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Biaryls Stilbenes Benzo [c]cinnolines and Dibenz [c mn] acridines from Sulfonamides.

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EFH]
r
1
COOCH,
[I71 R. F . Childs and A. W Johnson, Chem. Commun. 1965, 95; J.
Chem. SOC.C 1966,1950.
[I81 a) K . Hafner, Angew. Chem. 75, 1041 (1963); b) K . Hafner, D.
Zinser, and K.-L. Moritz, Tetrahedron Lett. 1964, 1733.
[I91 F. D. Marsh and H . E. Simmons, J. Amer. Chem. SOC.87, 3529
(1965).
[20] L. E. Chapman and R . F. Robbins, Chem. Ind. (London) 1966,
1266.
[21] In the case of the alkoxycarbonylazepines, it is not decisive for
COOCH,
N-CH,
QfH3
CH3
our arguments whether protonation occurs directly at nitrogen or-as
suggested [18a, 151-a' the alkoxycarbonyl group; the electron pair
on nitrogen will become involved in bonding in both cases: in the first
case by the formation of a IN-H bond; in the second case by the formation of a 'N=C bond.
COOCH,
COOCH,
In this process, the formation of the bicyclic azanorcaradiene ( 4 b ) is p r o p o ~ e d [ ' ~ * ' ~ *'I, ' ~ "whose
existence in
the equilibrium ( 3 b ) ~ ( 4 b )would be favored by protonation" '1.
Received: May 18,1972 [Z 670 IE]
German version: Angew. Chem. 84, 820 (1972)
[I]
We are grateful to the Deutsche Forschungsgemeinschaft for a
stipendium to W.-D. S., and to the National Science Foundation for
support of our research.
[2] R. Hofmann, Tetrahedron Lett. 1970,2907; R. Hofmann and W-D.
Stohrer, J. Amer. Chem. SOC.93,6941 (1971); R. Hofmann in: Special
Lectures at XXIIIrd International Congress of Pure and Applied
Chemistry, Butterworth, London 1971, Vol. 2, p. 233.
[3] See also H . Giinther, Tetrahedron Letters 1970, 5173.
[4] R. Hofmann, J. Chem. Phys. 39,1397 (1963); R . Hoffmann and W N .
Lipscomb, ibid. 36, 2179 (1962); 37, 2872 (1962). The aziridine ring
geometry was maintained on protonation.
[S] R. Bonaccorsi, E. Scrocco, and J . Tomasi, J. Chem. Phys. 52, 5270
(1970). We are grateful to Dr. Scrocco for communicating these results
to us.
[6] The argument involves a second order effect: R. Hofmann, L. Libit,
W-D. Stohrer, and J . Swenson, unpublished results.
[7] a) L. M . "refonas, R. Towns, and R. Majeste, J. Heterocyclic Chem.
4,511 (1967);L. M.Trejonasand R. Towns,ibid. 1,19(1964);b)Forsome
related aziridine structures see L. M . Trefonas and R . Majeste, J. Heterocyclic Chem. 2,80 (1965); L. M . 7kfonas and T Sato, ibid. 3,404 (1966);
H . M . Zacharis and L. M . Trefonas, ibid. 5,343 (1968); 7,755,1301 (1970);
J . N . Brown, R. L. R. Towns, and L. M . "refonas, ibid. 7, 1321 (1970).
[8] T E. Turner, V C. Fiora, and W M . J . Kendrick, J. Chem. Phys. 23,
1966 (1955).
[9] H . Ringertz, Acta Chem. Scand 23, 137 (1969).
Biaryls, Stilbenes, Benzo [c Jcinnolines,
and Dibenz [c, mn] acridines from Sulfonamides
By Eckart Waldau and Rolf Putter[*]
3'-Hydroxy-4-nitrobenzenesulFonanilide( 1 ) reacts with
alkali in water with formation of 3-amino-4-(4-nitropheny1)phenol (3).
H;O
F
2
NH,
H3d
(3)
(4)
If thepara-position to the hydroxyl group of compound ( I )
is substituted by a methyl group, the nitrophenyl group
enters between the hydroxyl and the amino group to form
(4). In each reaction no more than one biaryl compound
was isolated. The specificity strongly suggests an intramolecular reaction course.
This reaction has a field of general application :
[lo]
J . L. Atwoodand G. D.Stucky, J. Amer. Chem. Soc.92,285 (1970).
[Illa) E. Vogel, W A. Ball, and H . Giinther, Tetrahedron Letters 1965,
609; b) E . Vogel and H. Giinther, Angew. Chem. 79,429 (1967); Angew.
Chem. internat. Edit. 6, 385 (1967).
[I21 H . Prinzbach and P. Vogel, Helv. Chim. Acta 52, 396 (1969);
H . Prinzbach, P. Vogel, and W Auge, Chimia 21, 469 (1967).
[13] G. Maier, Angew. Chem. 79, 446 (1967); Angew. Chem. internat.
Edit. 6 , 402 (1967).
[I41 a) D.M . Jerina, J . W Daly, B. Mtkop, P. Zaltzman-Nirenberg, and
S. lidenfriend, J. Amer. Chem. SOC.90,6525 (1968); Biochemistry 9,147
(1970); b) D.M . Jerina, J . W Daly, and B. Witkop, J. Amer. Chem. SOC.
90,6523 (1968); c) G. J . Kasperek and ?: C . Bruice, J. Amer. Chem. SOC.
94,198 (1972); d) D.M . Jerina, N . Kaubisch, and J . W Duly, Proc. Natl.
Acad. Sci. (USA) 68, 2545 (1971); e) N . Kaubisch, J . W Duly, and
D.Jerina, Biochemistry, in press; fJG. J . Kasperek, T C . Bruice, H . Yagi,
N. Kaubisch, and D. M . Jerina, J. Amer. Chem. SOC.,in press. We are
grateful to Dr. Bruice for bringing this work to our attention.
[ I S ] L. A. Paquetre in: Nonbenzenoid Aromatics. Academic Press,
New York 1969. Vol. 1, p. 249; b) L. A . Paquerte, D.E. Kuhla, and J . H .
Barrett, J. Org. Chem. 31,2879 (1969).
see H . Prinzbach,
1161 For evidence for the equilibrium (3b)=(4b)
D. Stusche, and R . Kitzing, Angew. Chem. 82,393 (1970); Angew. Chem.
internat. Edit. 9, 377 (1970).
826
HO-Ar-NH-SO2-Ar1
+2
OH'
-+
HO
'Ar-Ar'
+ SO,"
+ H2O
H2N'
(5)
(61
In order that it may take place the starting compound ( 5 )
must fulfil the following conditions :
1. In the aromatic group denoted Ar one ortho- or periposition to the sulfonamide group, i. e. the position concerned in linkage to the other aromatic group Ar', must
be unsubstituted (7).
2. The hydroxyl group on Ar must enable electrophilic
entry of Ar' to occur by virtue of its negativating effect.
[*] Dr. E. Waldau and Dr. R. Putter
Bayer A G
509 Leverkusen (Germany)
Angew. Chem. internat. Edit. 1 Vol. I 1 (1972)
No. 9
Positivation also occurs if this carbon atom is a component
of an aromatic heterocyclic ring (19).
Thus its position decides the position at which linkage
occurs, which can be ortho or para to this hydroxyl group.
If Ar denotes a naphthalene derivative, then other positions
must also be considered ( 9 ) , (11).
AIr'
In special cases further reaction may take place after
formation of the biaryl. 3'-Hydroxy-2-nitrobenzenesulfonanilide (21) reacts with alkali in water at 250 "C to
yield 3-hydroxybenzo[c]cinnoline ( 2 4 ) , (22) and (23)
having been proved to be intermediates.
Ar'
I
Ar'
Ar' = G
N
O
3. During the reaction Ar' becomes bonded to Ar by the
carbon atom carrying the sulfonamide group. This carbon
atom must be rendered positive by Ar'. The positivation
can be effected by eiectron-withdrawing groups such as
nitro, sulfonyl, or carbonyl in the ortho- or para-position
(131, ( 1 5 ) .
,
(21)
(22)
Under the conditions chosen, reaction in dimethyl sulfoxide stops at the stage of 3-hydroxybenzo[c]cinnoline
6-N-oxide (23), whereas in water (23) is reduced to (24)
by the sulfite produced in the reaction. Because of its good
yields (approximately 70%) this procedure provides a
useful synthetic route to substituted benzo[c]cinnolines.
A subsequent reaction also occurs on treatment of 3'-hydroxyanthraquinone-I -suIfonanilide (25) ; 2-hydroxy-8H-dibenz[c,rnn]acridin-8-one (27) is formed and the
primary product (26) cannot be isolated.
If the para-position to the hydroxyl group of compound
(25) is substituted by a methyl group, then 4-hydroxy-lmethyldibenz[c,mn]acridin-8-one (28) is obtained in a
yield of 45%.
H,
The carbonyl group that positivates the aromatic group Ar'
may also be contained in a cyclic system (17).
Angew. Chem. mternaf. Edit. 1 Vol. I 1 (1972) 1 No. 9
827
Nitrostyrenesulfonamides (29), as vinylogs of nitrobenzenesulfonamides, are also amenable to this reaction.
Instead of biaryls one obtains stilbenes (30) with the
trans-configuration.
N H - SO,
"
O
-CH =
c H O N o ,
O
water or an organic solvent such as dimethyl sulfoxide
or hexamethylphosphorotriamide under the conditions
listed in Table 1. The crude product is precipitated by
dilute mineral acid and filtered off. The pure products are
obtained by recrystallization from alcohol or alcohol/
water mixtures, if necessary with chromatography on
alumina.
Table 1 gives a survey of the biarvls, benzocinnolines,
dibenzacridines, and stilbenes synthesized. The yields
were not optimized ; they increase with decreasing concentration of the sulfonamide if the electron-withdrawing
substituent can be reduced by the sulfite. Melting points
are uncorrected. The structures of the products accord
with elemental analyses and IR, NMR, and mass spectra.
(29)
General experimental procedure.
A sulfonamide of type (5) (0.1 mol) and potassium
hydroxide (0.3 mol) are allowed to react in 2-3 liters of
Received: June 28, 1972 [Z 672 IE]
German version: Angew Chem 84. 822 ( 1 972)
Table 1. Compounds prepared.
Starting material
Product
Conditions
Yield (%)
M.p.("C)
3'-Hydroxy-4-nitrobenzenesulfonanilide
3-Amino-4-(4-nitrophenyl)phenol
H2O
14 h, 100°C
80
180
3'-Hydroxy-4-(methylsuIfonyl)benzenesulfonanilide
3-Amino-4-(4-methyIsulfonylpheny1)phenol
HzO
1 h, 250°C
58.6
203
5'-Hydroxy-2'-methy1-4-nitrobenzenesulfonanilide
3-Amino-4-methyl-2-(4-nitropheny1)phenol
DMSO
30 min, 120'C
10
221
1 -H!droxy-3-(4-nitrobenzenesulfonylamino)-5-naphthalenesulfonic acid
3-Amino-l -hydroxy-4-(4-nitrophenl I)-5-naphthalenesulfonic
acid
H2O
14 h, l0O'C
50
> 360
5-(4-Nitrobenzenesulfonyl-
5-Amino-4-(4-nitrophenyl)-lnaphthol
11
203
amino)-1-naphthol
1-(4-NitrobenzenesuIfonyla m i ~ o ) - 7naphthol
-
8-Amino-I -(4-nitrophenyl)-2naphthol
H2O
12 h, 100'C
23
203
7-(4-Nitrobenzenesulfonylamino)-2-naphthol
2-Amino-I -(4-nitrophenyl)-7.
naphthol
DMSO
30 min, 120 "C
38
240
1-(4-NitrobenzenesulfonyIamino)-6-naphthol
1-Amino-2-(4-nitrophenyl)-6naphthol
55
230
45 min, 120'C
3"-Hydroxybenzophenone-4sulfonanilide
3-Amln o-4-(4-benzoxylphenyI)phenol
H2 0
1 h, 250°C
45
190
3'-Hydroxyanthraquinone-2sulfonanilide
3-Amino-4-(2-anthraquinonyl)~
phenol
DMSO
45 min, 60°C
18
238
3'-HydroxybenzothiazoIe-2sulfonanilide
3-Amino-4-(2-benzothiazolyl)phenol
€32 0
10 h, 1OO'C
44
191
3-Hydroxyanthraquinone- 1 sulfonanilide
2-Hydroxy-8 H-dibenz[c, mnlacridin-%one
DMSO
10 min, 120°C
73
348
5'-Hydroxy-2-methylanthraquinone-1-sulfonanilide
4-Hydroxy-1-melh?l-8 H-dibenr[ c . iiiri]acridin-X-onc
DMSO
2.5 h, 120°C
45
295
3'-Hydroxy-2-nitrobenzenesulfonanilide
3-Hydroxybenzo[c]cinnoline
H2 0
1 h, 250'C
67
283
3'- Hydroxy-2-nitrobenzenesulfonanilide
3-Hydroxybenzo[c]cinnoline6-N-oxide
DMSO
15 min, 120°C
67
272
4-Chloro-3'-hydroxy-2-nitrobenzenesulfonanilide
2-Chloro-3-hydroxybenzo[c]cinnolme
H2O
5 min, 250'C
49
287
3'-Hydroxy-4-nitrostyrene-Psulfonanilide
2-Aniiiio-4-hydroxy-4'nitrostilbene
DMSO
30 min, 120°C
58
199
3'-Hydroxy-2-nitrostyrene-Psulfonanilide
2-Amino-4-hydroxy-2'nitrostilbene
DMSO
30 min, 120°C
62
157
5'-Hydroxy-2-methy1-4-nitrostyrene-0-sulfonanilide
2-Amino-6-hydroxy-3-methyl4-nitrostilbene
DMSO
30 min, 120'C
35
201
828
DMSO
8 h, 120°C
DMSO
Anyew. Chem. internat. Edit.
Val. I I i 1972) 1 No. 9
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acridines, sulfonamide, benz, dibenz, biaryls, stilbene, cinnolines
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