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N-bromosuccinimide or dibromodimethylhydantoin on (2)
[4] and subsequent treatment with pyridine (yield c a . 1 5 04).
Accordingly, the so-called "pentatetraene" has the constitution (3) of tetra-(P,P-diphenylvinyl)ethylene, in agreement
with its N M R spectrum, molecular-weight measurements,
and other results.
(CsH5)2C==CH CH ~CH-C(CaH5)z
CH -C(CaH&
So far, all attempts to prepare genuine pentatetraenes have
resulted in ring-closure to yield derivatives of indene [ I ] or
dimerisation with or without partial hydrogenation.
Received, April 29tI1, 1963
[Z 492/325 IE]
German version: Ang-w. Chem. 75,452 (1963).
[I] Communication No. X V on Cumulenes; Communication
No. X I V : R . Kuhn and B. Schulz, Angew. Chem. 74,292 (1962);
Angew. Chem. internat. Edit. I , 211 (1962).
[2] F. Rohlmann and K . Kieslich, Abh. braunschweig. wiss. Ges.
I 9 5 7 , I X . 147.
[3] G. Mavin, Thkse Ingenieur Docteur, Paris 1960. See also: P .
Cadiot, W. Chodkiewicz, and J . Rams-Godinenu, Bull. SOC.chim.
France 1961, 2176.
[4] G. Witri,q and R . Ohermann, Ber. dtsch. chem. Ges. 68,2214
(1935). The structure given there is in agreement with the NMR
spectrum of (2) and its conversion by us into the octahydro compound (m.p. 181 "C).
Cobalt(I1) Cyanide, its lhree-dimensional Framework Structure and Zeolitic Compounds
By Prof. Dr. Arniin Weiss and cand. chem. W. Rothenstein
Institut fur anorganische Chemie der Universitat Heidelberg
The flesh-colored, hydrated form and the deep blue, anhydrous form of Co(CN)z both yield identical X-ray diagrams
indicating a cubic structure with a cell parameter of 10.12 A.
Since the hydrated form contains up to about 3 moles of H20
in the interior of the crystal, there must be large cavities
present in anhydrous Co(CN)>.
This is supported by its ability to form inclusion or zeolitic
compounds with a wide range of polar compounds X such as
n-alcohols, nitriles, aldehydes, carboxylic acids, amines, aryl
halides, e t c . These zeolitic compounds are characterized not
by a fixed molar ratio of Co(CN)2: X, but by a constant vol.
30 ml of each can be abume ratio V C ~ ( C N ) ~ : V XAbout
sorbed per mole of anhydrous Co(CN)z. The formation of
zeolitic compounds can readily be explained by reference to
the crystal structure of Co(<'N)z. It exists as a three-dimensional, coarse-meshed framework of Co(CN) -3 (Fig. 1).
By Prof. Dr. G . Wittig and Dr. G. Steinhoff
lnstitut fur Organische Chemie der Universitat Heidelberg
Following the synthesis of benzoazatriptycene [l], we have
now succeeded in preparing azatriptycene ( I ) in another way.
By application of the synthesis principle of ring-closing a dehydrobenzene intermediate [2], the compound ( I ) , m.p.
266-267 "C, is obtained in 54 yield by treating 9-o-chlorophenyl-9,lO-dihydroacridine(2) with KNH2 in liquid NH3.
Received, M a y 6th, 1963
[Z 499/328 IE]
German version: Angew. Chem. 75, 575 (1963).
In the case of the analogous preparation of the compound ( I )
from 9-m-chlorophenyl-9,10-dihydroacridine(3), the yield
dropped to 17 "/,. Compounds (2) and (3) were made according to Bernthsen [3] by treating diphenylamine with the corresponding chlorobenzoic acid and subsequent reduction.
Infrared, ultraviolet, and nuclear magnetic resonance spectra
established the structure of ( I ) . The ultraviolet spectrum of
( I ) was, as expected, in complete accord with that of the isosteric compound triptycene [ ( I ) , C H instead of N]; on mixing
( I ) with triptycene (m.p. 256"), no depression of the m.p.
was observed. The formation of the methiodide of ( I ) in
isolated as its tetramethyl iodide at room temperature
phenyl borate, m. p. 289.5 29 I "C (decomp.) - demonstrates
that the amine ( I ) is much more basic than triphenylamine.
Received, May Znd, 1963
[Z 494/327 IE]
German version: Angew. Chem. 75,453 (1963).
[l] G. Witrig and G. Srrinhof, Chem. Ber. 95,203 (1962).
[2] Cf. G. Witrig and L. P o h n ~ e r Chem.
Ber. 89, 1337 (1956);
R . Huisgen and J . Sauer, Angew. Chem. 72, 97 (1960); J. F.
Bunnett, J. chem. Educ. 38,282 (1961).
[3] A . Bernthsm, Liebigs Ann. Chem. 224, 1 (1884).
T o fulfil the conditions of stoichiometry for Co(CN)z, every
second cube contains a Co2' ion. The striicture of Co(CN)2
can therefore be represented as CO[CO(CN)~]-Z.
It cannot be
decided by X-ray analysis whether the Co atoms in the threedimensional skeleton are surrounded alternately by 6 C or
6 N atoms ( i . e . whether [Co(CN)#
occurs) or by 3 C and
3 N atoms together. Molecules whose least van der Waals diameter substantially exceeds 3.6 A cannot penetrate into the
framework. Hence Co(CN), has the properties of a rnolecular sieve.
The structure is similar to those of Fe$+[Fe3'(CN)& and
CO:+[C03+(CN)& [ l , 21. Co(CN)zcan also absorb HCN molecules into the interior of the crystal and thus, o n the basis
of a n analytical Co:CN ratio > I :2, can simulate partial
oxidation of Coz' to Co3 I .
[l] J . F. Keggin and F. D . Miles, Nature (London), 137, 577
[2] A . Vaciago and A. Mugnoli. Accad. naz. Sincei, Rend., CI.
Sci. fisiche, mat. Natur 8, 25. 531 (1958).
A New Synthesis of Fulvenes 111
By Dr. W. Freiesleben
Consortium fur elektrochemische lndustrie GmbH,
Munchen (Germany)
Previously, it was only possible to prepare fulvenes in yields
of 8 0 % at the best by condensing cyclopentadiene or
analogous compounds with carbonyl compounds in the presence of strong alkalis. The products contained considerable
amounts ofresinous impurities.We now useprimaryor secondary aniines as condensing agents. The catalytic activity of the
amines probably results froin their ability to react with carbonyl compounds to form imines or, in the presence of monomeric cyclopentadiene, Mannich bases.
Angew. Chem. intc~rnat.E d i t . I Vol. 2 (1963)
No. 7
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