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An Explosion of Tropylium Perchlorate.

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its composition, and its IR, UV, and HI-NMR spectra.
On complex formation, the C=O band of tocoquinone
The infrared spectrum of the 2,2-dimethyltriazanium ion
shows a striking similarity with that of the tetramethylammonium ion [2]. Some bands can be assigned to the NHzgroups.
The corresponding oxalate, as well as tetraphenylborate,
were prepared from (11). The borate is difficultly soluble
in water. A salt of composition [CSH~N(NHZ)Z][CSH~ONHNH21S04 was obtained from N-aminopiperidine and (I).
Received, May 21st. 1962
is displaced by 114 cm-1 from 1647 to 1533 cm-1 and
bands at 779, 824, and 860 cm-1 characteristic of symmetrically x-complexed cycloocta-1,S-diene appear. The UV
spectrum closely resembles that of cycloocta-1,5-diene-Ni(O)duroquinone. In the proton resonance spectrum, the signal
due to the four olefinic protons of the x-complexed cyclooctadiene appears at T = 2.28, while that due to aliphatic
protons of the diene is found at T = 1.90 (40 x 106 cps). The
remainder of the NMR spectrum resembles that of DL-a-tocoquinone. The compound, which is stable in air for considerable periods, is soluble in benzene, halogenated hydrocarbons, alcohols, ethers, and acetone, but is insoluble in water.
It is the first well-defined x-complex of a transition metal
with a natural product; in view of the possible carcinogenic
properties of nickel, the physiological evaluation of (I), which
is in progress, promises to be of considerable interest.
Received, May 21st. 1962 [Z 289/120 IE]
111 Part 4 of a series on complexes of the bis-duroquinonenickel(0) type. Part 3 : G. N . Schraurer and H . Thyret, Z. Naturforsch. 176, 73 (1962).
(21 G. N. Schrauzer and H. Thyret, J. Amer. chem. SOC.82, 6420
(1960); Z. Naturforsch. ldb, 353 (1961). - Interaction of D L - a tocoquinone and nickel carbonyl yields paramagnetic, salt-like,
insoluble compounds incorporating divalent nickel (as in the
reaction product of benzoquinone and nickel carbonyl).
2,2-Dialkyltriazanium Salts
By Dr. R. Gosl
Institut fur Anorganische Chemie
der Universitat Erlangen-Niirnberg (Germany)
1,I-Dialkylhydrazines form quaternary ammonium salts
with hydroxylamine-0-sulfonic acid (I); these salts contain
the triazane structure:
R
H2N-N
I
I
R
R
+ H2NOSOI
18
+ HzN-N-NHz
1.
SO?
I
R
The amination of the hydrazine nitrogen provides a route
into the still little explored class of “paraffin aza-compounds”
and suggests that, in the Raschig synthesis, the oxidative
destruction of hydrazine or mono-substituted hydrazine by
the acid (I) or monochloramine also takes place via amination [l].
The colourless and crystalline 2,2-dimethyltriazanium sulfate
[(CH&N(NHz)&SO4 (II), obtainable from 1,l-dimethylhydrazine with yields of 70-80 %, is stable up to approximately 115 “C. A dilute aqueous and neutral solution is
stable at room temperature, whilst the action of alkali or
acid results in rapid decomposition. Ag(NH&+ is reduced
only after a certain time or on heating. On the other hand,
free iodine is quickly liberated from acidified iodide solution.
8
RrN(NHd2
8
+ 3 H8+ 2 I0+ Iz + R z8N H - N H ~+ NH4
This reaction makes possible the simple determination of the
triazanium portion of such salts.
Angew. Chem. internat. Edit.
Vol. 1 (1962) No. 7
[Z 284/118 IE]
111 Cf. R. G o d and A. Meuwsen, Chem. Ber. 92, 2525 (1959);
J. W. Cahn and R . E. Powell, J. Amer. chem. SOC.76,2565 (1954).
121 F. Nerdet and W. Lehrnann, Chem. Ber. 92, 2460 (1959).
An Explosion of Tropylium Perchlorate
By Dr. P. G. Ferrini and Priv.-Doz. Dr. A. Marxer
Forschungslaboratorien der CIBA Aktiengesellschaft,
Pharmazeutische Abteilung, Base1 (Switzerland)
A chemist was seriously injured, and a laboratory assistant
dangerously wounded, by a violent explosion of tropylium
perchlorate. This compound has been described frequently
in the literature and is often used as a starting material for
syntheses. After normal reactions on a 0.1 molar scale, a
larger amount (80 g.) was being transferred into a roundbottomed flask via a powder funnel. It was intended to push
the compound that had heaped up in the funnel through the
relatively wide mouth of the funnel using a glass rod. On
coming into contact with the glass rod (static electricity?),
the tropylium perchlorate detonated. The force of the explosion shattered the bench-top and broke solvent bottles
stored beneath it. The spilt solvents caught fire. A paper by
A. P. ter Borg et al. (Shell Laboratoires, Amsterdam) [l],
received after the explosion, mentions the explosive nature of
tropylium perchlorate in the experimental section. Since this
unobtrusive notice, based on observations by A. Dreiding
(University of Zurich), might be overlooked, we consider it
essential to draw attention to the dangerous nature of this
substance.
Received, May 25th. 1962
[Z 292/123 IE]
[I] Rec. Trav. chim. Pays-Bas 81, 164 (1962).
J3-Asp1,Vals-HypertensinII, a Hypertensin
Analogue of Extremely High Biological Activity
By Dr. B. Riniker, Dr. H. Brunner [l], and
Prof. Dr. R. Schwyzer
Pharmazeutische Abteilung, Forschungslaboratorium der
CIBA Aktiengesellschaft, Base1 (Switzerland)
Acid hydrolysis of A3p(NH;?)1,Vals-hypertensinI1 (A) results
in a good yield of Vals-hypertensin I1 (Vals-angiotensin 11,
B) [2]; an analogous reaction occurs on heating in aqueous
solution [3]. Detailed study of the preparative value of this
latter reaction has shown however that it yields appreciable
amounts of an isomeric octapeptide D in addition to product
B and the heptapeptide C. None of the solvents studied by us
were capable of distinguishing D from B by either thin-layer
or paper chromatography. Separation was achieved, however, by using basic eluents on aluminum oxide layers, or by
electrophoresis on a carrier at either pH 2.1 or 9.1.
Quantitative separation of D from B was achieved by means
of chromatography on neutral A1203, using methanol/2 Mammonia ( l : l , v/v). Analysis of the products of digestion
with trypsin indicated the constitution of compound D. These
products were the hexapeptidc (E) and the dipeptide (F); the
latter was identified bp comparison with a synthetic prepara-
405
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