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Model Reactions for Biological Ring Opening of Anthraquinones.

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both under thermodynamical control, to give a stable substitution product.
Received: August 9th, 1967
12 603 IE]
German version: Angew. Chem. 79, 936 (1967)
[*I Doz. Dr. F. Etrenberger and Dip1.-Chem. G. Kiefer
Institut fur Organische Chemie der Universitat
Azenbergstr. 14/16
7 Stuttgart (Germany)
[l! This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
[2] F. Efenberger and R . Gleiter, Chem. Eer. 97, 1576 (1964).
[3] R. Huisgen, L. Feiler, and G. Binsch, Angew. Cliem. 76, 892
(1964); Angew. Chem. internat. Edit. 3, 753 (1964).
[4] K. D . Barrow and T. M . Spotswood, Tetrahedron Letters
1965, 3325.
[S] F. Efenberger and R . Gleiter, Chem. Ber. 99, 3903 (1966).
[6] R. Huisgen, R. Grashey, and I. Sauer in S. Patai: The
Chemistry of Alkenes. Interscience, New York 1964, pp. 786-757.
The structure of compounds ( l a ) to ( l c ) follows from their
elemental analysis, IR and IH-NMR spectra, and the lack
of conductivity of freshly prepared solutions.
The behavior of the compounds is similar to that of the SO,amine adducls, e.g. stronger bases replace weaker ones from
their linkage to the S atom. With liquid ammonia they give a
quantitative yield of the NH4+ salt of imidobissulfamide,
which was identified by conversion into free imidobissulfa().
151.
mide 7
The action of primary or secondary amines on compounds
(In) to ( I c ) provides a synthesis of trialkylammonium salts
of monosubstituted (4) and asymmetrically di-N-substituted
imidobissulfamides (5). They can be converted by ionexchangers or by treatment of their silver salts with the
calculated amounts of hydrochloric acid into the free,
hitherto unknown asymmetrically substituted imidobissulfamides (6) and (7) in yields exceeding 90 %.
Derivatives of Imidobissulfamide
By R. AppeI and R . Helwerth[*I
Sulfimide, HNS02, has been assumed to be a reactive intermediate in the reaction of sulfamoyl chloride with nitrogenous bases. Hitherto, however, it has been isolated only as
the pyridinium salts of the oligomers, tri- and tetra-sulfimidefzl. Atkins and BurgessC31 proved the formation of Nsubstituted derivatives of sulfimide, RNS02 (N-sulfonylamines), on treatment of N-substituted sulfamoyl chlorides
with tertiary amines at -78 "C.
We have found that sulfamoyl(trialky1ammonio)suIfonyl
imides ( I ) are formed when a solution of sulfamoyl chloride
in acetonitrile is treated at -40 "C with tertiary nitrogenous
bases such as trimethyl- or triethyl-amine or pyridine in the
molar ratio 2:3. They are nitrogen analogues of the mesylsulfenamine adductsi recently described by Opitz and Biicher 141.
2 HzNSOzCl
+ 3 XR3
0
+
Q
HzN-S02-N-S02-NR3 ( I )
R'
M.p. ("C)
Liquid
110-112
167- 168
124- 125
154-155
97-100
Compounds (6) and (7) dissolve readily in water, giving
strongly acid solutions. Sulfate ions can be detected therein
only after addition of sodium nitrite. These well-crystalline
materials are stable in air.
Received: August 7th. 1967
[Z 605 IE]
German version: Angew. Chern. 79, 937 (1967)
+
~
[*I Prof. Dr. R. Appel and Dip1.-Chem. R. Helwerth
IR
(Ic)
CH3
CzKs
NR3 == CSHSN
1
I
Yield
(%)
154-156
94-96
Rearrangement above 105 "C
The compounds ( I ) are precipitated, sometimes with the
amine hydrochlorides, from which they can be separated
readily by utilizing their poor solubility in cold water.
When sulfamoyl chloride is treated with pyridine below
-80 ' C , a very reactive intermediate (m.p. 57-65 "C) can be
isolated, which dissolves in water to an acid solution. Within
a few seconds this clear solution deposits the neutral compound ( I c ) . Slow heating of the reactive intermediate affords
first this product flc), which, when further heated, resolidifies and is converted into the known pyridinium salts of triand tetra-sulfimide 121. Further experiments areto be performed
to decide whether the reactive intermediate is the pyridine
adduct (2) of monomeric HNS02, which is isoelectronic
with the known pyridine-SO3 adduct (3).
952
Anorganisch-Chemisches Institut der Universitlt
Meckenheimer Allee 168
53 Bonn (Germany)
[l] Part 111 of Investigations on Sulfimide - Part 11: [2].
[Z] R. Appel and G. Berger, 2. anorg. allg. Chem. 327,114 (1964).
[3] G. M. Atkins and E. M. Burges, J . Amer. chem. SOC.89,2502
(1967).
[4] C. Opitz and D. Bucher, Tetrahedron Letters 43, 5263 (1966).
(51 A. V. Kirsanov and M. Zolotov,
obSE. Chim. 20, 165@
(1950); Chem. Abstr. 45, 1950 c-i (1951).
z.
Model Reactions for Biological Ring Opening of
Anthraquinones
By B. Franck, V. Radtke, and U . ZeidIer[*]
Although the biosynthesis of more than 100 natural anthraquinone pigments is largely clarified [ 3 , 4 1 , very little is known
about their biological degradation. This must begin with an
oxidative opening of the quinonoid ring. We have previously
reported the detection of such a ring opening as a metabolic
reaction[21. It was shown by feeding experiments with
radioactively labeled precursors that ergochromes [51, e.g.
secalonic acid A (3), are formed from emodin (1) by way of
the acid (2). We have now found a reaction sequence thai may
serve to explain this oxidative ring opening ( I ) + (2) that
was previously unknown in anthraquinone chemistry.
Angew. Chem. internat. Edit. / Vol. 6 (1967) / N o . I 1
with the material previously described as (8) 171. There is no
doubt that its structure is that of (7) [81, as is shown by, inter
a h , its anthrone-like U V spectrum in cyclohexane (A,
=
219, 271 nm) and its IR spectrum in KBr ( v c - 0 = 1640
cm-I); further, mass and N M R spectra support structure (7).
HO
0
Received. August 7th. 1967
[Z 604 IE]
German version: Angew. Chem. 79, 935 (1967)
[*I Prof. Dr. B. Franck, Dip1.-Chem. V. Radtke, and
We first ascertained that 19 systematically selected hydroxyanthraquinones, including emodin ( I ) , were stable t o peracids (perbenzoic acid, peracetic acid, and trifluoroperacetic
acid) which seemed most likely to effect ring opening, whereas
benzophenone was cleaved smoothly thereby. Thus it is
unlikely that anthraquinones themselves are liable t o biological ring opening. Anthrones (4), on the other hand, which are
biogenetic precursors or reduction products of anthraquinones, can be considered as starting products for the ring
cleavage.
Dip1.-Chem. U. Zeidler
Institut fur Organische Chemie der Universitat
Neue Universitat
Olshamenstr. 40- 60
23 Kiel (Germany)
[ l ] Part 16 of Ergot Pigments. - Pait 15: [2].
[2] B. Franck, F. Hiiper, D. Griiger, and D.Erge, Angew. Chern.
78, 752 (1966): Angew. Chem. internat. Edit. 5, 728 (1966).
[3] J . H. Richards and J . B. Hendrickson: The Biosynthesis of
Steroids, Terpenes and Acetogenins. W. A. Benjamin, New York
1964, p. 151.
141 E. Leistner and M. H . Zenk, Tetrahedron Letters 1967, 475.
[5] B. Franck, E.-M. Gottschalk, U. Ohnsorge, and F. Iiiiprr,
Chem. Ber. 99,3842 (1966); B. Franck, E.-M. Gnrrschalk, U.Ohnsorge, and G. Baunmnn, Angew. Chern. 76, 438 (1964); Angew.
Chem. internat. Edit. 3, 441 (1964).
[6] T. Money, Nature 199, 592 (1963).
[7] P. L. Julian, W. Cole, and G. Diemer, J. Amer. chem. S O C .
67, 1721 (1945).
[8] C . Dufraisse, A . Efienne, and J . Riguudy, Bull. SOC.chim.
France 15, 804 (1948), had previously shown that a product
believed to be a transannular peroxide corresponding to (8) [7]
was in fact the analogous 10-phenylanthryl hydroperoxide.
I
0, 61%
Bis(tripheny1phosphine)triazenium
Tetrachloroantimonate(II1) [' 1
By N. Wiberg and K . H . Schrnid[*I
OH
O:\ c
Antimony azide tetrachloride ( I ) contains [21 N-diazenium
groups. An ability to add bases is typical of diazenium groups
attached to carbon. I n order to see whether this ability is
possessed by azenium groups bonded t o nitrogen we treated
the salt ( I ) with triphenylphosphine.
This reaction, however, did not lead to the adduct containing
\@
CH,
6H3
10-Methylanthrone ( 5 ) , which was prepared from anthrone
(4), gave o n reaction with Oz/azobisisobutyronitrile in benzene the hitherto unrecorded 10-methylanthronyl hydroperoxide ( 7 ) [m.p. 159-161 OC (decomp.)]. This was rearranged by CH,COzH/4 N H2SO4 (4: 3), with ring opening,
t o 2-acetyl-2'-hydroxybenzophenone (6) (m.p. 108 "C); an
approximately equal yield of anthraquinone, formed by
elimination of methanol, was also obtained. The structure of
(6) was confirmed by elemental analysis, UV spectrum in
= 253, 328 nm), IR spectrum in KBr (vc-0,
CH3OH (A,
chelated = 1635, v c - 0 = 1685 cm-l), and mass spectrum
[ m / e = 240 (M@, 100%) 197 (M-CH,CO),
147 ( M C&OH), 121 (M - C&.+CO-CH3)]. The proton-catalysed
rearrangement of (7) is analogous to the rearrangement of
cumyl hydroperoxide and may follow the same mechanistic
route. Attempts by Muney[61 and by us to effect this ring
opening with anthrone (4)or anthranol in place of (5) failed
because of the instabiiity of the corresponding hydroperoxides.
10-Methylanthronyl hydroperoxide (7) was obtained, not
only by autoxidation of 10-methylanthrone (5), but also by
another route which was stated by Julian, Cole, and Diemer [ 7 ] t o lead to 9,10-epidioxy-10-methylanthranol(8). The
action of CH3MgI o n 10-methylanthryl acetate (9) and subsequent autoxidation gave a product C15H12O3 that agreed
in m.p. and other properties with the hydroperoxide ( 7 ) and
Angew. Chem. internat. Edit. Vol. 6 (1967)
No. 1 1
the group ,N=N-N=PPh3. The adduct is probably formed
as intermediate but at once decomposes t o other products.
The course of the reaction is determined by the redox
reaction:
Sb(V) i- P(111)
-+
Sb(III)
+ P(v)
When (I) is treated in benzene with PPh3 in the molar ratio
1 :4 (2 h at 20 "C), the antimony is reduced, the phosphorus
is oxidized, and a quantitalive yield of bis(tripheny1phosphine)-triazenium tetrachloroantimonate(~~i)(2) is obtained as insoluble product [31.
The cation (2), a n aza vinylogue of the known cation
Ph3PNPPh3+141, is the first example of a compound containing a P N N N P group. The salt (2) forms yellow crystals,
r
c1 4
..
0
Ph3P=N-NzN-PPh3
I
which melt at 90 "C with decomposition and are insoluble in
apolar solvents but soluble in CHZC12. The charge o n the
cation is spread equally over the P N N N P group, since only
one signal appears in the 31P-NMR spectrum.
953
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