acidic to exchange hydrogen for deuterium in CH3OD/CH30Na at room temperature. However, with sodium niethylsulfinylmethylide
(CH3SOCHzeNa@)[61 in [Dsldimethyl sulfoxide a brownishred solution is formed at once, in whose N M R spectrum the
following signals appear: a double doublet at T = 3.2 (2), a
and an AB system at 7 = 10.7
multiplet at T = 4.0-4.6 (9,
and 11.2 (2) with J = 7.5 cps. The changes from the spectrum
of the hydrocarbon ( 9 ) , and in particular the shift ofthe signals for the bridgehead protons to higher field and the increase
in the geminal coupling constant from 3.0 to 7.5 cps. indicate
formation of the bridged cyclononatetraenyl anion ( I I) and
the presence o f a ring current in the Cg perimeter. On addition
of an excess of ( 9 ) to the solution of sodium niethylsulfinylmethylide in [Dhldimethyl sulfoxide the spectrum of the
hydrocarbon appears together with that of the anion. It is
thus shown that (9) is converted completely into (11) by the
base, and that the N M R spectrum observed is not due to
rapid proton exchange between ( 9 ) and (11). Introduction
of deuterium into (11) by [Dsldimethyl sulfoxide at room
temperature was not observed. If the solution of (11) in
dimethyl sulfoxide is added to an excess of D20 a 45 7;
yield of compound (9), which is 91 % deuterated at position
9, is obtained.
R e c i v e d : May loth, 1966
[Z 235 IE]
German version: Angew. Chem. 78, 643 (1966)
[I] E. Vogeland H. D. Rotlr, Angcw. Chern. 76, 1-15 (1963); A n gcw. Chem. intcrnit. Edit. 3, 228 (1954); €. Vogel m d 14'. A .
Boll, Angew. Chem. 76, 784 (1964); .\ngew. Ch2.n. intcrn3t.
Edit. 3, 642 (1964).
[2] W. G t ' i ~ n CH.
, H o f f ; ~ 7 i r nand
,
E. Vogtl, Anpew. Chc,ix 77.
345 (1965); Angew. Chem. internal. Edit. 4 , 354 (1965).
Angew. Clieni. intermit. Edit. , Vol. 5 (1966) / No. 6
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