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Attempted Preparation of 7 8 15 16-Tetradehydrodinaphtho[1 8-ab; 1 8-fg]cyclodecene.

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cule, the formation of (2 ) as an intermediate should involve
a racemization as well as a novel rearrangement of the
( l b ) . Experiments t o settle this
carbon skeleton ( l a )
question are in progress.
+
[Z 718a IE]
Received: February 20 and February 27, 1968
German version: Angew. Chem. 80,240 (1968)
[*I Prof. Dr. H. A. Staab and Dip1.-Chem. E. Wehinger
Jnstitut fur Organische Chemie der Universitat
69 Heidelberg, Tiergartenstr. (Germany)
[I] We recently reported on unsuccessful attempts to prepare ( I )
by another route: H . A . Staab, H. Mack, and E. Wehinger, Tetrahedron letters, in press.
[2] G . Wittig, G. Koenig, and K . Clauss, Liebigs Ann. Chem. 593,
127 (1955).
[3] Cf. G. Briegteb in Houben- Weyl: Methoden der Organischen
Chemie. 4th Edit. Thieme, Stuttgart 1955, Vol. III/l, p. 545.
[4] We thank Dr. B. Schrader, Institut fiir Spektrochemie Dortmund, for recording the Raman spectrum.
Attempted Preparation of 7,8,15,16-Tetradehydrodinaphtho[l,8-ab; 1,8-fs]cyclodecene
By H . A . Staab, A . Nissen, and J. Ipaktschi[*I
In connection with investigations of intramolecular interactions between triple bonds [1*21, our interest became
1,S-fg]centered o n 7,8,15,16-tetradehydrodinaphtho[l,8-a6;
cyclodecene ( I ) , whose triple bonds should be even more
rigidly fixed in a paraliel arrangement than those of 1,sdiethynylnaphthalenes 111. This should particularly favor
overlapping of the in-plane TC electrons, which in the extreme
case would lead to a cyclobutadiene system (2) with rehybridized u bonds.
It appears that compound (4)is formed from ( I ) , which is
not stable under the conditions of reaction, for the presence
of compound (4) was also established during an attempt to
prepare ( I ) by coupling of the dicopper compound of 1.8diethynylnaphthalene ( 5 ) with 1,s-diiodonaphthalene. Compound ( 5 ) . m.p. 75 "C, was obtained in very good yield from
1,s - divinylnaphthaleneI51 viu the tetrabromide (m.p.
127-129 "C) after dehydrobromination with potassium
tert-butoxide in tetrahydrofuran.
The reactions of compound (5) also evidence special intramolecular interactions between the spatially proximate
triple bonds. Thus hydrogenation with Lindlar catalyst
gives predominately (50 % yield) 1.2-dimethylacenaphthylene
(6). Evidence for the intermediacy of 1,2-dimethyleneacenaphthene (7) was obtained when (7) was trapped during
hydrogenation of (5) (Lindlar catalyst, tetrahydrofuran) in
the presence of maleic anhydride as the 1 : l adduct (m.p.
191-195 "C, 30 % yield 161.
Received: February 20, 1968
[ Z 718b 1EJ
German version: Angew. Chem. 80,241 (1968)
[*] Prof. Dr. H. A. Staab, A. Nissen, and Dr. J. Ipaktschi
Institut fur Organische Chemie der Universitat
69 Heidelberg, Tiergartenstr. (Germany)
1-Ethynyl-8-iodonaphthalene ( 3 ) , m.p. 75-76 O C . was
obtained from 8-iodo-1-naphthoyl chloride 131 via l-acetyl-diodonaphthalene and 1-(1-chlorovinyl)-8-iodonaphthalene.
However, coupling of the copper compound of ( 3 ) in pyridine
(8 h, 115 "C) yielded not ( I ) . but a compound (yield 50 %)
containing two more hydrogen atoms that was identified
as zethrene (4) (41.
226
[I] J. Ipaktschi and H. A . Staab, Tetrahedron Letters 1967,4403.
121 H, A . Staab, H. Mack, and E. Wehinger, Tetrahedron Letters,
in press; H . A . Staab and E. Wehinger, Angew. Chem. 80, 240
(1968); Angew. Chem. internat. Edit. 7, 225 (1968).
[3] H.Goldstein and P. Francey, Helv. chim. Acta 15, 1362 (1932).
141 E. Clar, K . F. Lang, and H . Schulz-Kiesow, Chem. Ber. 88,
1520 (1955); we thank Professor Clar, Glasgow, for an authentic
sample of compound ( 4 ) .
f5] J . K . Stille and R . T. Foster, J. org. Chemistry 28,2703 (1963).
[6] R . H. Mitchell and F. Sondheirner, who recently also reported
the synthesis of ( 5 ) [Tetrahedron 24, 1397 (1968)], obtained
1$3-diethylnaphthalene and 1,8-diethyltetralin on hydrogenation
of (5) with platinum catalyst in acetic ester.
Angew. Chem. internat. Edit.
1 VoI. 7 (1968) 1 No. 3
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