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Identification of the Subsidiary Steroids from the Prothoracic Protective Gland System of Dytiscus marginalis.

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ma1 at the end of the log phase and in the stationary phase
(24-30 h). The amounts of A P I, A P Il, and A P 111 present in
stearothcrnlopllilus vary according to the strain.
Obligatory thermophilic strains (temperature optimum 55 "C,
no growth at 37 "C) produce much A P I and AP I1 and little
A P 111, whereas obligatory mesophilic strains (temperature
optimum 37 "C, no growth at 55 "C) contain much A P 111 and
very little A P I or A P 11. Facultative strains (growth at 37 OC
and 55 "C) may contain the three aminopeptidases in comparable amounts.
For preparation of the crude enzyme mixture the bacteria
were opened up by ultrasonic vibrations or in a sand mill.
Treatment with lysozyme liberated only A P I1 and A P 111;
A P I seems to be more firmly bound to the cell membranes.
The aminopeptidases were obtained from the culture medium
by adsorption on DEAE-Sephadex (pH = 7.2) and elution
with 1 M NaCl solution (0.05 M Tris-HCI buffer, p H =- 7.2,
10-3 M ~02.1).
[ Z 582 IE]
Received: July 7th, 1967; revised: August Sth, 1967
German version: Angew. Chem. 79, 906 (1967)
[ * ] Dr. H. Zuber and Dr. G. Roncari
Laboratorium fur Molekularbiologie der
Eidgenossischen Technischen Hochschule
Universitatsstr. 6
CH-8006 Zurich (Switzerland)
[I] This work was supported by the Schweizerische Nationalfonds zur Forderung der wissenschaftlichen Forschung (Project
No. 3426).
[2] ATCC 7953, 7954; NCIB 8924, 8157, 8920, 8222.
[3] E . L. Srnifh and 1). H . Spackrnan, J. bioi. Chemistry 212, 271
141 B. J . Davis, Ann. New York, Acad. SCI.121,404 (1964).
Synthesis of Hydridopentacyanoiridate Complexes
shoulder at 364 nm (E = 36) [()I. In DzO, there is a IH--NM R
signal at X =:- +1730 Hz (reference signal: HDO) or T 23.9
ppm 151, as expected 121. All known data confirm CJ, symmetry
for the complex.
Prcpurufion: 3.25 g (50.0 mmole) of KCN is dissolved in
200 ml of water-free C H 3 0 H and then 1.94 g (5.00 mmole) of
Ir(CoH&CI or 1.96 g of Ir(C6Hl&Ci is added. The yellow
color of the solution disappears within minutes. Olefin,
together with CH30H, is driven off from the solution by
distillation. Methanol must be added t o the solution during
the distillation until all the liberated olefin has been removed.
Within 3 h the desired complex separates from the solution
as a white, finely crystalline mass, which can be dried under
vacuum (yield 85 04).
Received: July 21st, 1967
[Z 583 IE]
German version: Angew. Chem. 79, 902 (1967)
[ * ] Priv.-Doz. Dr. K. Krogmann and Dip1.-Chem. W. Binder
Ldboratorium fur anorganische Chemie der
Technischen Hochschule
Schellingstr. 26
7 Stuttgart-N (Germany)
[I] W. P. Griffifh and G . Wilkinson, J. chern. SOC.(London)
1959, 2757.
[2] M . L. H . Green and D . J . Jones, Adv. Inorg. Chem. and Radiochern. 7, 165 (1965).
[3] D.N . Lawson, M . J. Muys, and G. Wilkinson, J. chem. SOC.
(London) A 1966, 52.
[4] G. Winlchaus and H . Singer, Chem. Ber. 99, 3610 (1966)
[ 5 ] Thanks are due to Prof. C . Laukien (Karlsruhe) and Mr.
T . Keller for recording the NMR spectrum.
Identification of the Subsidiary Steroids from the
Prothoracic Protective Gland System of
Dyiiscus marginalis 11,*1
By K. Krogmann and W. Binder[*]
Suggestions that complexes of the type [MH(CN),]3- (M =
Co, Rh, Ir) exist in solution [Is21 have been questionedC31
since, hitherto, such compounds have not been successfully
isolated. We have now been able t o prepare iridium compounds of this type by reaction of bis(l,3-cyclohexadiene)iridium chloride[4], Ir(C6H&Cl, or bis(2,3-dimethylbutadiene)iridium chloride, IT(C&&CI,
with excess K C N in
CH30H :
Ir(C6H&Cl+ 5 KCN CH30H
+ K3[IrH(CN)5]
+ KCI + KOCH3 + 2 Cf&.
K3[IrH(CN)s] is a white, crystalline, diamagnetic compound, which is unaffected by air; it is very soluble in water
and moderately soluble in CH30H. It reduces two equivalents of iodine per mole Ir. Aqueous solutions are stable at
room temperature for many hours, after which a grey-white
polymer begins t o deposit. The free acid, which may be prepared from the potassium salt by cation exchange, contains
three strongly acidic protons, which can be titrated. It may be
isolated as white (H30)3[IrH(CN)s]. Addition of AgN03
solution leads t o the precipitation of white, insoluble
Ag3[IrH(CN)s], which turns dark at the surface o n standing.
N o deuterium exchange was observed in a solution of
K3[IrH(CN)51 in D20, even after 7 days at 20 "C.
1R-spectra of K3[IrH(CN)s] (in KBr, nujol, and Hostaflon)
show bands a t 2110 cm-1 (vs) [shoulder at 2127 and at 2152
cm-11, and 2043 cm-1 (m) as C-N- and Ir-H- stretching
frequencies. Further bands occur at 810 (s, shoulder at 855),
533 (s), 513 (s), 454 (w), 404 (s), 386 (s), 333 (w). and 302
cm-1 (w)[sl. We assume v(Ir-H) t o be at 2043, 8(Ir--H) at
810 cm-1.
The UV-spectrum of the aqueous solution of K3[lrH(CN)j]
has an absorption maximum at 470 nm (E = 540) and a
Angew. Chem. internat. Edit.
Val. 6 (1967) No. 10
By H. Schildknecht and D . Hotr [*I
The methanol-soluble part of the secretion from the prothor a c k protective glands of Dytiscus marginalis contains cortexone as main component [31. When this steroid is isolated
as previously described [41, it contains as impurities substances
whose molecular weights are shown by their mass spectra to
be 316 and 314. If, however, the gland secretion is worked up
by thin-layer chromatography [silica gel G and cyclohexane/
ethyl acetate (1 :1)1, these subsidiary products are found to be
enriched together in the zone immediately above that of cortexone. By repeated chromatography 151 this mixture can be
separated into two components with absorption maxima at
283 and 240 nm.
Help with identification of these compounds was obtained
from the circular dichroism of the less polar compound whose
absorption maximum is at 240 nm. The position and fine
structure of the maximum at 331 n m indicated a 3-oxo-A4steroid 161, and indeed we found in the mass spectrum a peak
at m / e = 124 characteristic of such a steroid [71. Comparison
with the mass spectrum of a steroid that we had isolated from
the prothoracic protective glands of the water beetle Acilius
sulcatus[sl enabled the Dytiscus steroid of m / e 316 t o be identified as 20a-hydroxy-4-pregnen-3-one( I ) .
Our assumption that, as with Acilius sulcurris and Cybister
/nterulimurginulis 181, the second subsidiary steroid would be
the corresponding 6,7-dehydro compound was confirmed by
88 1
IR spectroscopy. However, this 20a-hydroxy-4,6-pregnadien3-one (cybisterone) occurs in vanishingly small amounts compared with ( I ) .
Received: July 24th, 1967
[ Z 584 IE]
German version: Angew. Chem. 79, 902 (1967)
[*] Prof. H. Schildknecht and Dip1.-Chem. D. Hotz
Organisch-Chemisches institut der Universitat
69 Heideiberg (Germany)
[l] Part 29 of Protective Substances of Arthropods. - Part 28:
H . Schildknecht, H. Winkler, D. Kraus, and U. Maschwitz,
Z. Naturforsch., in press.
[2] This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. We thank
Dr. Wiechert (Schering, Berlin) for samples.
[3] H. Schildknecht, R. Siewerdt, and U . Maschwitz, Angew.
Chem. 78, 392 (1966); Angew. Chem. internat. Edit. 5,421 (1966).
[4] H. Schildknecht: Symposium o n Animal Poisons, Sao Paulo
1966, in press.
[5] H. Schildknecht, D. Hotr, and U . Maschwitz, 2. Naturforsch. 22b, 938-944 (1967).
[6] L. Velluz and M . Legrand, Angew. Chem. 73, 603 (1961).
[7] R . H. Shapiro and C. Djerassi, J. Amer. chem. SOC.86, 2825
[8] H. Schildknecht, R . Siewerdt, and U . Maschwitz, Liebigs
Ann. Chem. 703,182 (1967).
Preparation of N-(Dichloromethy1ene)-chlorosulfonamide and -fluorosulfonamide [l]
By H. W . Roesky and U . Biermann[*]
Chlorosulfonyl isocyanate ( I ) [21 reacts with phosphorus
pentachloride (2) to give N-(dichloromethylene)chlorosulfonamide (3).
+ PC1,
The IR spectrum of (5) contains bands at 1615, 1440, 1220,
950, 850, 798, 628, 570, and 500 cm-1. Provisional assignments are: v(C=N) 1615, vas(S0) 1440, v,(SO) 1220,vas(C-CI)
950, v(SF) 850, vs(C-CI) 798, v(SN) 628, and deformation
vibrations. The 19F-NMR spectrum contains a signal at 6 =
--54.2 ppm referred to CC13F as external standard. The mass
spectrum shows, besides the moIecular ion at m/e = 179, fragments FSOzNCCl (144), SOpF (83), SF (51), and SO (48).
Received: July 26th. 1967
[Z 585 IE]
German version: Angew. Chem. 79,904 (1967)
[*] Dr. H. W. Roesky and Dip1.-Cbem. U. Biermann
Anorganisch-Chemisches Institut der Universitat
Hospitalstr. 8/9
34 Gottingen (Germany)
111 Part V of Sulfur-Nitrogen Compounds. - Part IV: H. W.
Roesky, Angew. Chem. 79, 724 (1967); Angew. Chem. internal. Edit. 6, 711 (1967).
[2] We thank Farbwerke Hoechst for the chlorosulfonyl isocyanate.
Adsorption of Nitrogen on Iron
By R. Brili, E.-L. Richter, and E. Ruch[*]
In connection with investigations on the catalysis of NH3
synthesis by iron, experiments on the adsorption of nitrogen
on iron tips were performed by means of the field electron
microscope. Fig. l a shows the emission picture of the clean
tip prepared by field evaporation in presence of hydrogen.
The crystal is oriented with the axis of the tip perpendicular
to 110. Fig. l b shows the effect of physical adsorption of N2
at the temperature of liquid nitrogen. The pattern shown in
Fig. l c was obtained after the tip with physically adsorbed N2
had been heated, without field, for 3 seconds to a temperature
of about 400 'C. It can easily be seen that the main change
takes place at the 111 faces. Here the work function is remarkably large. (Some change also occurs at the 100 poles and in
a circular zone around them. This circular zone probably represents a series of steps.)
0.1 mole each of ( I ) and (2) are heated together in a sealed,
thick-walled glass tube for 1.5 h a t 210°C. The tubes may be
opened at room temperature without cooling. ( I ) and (4) are
distilled off at atmospheric pressure, and (3) is then distilled
off in a water-pump vacuum (b.p. 71-72'C/15-16
32-33 "(70.2 mm; yield 10 %). At this stage, the product (3)
contains (CNC1)3 as impurity; it is obtained pure by repeated
The mass spectrum contains, besides the molecular ion at
m/e 195, peaks for the following fragments: SOzNCClz (160),
SO2CI (99), NCC12 (.96), SO2 (64), NCCl (61), SO (48), and
CCl (47). The IR spectrum (capillary film) in the NaCl and
KBr regions contains bands at 1608, 1570, 1402, 1180, 940,
790, 627, 593, 550, and 530 cm-1. These are provisionally assigned as follows: v(C=N) 1608 and 1570 (because of Fermi
splitting) vas(SO) 1402, vs(SO) 1180, vas(CC1) 940, vs(CCI)
790, v(S-N) 627, v(S-Cl) 593, and deformation vibrations.
The compound (3) reacts with antimony trifluoride t o afford
N-(dichloromethy1ene)fluorosulfonamide (5).
0.3 mole of (3) is heated with a n excess of SbF3 (SbC15 as
catalyst) for 2 h at 60 O C and for a further 2 h at 85 "C. The
mixture is then distilled in an oil-pump vacuum. The product
(5) is collected in a cold trap (liquid nitrogen) and then refractionated. Crude yield, 0.2 mole; pure yield, 0.05 mole
(b.p. 114-115 "C). Compound (5) can also be obtained from
fluorosulfonyl isocyanate and phosphorus pentachloride in a
sealed tube, the yield being 5 %.
Fig. 1. Field electron microscope patterns. (a) A clean iron tip (longitudinal axis of iron tip perpendicular to the 110 face), (b) the same tip
after adsorption of N2 at 76 "K, and (c) after adsorption of Nz and subsequent heating at ca. 400 "C for about 3 sec.
From these experimental results the following conclusions
may be drawn :
1. N Z is preferentially chemisorbed at the 111 face of iron.
Angew. Chem. internat. Edit. J Vol. 6 (1967) 1 No. 10
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steroid, protection, gland, subsidiary, prothoracic, identification, marginal, system, dytiscus
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