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Constitution and Confliguration of Cycloneosamandione.

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Constitution and Configuration
of Cycloneosamandione [11
3-aza-A-homo-Sa- and -5a-androstunes prepared by Shoppee
and Krueger [4] is therefore understandable.
Rewiwd, JMUW
By Dr. G. Habermehl and Dr. S. GCIttlicher
lnstitut fur Organische Chemie and Eduard-Zintl-lnstitut
der Technischen Hochschule Darmstadt (Germany)
Structures ( I ) and (2) have been considered for cycloneosamandione, an alkaloid isolated from the skin-gland venom
of the fire salamander (Salumundru maculosa Laur.) [2]. The
group in these structures can react tautomerically
’ I
as ‘NH and O<.
30th. 1963
[Z4381267 IB]
[I] Communication No. 10 in the wries “On samandarine and
related alkaloids” begun by C. Schdpf and coworkers; Communication No.9: G. Habermehl, Chem. Ber. 96, (1963). in the press.
This work will be published in full in Chern. Ber.
121 C. Schdpf and 0. W. Miiller, Licbigs Ann. Chem. 633, 127
131 J. F. King and B. Vig, Canad. J. Chem. 40, 1023 (1962).
[4] C. W.Shoppee and G. Krueger, J. chem. Soc. (London) 3641
A Semiaminal of Diiide
By Doz. Dr. Ernst Schmitz, Dr. R. Ohme
and cand. chem. S. Schramm
Institut f i r Organische Chemie der Deutschen Akademie
der Wissenschaften, Rerlin-Adlershof (Germany)
The infrared spectra of two derivatives of this “open” form,
viz. N-acetylneosamandione and N-methylneosamandione
iodomethylate, show that the carbonyl group which takes
part in either an aldehyde ammonia or a ketone ammonia
grouping in cycloneosamandione, is in fact an aldehyde
group. Both compounds give a V-CH + a-CO combination
band characteristic of an aldehyde group 131 at 2.30 p
(4350 cm-1); the v-CH-band of the aldehyde at 3.70 p
(2705 cm-I), on the other hand, is well developed only in Nacetylneosamandione. We have investigated orthorhombic
crystals of cycloneosamandione hydroiodide with X-rays
(lattice constants: a = 10.87 A, b = 9.59 A, c = 19.51 A;
space group P 212121; four molecules per unit cell). A twodimensional electron density projection along the b-axis
indicated structure (3) for cycloneosamandione. The Rifactor was 0.21. This indicates that cycloneosamandione has
the same C,N skeleton as samandarine with the difference
that the @-methylgroup at C-I0 in samandarine is replaced by
an aldehyde group in the a-position in cycloneosamandione.
The arrangement of the C and D rings as well as the absolute
configuration were indicated moreover by the rotatory dispersion curve of cycloneosamandione (strong, negative
Cotton effect at 325 mp).
Formation of diimide on decomposition of hydi oxylamine0-sulfonic acid with alkali has been established [l]. Treatment of hydroxylamine-0-sulfonicacid with cyclohexanone
in alkaline solution at 10°C affords a 44 % yield of a crystalline compound which proves to bc I,l‘-dihydroxyazocyclohexane (2). An iso-oxime ofcyclohexanone (I) occurs as an
intermediate in the formation of (2).
Compound (2) can be regarded as a semiaminal of diimide.
It decomposes rapidly even at room temperature into cyclohexanone, nitrogen, and hydrazine in the proportion 4: 1: 1.
This decomposition proceeds by way of diimide (3): decomposition in the presence of quinone gave hydroquinone
in 49% yield; analogously, azobenzene was reduced to
hydrazobenzene in 55 % yield, the latter being identified as
benzidine [2].
If (2) is stored with access to air at - 15OC, the entire nitrogen
content of the molecule disappears within several days. Di-lhydroxycyclohexyl peroxide (4), m.p. and mixed m.p. [3]
65-66 OCSis isolated in ca. 80 % yield.
Received, January 2nd. 1963
It is thus probable that a steroid with the anomalous configuration at C-I0 has beem found in nature for the fust time.
A three-dimensional structural determination is being performed.
It follows from structure (3) that the neosaman obtained by
WoltT-Kishner reduction of cycloneosamandione by Schopf
and Miiller has the structure (4); its non-identity with the
Angew. Chern. internal. Edir. I Vol.2 (1963) No.3
[Z4241255 I61
[l] Ernst Schmitz and R. Ohme. Angcw. Chem. 73, 807 (1961);
R. Appel and W. Buchner, ibid. 73,807 (1961).
[2] Reductions with diimide: S. Hiinig, If. R. Miiller, and W.
Thier, Tetrahedron Letters 1961,353; E. J. Corey, W. L. Mock,
and D. J. Pasto, ibid. 1961,347; E. E. van Tatnelen et al., J. Amer.
chem. Soc. 83,3725,3729 (1961).
[3] N. A. Milas, S. A. Harriss and P. C. Panagiotakos, J. h e r .
chem. Soc. 61,2431 (1939).
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constitutions, confliguration, cycloneosamandione
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