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One-Step Entry to N-Cyanimines and to N N-Dicyanoquinonediimines a Novel Class of Electron-Acceptors.

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Table 2. I3C-NMR data of 2a, 3, l c , and Id (100.62 MHz, &values, solvent as internal standard).
c-l
c-2
c-3
c-4
C-4a
c-5
C-6
c-7
c-8
C-8a
c-9
c-10
2a ([D,]DMSO]
3 (CDC13)
130.60 d 7.1
142.57 d 2.3
121.86 D 162
127.96 dd 5 / 1 3
125.67 dd 8.6/1.2
131.16 Dd 165/6.5
128.92* br. s
126.09 Dd 165/7.4
125.29* br. s
119.94 d d 6.8/7.3
173.03 d 4.5
154.75 s
142.41 dq 6.U3.8
148.87 dq 2.W3.8
119.55 D 160
123.80 dd 4.8/1.9
128.01 dd W1.2
129.66 Dd 162/6
133.92 br. s
128.23 Dd 16417.3
125.01 br. s
126.74 dd 6.7/6.6
187.30 d 4.8
161.19 q 3.8
C-l'/ 1"
C-2'/2"
C-3'/3"
C-4'/4"
C-5'/5"
C-6'/6"
C-7'/7"
C$j'/8''**
c-9'/9"*
*
C-10'/10"
2a ([D6]DMSO)
3 (CDCI,)
IC(CD3OD)
Id (CDCI,)
168.50 s
168.51 s
95.30 d 4.8
93.44 dd 4.3/4.0
166.72 s
166.92 s
151.54 s
151.89 s
117.89 t 3.9
117.93 t 3.9
171.38 s
172.23 s
126.16 t 8
126.33 t 8
131.44 Dd 162/7.2
131.46 Dd 162/1.2
114.02 Dd 159/4.8
114.16 Dd 159/4.8
156.47 tt 9/2.7
156.59 tt 9/2.7
167.40 s
168.00 s
102.70 d 5
106.20 t 4.8
163.65 q 3.8
164.45 q 3.8
139.42 s
139.79 s
117.09 t 4.2
117.69 t 4.2
166.87 q 3.8
166.96 q 3.8
123.29 t 8
123.43 t 8
130.88 Dd 161/7.3
130.93 Dd 16V7.3
114.32 Dd 161/5
114.35 Dd 161/5
160.57 m
160.69 m
168.7 s
168.1 s
105.0 t 4.3
108.2 t 4.3
160.8 s
162.2 s
154.6 s
140.3 s
I 18.3t 4.0
115.6 t 4.2
174.8 s
167.4 q 4
125.6 t 8.2
122.1 t 8.2
130.3 Dd 160/7.2
132.7 Dd 150/7.2
115.6 Dd 160/4.6
116.2 Dd 160/4.6
158.6 m
158.7 m
123.6 t 8
120.6 t 8
130.8 Dd
131.0 Dd
114.0 Dd
114.3 Dd
160.1 m
160.5 m
161/7
161/7
160/5
160/5
3: 1-OCHg (60.5, Q, J = 146.4 Hz), 2-OCH3 (56.7, 145.0), 10-OCHs (52.9, 148.1), 3'/3"-OCH3 (60.8/61.8, 148.4/148.4), 6'/6"-OCH3 (52.7/52.8, 147.6/147.6), lo'/
10"-OCH, (55.32/55.33, 144.2/144.2); Id : 3'-OCHs (60.9, Q, J= 147.7 Hz), 6'-OCH3 (52.7, 147.7), 10'/10"-OCH3 (55.3, 144.6)
[*I Assignment may be reversed. [**I Signals for double the number of C atoms.
naphthalene moiety with two pulvinic acid side chains.
The side chain at the 8-position, however, is one carbon
atom shorter than the other, and forms a y-lactone with the
I-OH group (13C-NMR: 6(9-C0)= 167.12, d, 5=3.5 Hz, in
[D,]DMSO).
Apparently, the component 2a of the fungus is capable
of further degradation; in bisnorbadioquinone A 5aL6]the
side chain at the 8-position is missing, and the hydroxy
groups are oxidized.
Formation of pulviquinone A 6a from 5a by oxidative
elimination of the pulvinic acid chain at the 4-position is
conceivable. The brownish red pigment is isolated as the
methyl ether 6b, which is most likely formed during the
extraction with acidified methanol. In order to demonstrate the role of xerocomic acid l a as a biogenetic precursor of badion A 2a, a portion of the cap cuticle was removed from a bay boletus and the underlying white flesh
treated with aqueous xerocomic acid solution. The resulting yellow spot became bluish green within a few minutes
and gradually turned brown in color. After extraction and
chromatographic separation of the resulting pigment, 2a
could be detected 'H-NMR spectroscopically. Thus, the
enzymes necessary for the oxidative dimerization of l a appear to be fixed to the cap cuticle. Badion A 2a is also the
pigment of Boletus pinicola Vitt., a close relative of the cep.
Interestingly, in Boletus erythropus (Fr. ex Fr.) Pers. it is replaced by badion B 2b, which is biogenetically derived
from variegatic acid lb['I.
Received: February 9, 1984 [Z 704 IE]
German version: Angew. Chem. 96 (1984) 435
CAS-Registry numbers:
lc, 90320-59-5; Id, 90295-65-1 ; 2a, 90295-66-2; 3, 90295-67-3; 4a, 90295-684; 4b, 90295-69-5; 5a, 90295-70-8; 6b, 90295-71-9.
[5] W. Steglich, H. Bed, K. Zipfel, Z . Naturfor.sch. 8 2 9 (1974) 96.
[6] UV (MeOH). 4a:Am,,=260, 367,406 om (sh); 4a: 250 (sh), 307,356,415
nm (sh); 6a: 265 (sh), 278,312,354,422 nm.-'H-NMR ([D6]DMSO). 4a:
F=6.76, 6.79, 7.09, 7.12 (each d, J=8.9 Hz, XH), 7.39 (s, 1 H), 9.04, 9.44
(each d, J=0.9 Hz, 2H); 5a: 6.45 (s, 1 H), 6.73, 6.75, 7.05, 7.08 (each d,
J = ~ S H Z , ~ H ) , ~ . ~ ~ ( ~ , J I=HX) , .8 ~. 3H
3 (Z
d d, , J = 8 . 2 a n d 1 . 5 H z , I H ) ,
8.53 (d, J=1.5 Hz, lH), 9.46, 9.50, 17.56, 17.83 (each br. s, 4 0 H ) ; 6b:
3.83 (s, 3H), 6.28 (s, lH), 6.73, 7.07 (each d, J=8.5 Hz, 4H), 7.93 (d,
J=8.3 Hz, 1 H), 8.56 (dd, J=8.3 and 1.6 Hz, 1 H), 8.82 (d, J = 1.6 Hz,
1 H).
[7] P. C. Beaumont, R. L. Edwards, G. C . Elsworthy, J . Chem. SOC.C 1968,
2968.
One-Step Entry to N-Cyanimines and to
N, N'-Dicyanoquinonediimines,
a Novel Class of Electron-Acceptors**
By Alexander Aumiiller and Siegfried Hiinig*
N-Cyanimines 3 are accessible from alkenes and cyanazide"', as well as from certain carbodiimides and isothiocyanates[']. Hitherto all reactions in which ketones have
been used as starting substances have involved several
stepsL3]. Herein we describe the one-step conversion
>C=O+>C=N-CN,
which can be applied to (nonenolizing) ketones and to p-quinones. The crucial reagent
is bis(trimethylsily1)carbodiimide 2 14],which converts, e.g.,
benzophenone (62-70%)['] and fluorenone (75Y0)[~linto 3
in the presence of fluoride or cyanide catalysts according
to equation (a).
RxR
+
CrF or
KCNI[ 181-crown-6
Me3Si-N=C=N-SiMe,
CHsCN, 22 h
1
"
R
+
3
[l]
[2]
[3]
[4]
W. Furtner, Dissertation, Technische Universitat Miinchen 1969.
W. Steglich, W. Furtner, A. Prox, Z . Naturforsch. 8 2 3 (1968) 1044.
R. Herrmann, B. Steffan, W. Steglich, unpublished.
A yellow pigment containing a naphtho[l,8-bc]pyrandionesystem has
also been isolated from the culture filtrate of the phytopathogenic fungus
Gremmeniella abietinat W. A. Ayer, Y. Hoyano, I. Altena, Y . Hiratsuka,
Rev. Latinoam. Quim. 1982, 84.
Angew. Chem. Int. Ed. Engl. 23 (1984) No. 6
(Me3Si),0
4
4
[*I Prof. Dr. S. Hiinig, Dipl.-Chem. A. Aumiiller
Institut fur Organische Chemie der Universitat
Am Hubland, D-8700 Wiirzburg (FRG)
[**I This work was supported by the Stirtung Volkswagenwerk, by the Fonds
der Chemischen Industrie, and by BASF AG.
0 Verlag Chemie GmbH. 0-6940 Weinheim, 1984
0570/0833/84/0606-0447 $02.5010
447
($p
However, under these basic conditions the reaction fails
in the case of, e.g., 5 (acid cleavage) and quinones 8.
These tend to undergo 1,4-addition and are more readily
reduced than anthraquinone 8i, which affords 62% 9i with
2 and CsF.
NC
,CN
llh
11
CN
lli
N'
A Me
Ph
6 (47":")
5
7 (23%)
This problem can be overcome, however, by using titanium tetrachloride as auxiliary reagent. For example, 6
(47%, m.p. 143-144°C) can then be prepared quite
smoothly, and even the enolizable acetophenone affords
23% 7[3a1,while N-cyanocyclohexanimine['I is not detectable. Presumably the silyl groups are not eliminated as 4 in
the presence of TiCI4, but as 10 [cf. eq. (b)].
sured in lgKsEMvalues--frequently exceed even those of
the quinone systems 8. Because of the chemical analogy
between the groups =C(CN)2 and =N-CN['], the systems
9 ("DCNQI") have acquired considerable importance as
alternatives to derivatives of tetracyanoquinodimethane
("TCNQ") 11, R'-R4= H, being acceptor components
for electrically conducting CT complexes[*I. X-ray structure analyses of all the compounds reveal that the planarity required for this purpose is assured in the case of 9h['],
and probably also in the case of 9a-g and 9 4 but is not
so in the analogues of 9h and 9i, the dicyanomethylene
derivatives 1lL9Iand lli['O1.
Received: February 27, 1984 [Z 723 IE]
German version: Angew. Chem. 96 (1984) 437
+
+
2 Me,Si-N=:C=N-SiMe,
0
8
TiC1,
CH2CIz
RT
'0:;
+
Ti0,
+ 4 Me,SiCl
R3
N
cP
10
9
The first synthesis of the N,N'-dicyanoquinonediimines
9I6I counts among the few reactions involving condensation at the carbonyl group of the quinones 8. The selected
examples 9a-i demonstrate the broad spectrum of quinone substituents tolerated with regard to changes in potential and spatial requirements (Table l).
[I] F. D. Marsh, M. E. Hermes, J . Am. Chem. Sac. 86 (1964) 4506.
[2] J. C. Jochims, M. A. Rahmann, Chem. Ber. 117 (1984) 502.
[3] a) A. Shafiee, 1. Lalezari, M Yalpani, J. Org. Chem. 37 (1972) 2052; h)
P. Horsewood, G. W. Kirby, R. P. Sharma, J. G. Sweeny, J. Chem. Soc.
Perkin Trans. 1 1981, 1802.
[4] L. Birkofer, Tetrahedron L a / . 1962, 195.
[5] Melting points and spectral data are in agreement with those quoted in
the literature (cf. [3a] and [3h]).
[6] Procedure: Under exclusion of moisture, a solution of 8 in CH2C12 is
treated consecutively with l'iC14 and a solution of 2 in CH2C12 (both
reagents in 2- to 25-fold excess). The reaction is monitored by thin-layer
chromatography (SiO2/CH,('l,).-Work-up: a) The reaction mixture is
filtered through a short silica gel column (10 cm Woelm 0.063-0.200 silica gel) and washed with CH2C12(9b, 9c).-h) The reaction mixture is
poured into petroleum ether (30--75"C), the precipitate filtered off, extracted with benzene, and the product re-precipitated with petroleum
ether (9a, 9h).-c) After shaking with ice-water, the organic phase is
dried over MgS04 and the product precipitated with petroleum ether
(9d, 9e).-d) After addition of CH2C12 and granulated active charcoal
Table 1. Yields, melting points and electrochemical data of the N,N'-dicyanoquinonediimines 9a-i.
H
H
H
Me
Me
Me
H
tBu
H
OMe
OMe
OMe
CI
CI
H
H
-(CH= =CH)2-
H
Me
Me
tBu
OMe
OMe
CI
-(CH=CH)Z-(CH=CH)z-
H
H
Me
H
H
OMe
CI
64
I5
49
58
84
59
26
41
34
165
320-321
125-127
241
265
172-173
258
255
226-226
-0.26
- 0.44
- 0.40
- 0.50
- 0.45
- 0.38
+0.16
-0.38
- 0.46
+0.38
+0.17
0.05
+0.16
+0.15
0.2 1
0.76
+0.28
-0.11
+
+
+
10.90
10.30
7.49
11.20
10.12
9.90
10.12
11.19
6.07
[a] After recrystallization. [b] In CH2C12,[nBu,N]BF, as supporting electrolyte; Ft' electrodes vs Ag/AgCI in CH'CN
According to the "C-NMR spectrum (CDC13), 9a is
present as a syn/anti mixture, whereas all 2,5-disubstituted
derivatives (9b, d , e) have an anti-configuration, but 2,3disubstituted derivatives (9h) a syn-configuration. Tetrasubstitution lowers the conversion barrier (syn +anti) to
-
_.1I L7
1.,1
/--l
hbaii IIIUI.
9a-i form two-step, reversible redox systems in which
the thermodynamic stability of the radical anions-mea448
0 Verlag Chemie GmbH, 0-6940 Weinheim, 1984
the mixture is stirred for a short while, filtered, and the product precipitated with petroleum ether (Yf, 9i).-e) The product precipitating is filtered off (9s).
[7] a) E. Allenstein, Chem. Eer. 101 (1968) 1232; h) H. Kohler, B. Eichler, R.
Salewski, 2. Anorg. ANg. C h m . 379 (1970) 183; c) H. Kohler, B. Kotte,
Z . Chem. 13 (1973) 350.
181
. . Cf. A. Aumiiller. E. Hadicke. S. Hiinig. A. Schatzle. J. U. von Schiitz.
Angew. Chem. 96 (1984) 439; Angew. Chem. Int. Ed. Engl. 23 (1984) 449.
191. F. Iwasaki, Acta Crystalloqr.
.
.
. B27 (1971)
.
, 1360.
(101 u. Schubert, A. Aumiiller, s. Hiinig, unpublished results.
0570/0833/84/0606-0448 $02.50/0
Angew.
Chem. Int. Ed. Engl. 23 (1984) No. 6
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