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An Aza[13]- and an Aza[17]annulenyl Anion.

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4-Azulenylacetic acid ( 4 ) (m. p. 122 T , d e ~ o m p . ) ' ~prepared
],
in 75 O h yield by reaction of 4-methyla~ulene[~~
with sodium
N-methylanilide and subsequent carboxylation of the resulting
sodium 4-methylenea~ulenide~'J,
proved to be useful as starting
material for the synthesis of (1). By treatment with sulfinylbis(dimethylamine)f81 in benzene for 2 h at 6 0 ' C ( 4 ) can be
converted almost quantitatively into the carboxamide ( 5 ) .
Cyclization in POCl3 (60-C,2 h) yields 95 O/O of the ketimonium
chloride (6) (perchlorate :red-brown crystals, m. p. 243 to
244 C, decomp.). Reduction of (6) by NaBH4 in methanol
at 20 C followed by quaternization with methyl iodide affords
the iodide (7) (yield 90%; blue-violet crystals, decomp.
> 1 10 'C), and Hofmann degradation with 2~ NaOH at 20'C
finally gives rise to a 90% yield of the hydrocarbon ( I )
(brown leaflets having metallic luster, m. p. 69-70 'C,
decomp.). Compound ( l ) is yellowish brown in solution and
prone to autoxidation but thermally stable.
The 60 MHz 'H-NMR spectrum of ( 1 ) (in CCI,), which provides structural proof for the compound, contains a multiplet
centered at T = 1.93 for the four protons of the seven-membered
ring in addition to the signals of the two AB systems for
the protons of the five-membered rings at r=3.18 and 2.54
( J A ~ = 4 .Hz).
5 The electronic spectrum of ( I ) (in n-hexane)
shows a pronounced vibrational structure in the UV and
visible regions.
Reduction of the quaternary salt (7) by NaBH4 in methanol
at 0 'C yields I ,2-dihydrocyclopent[cd]azulene (8) (yield 37 YO;
dark blue needles, m. p. 71 "C) which is isomeric to (2) and
whose 2-0x0 derivative (9) is accessible by direct cyclization
of ( 4 ) in acetic anhydride/pyridine (yield 83 %; red-brown
crystals, m. p. 131--132^C). Oxidation of (9) with selenium
needles, decomp. > 270 C). Reduction (NaBH4)and quaternization with methyl iodide finally yield the iodide ( 1 4 ) (airsensitive blue powder). Treatment of ( 1 4 ) with potassium
trrt-butoxide in tetrahydrofuran at - 20 T furnishes the highly
strained, thermally unstable tetracyclic hydrocarbon (3) which
is yellowish green in solution and could hitherto only been
trapped as the cycloadduct ( 1 5 ) (dark green crystals, m. p.
108°C) by reaction with dimethyl acetylenedicarboxylate at
0°C. Reduction of (14) by lithium tetrahydridoaluminate in
ether at 20°C affords 1,2,4,5-tetrahydrodicyclopent[cd,ij]azulene (16) as pale blue needles (m.p. 180°C,decomp.;
yield 85%).
Received: December 27. 1973 [ Z 976 IE]
German version: Angew. Chem. 86,235 (1974)
K . Hafner and J . Schnrider, Liebigs Ann. Chem. 624, 37 (1959); K .
Hafner and K . F. Bangert, ihid. 650, 98 (1961): K . Hafner, Angew. Chem.
75, 1041 (1963): Angew. Chem. intcrnat. Edit. 3, 165 (1964): K . Hafnrr,
Pure Appl. Chem. 28, 153 (1971).
[I]
[2] K . Hafnrr and R . Flrischer, Angew. Chem. 82,217 (1970): Angew. Chem.
internat. Edit. 9, 247 (1970); K. Hafner and W Rieper, Angew. Chem. 82,
218 (1970); Angew. Chem. internat. Edit. 9, 248 (1970).
[3] L. A. Puquette, R. A. Wingard, J r , and R. K . Russell, J. Amer. Chcm.
SOC. 94, 4739 (1972): G. P. Ceasar, J . Green, L. A. Paquettc,. and R . E.
Wingard. Jr., Tetrahedron Lett. 1973, 1721.
[4] E. Vogrl, U . H . Brinker, K . Nachtkamp, J . Wassen, and K . M u l l e n , Angew.
Chern. 85, 760 (1973); Angew. Chern. internat. Edit. 12, 758 (1973).
[5] The structures of the products described were confirmed by elemental
analysis, and UV, NMR, and M S spectra.
[6] K. Hafner and H. Mddes, Liebigs Ann. Chem. 606. 90 (1957).
171 Cf. K . Hafner, H. Pelster, and H. Parzelr, Liebigs Ann. Chem. 650,
80 (1961).
[S] G. Rosini, G . Baccolini, and S . Cucchi, Farmaco, Ed. Sci. 26, 153 (1971).
An Aza[l3]- and an Aza[ 17]annuIenyl
Anion['][**]
By Gerhard Schroder, Giinter Frank, Herbert Rottele, and Jean
F. M. Othr']
The pyrrolyl or aza[5]annulenyl anion has long been known
and possesses considerable interest from both a theoretical
and a preparative standpoint[''. The synthesis and properties
of the azoninyl or all-cis-aza[9]annulenyl anion have recently
been described"! We now wish to report an aza[13]- (2)
and an aza[ 17]annulenyl anion ( 5 ) .
("c3
p:
COOCvHx
I . .
( I ) , t w o isomers L4'
@
'.
dioxide in dioxane (60 'C, 3 h) affords cyclopent[cd]azulene1,2-dione (10) (10% yield, dark green needles, decomp.
> 240 C), an isomer of acenaphthenequinone.
Compound (3) was prepared similarly to ( 1 ) starting from
4,8-dimethyla~ulene'~~.
5-Methyl-l,2-dihydrocyclopent[cd]azulene ( I I ) (blue needles, m. p. 132 "C) obtained analogously
to (8) is converted into the carboxamide (12) (yield 95% ;blue
rhomboids, m. p. 1 I5 C) which is cyclized to the tetracyclic
ketimonium salt (13) (yield 45 %; perchlorate: red-brown
Anyew. Chem. internat. Edit.
1 Vol. 13 11974) No. 3
Photolysis of the adduct of ethoxycarbonylnitrene to the double bond of the four-membered ring in tricycl0[6.4.0.0~~~
']dodeca-2,4,6,10-tetraene at - 70°C affords two isomeric N [*] Prof. Dr. G Schroder, DipLChem. G. Frank, and Dr. H.Rottele
Institut fur Organische Chemie der UniversitPt
75 Karlsruhe, Richard-Willstatter-AIlee (Germany)
Prof. Dr. J . F. M. 0 t h
Organisch-Chemisches Laboratorium der ETH Zurich (Switzerland)
[**I We are grateful to Badische Anilin- & Soda-Fabrik AG, Ludwigshafen,
for a gift of cyclooctattrtraene.
205
ethoxycarbonylaza[l3]annulenes (1) [41. Photolysis of the
addition product of ethoxycarbonylnitrene to tricyclo[8.6.O.O2v9] hexadeca-3,5,7,11,13,15-hexaeneleads to three isomeric N-ethoxycarbonylaza[ 17lannulenes ( 4 ) ['I.
Treatment of the azaannulenes ( I ) and ( 4 ) respectively with
potassium tert-butoxide in T H F at 0°C alway furnishes the
same aza[ 133- and am[ 17lannulenyl anions, according to
NMR spectroscopicevidence. O n the basis of the NMR spectra
(see Table 1) and double resonance experiments considering
in particular the number of inner and outer protons, the
characteristic absorptions of the protons in (x and p position
to the nitrogen, and the coupling constants, these anions
must be assigned the configurations (2) and (5)I6]respectively.
The following three points warrant attention:
1) The configurationally isomeric azaannulene ( I ) or ( 4 )
gives rise to only one azaannulenyl anion, (2) or (5). We
thus conclude that the aza[ 131- and the am[ 17]annulenyl
anions must be configurationally labile.
2) The nonbonding electron pair on the nitrogen of (2) and
( 5 ) is directed towards the center of the ring. Taking account
of the statements made under 1, we deduce that the spatial
requirement of a hydrogen on the sp' C atom is greater
than that of the lone pair of the sp' N atom.
3) The difference between the resonance signals for the inner
and outer protons is ca. 10ppm for (2) and ca. 14ppm for
( 5 ) . These values indicate that the magnetic field induces a
considerable diamagnetic ring current in these species.
Protonation of (2) and ( 5 ) with water-saturated ether containing a small amount of acetic acid yields crystals of am[ 131(3) and aza[17]annulene (61, respectively, which decompose
on attempted melting-point determination. The compounds
were purified by column chromatography [ ( 3 ) :AI2O3 (basic);
Cpd.
Yield
(2)
0"'1
= 100 [b]
red-brown
(3)
yellow
.= 80 [b]
(5)
22
100 [c]
blue-green
(61
red
.= 60 [c]
'H-NMR,
7
Received: January 2, 1974 [Z 978 IE]
German version: Angew. Chem. 86, 237 (1974)
[ I ] Annulenes, Part 22.-Part
21: G . Schroder, G . Kirsch, and J. F . M .
Orh, Chem. Ber. 107, 460 (1974).
[2] See, e.g., M . H . Palmer: The Structure and Reactions of Heterocyclic
Compounds. E. Arnold, London 1967.
[3] A. G. Anastassiou, Accounts Chem. Res. 5 , 281 (1972): A. G . Anastassiorr
and S. W Eachus, J. Amer. Chem. SOC.94, 2537 (1972): R. T Seidner and
S. Masamune, J. C. S. Chem. Comm. 1972, 149.
[4] G. Srhroder, G. Frank, and J. F. M . 0 t h . Angew. Chem. 85, 353 (1973):
Angew. Chem. internat. Edit. 12, 328 (1973).
[ S ] G. Schrodcr, G. Heil, H . Riittele, and J. F. M . Oth, Angew. Chem. 84,
474 (1972): Angew. Chem. internat. Edit. 1 1 , 426 (1972).
[6] We cannot rule out a positional isomer of ( 5 ) in which the nitrogen
shows up at position 5 (retaining the numbering given in ( 5 ) ) .
A Simple Synthesis of 3(5)-Aminopyrazole[**]
By Giinter Eye and Philipp Arnold[']
Dedicated to Professor Hans Plieninger on the occasion of
his 60th birthday
[ppm] [a]
0.45 (la-H/d; J = 7 Hz),
0.58 (la-H/d; J=7.5 Hz),
1.90 (4H/m),
2.60 ( I H/t ; J = 9 Hz),
2.72(lH/t. J=10.5Hz),
3.08 ( I P-H/t; J = 7 Hz),
3.24 (IP-H/dd, J=7.5/10.5Hz).
12.27 ( l H / t ; J=13.5Hz),
13.05 ( I H/t; J = 14Hz)
2.72 (Iz-H/d: J = 8.5 Hz),
2.8-3.8 (7 H/m),
4.34 ( I P-H/dd; J = 6.5/8.5 Hz),
4.55 (IP-HIt: J=8.5Hz),
7.20 ( I N-H/br. s),
7.71 ( I H / t . J = 1 3 H z ) ,
7.99(IH/dd: J=11/17.5Hz)
-0.35 (Zx-H/two d ; J=6/7Hz),
0.5-1.1 (7H/m),
1.40 I I a-H (l6-H)/d.d: J = 6 / 1 3 Hz),
2 . 0 5 ( l H (10-H/t; J=lOHz),
2.70 (IP-H (3-H)/d,d: J=7/10Hz).
14.9 (4H/four t; J = 13Hz)
2.2-3.0 (9H/m) [d],
3.25 ( I P-H/d,d; J = 8 / l 1 Hz),
3.45 (lP-H/d,d; J=8/13Hz),
4.24 ( I H (10-H)/t: J=8.5Hz),
7.55(1H/t; J = 13Hz),
7.98 (IH/d,d; J = 10.5/14.5Hz),
8.5 (3 H/m, one of which is I H N-H,
(6): S i 0 2 (pentane/ether 95: 5 ) ] ; they are highly sensitive
to oxygen. The configurations ( 3 ) and (6) are unequivocally
confirmed by NMR data (see Table 1) and by the following
experiment: If a solution of ( 3 ) or (6) in CS2 is shaken
with D,O in a NMR sample tube, the intensities of the
upfield signals at t =7.20 and 8.5 respectively are each reduced
by about 1 H.
We assign the upfield signals in the 'H-NMR spectrum of
(3) and (6) to the inner protons, and the downfield signals
to the outer protons. The difference in the center of gravity
of these signals amounts to ca. 4.7 ppm for ( 3 ) and ca. 5 ppm
for (6). The induced diamagnetic ring current is now considerably smaller than in (2) and (S), but, unlike that in (1)14]
and ( 4 ) [ ' ] , it is however still readily detectable. This finding
accords with previous results for aza[9]ann~lenes'~l.
3(5)-Aminopyrazole has formerly been accessible only by way
of multistage syntheses" - '1. We now report a one-stage preparation of 3(5)-aminopyrazole (2) utilizing commercially
available starting materials and giving 70% yields of the
pure product. The reaction involves addition of aqueous hydrazine solution to 2-chloroacrylonitrile in alkaline solution
(potassium carbonate).
HA
lN$NH]
-
H
HB
H
N$NH2
H
(3)
see text)
-
[a] 100 and 60 MHz spectra, ( 2 ) and ( 5 ) in THF, ( 3 ) and (6) in C S 2 ;
<a. 25 C; TMS as standard.
[b] Based on ( I ).
[c] Based on ( 4 ) .
[d] The two r* protons appear as two doublets at 7 = 1.95 in D8-THF at
-60 C.
206
[*] Prof. Dr. G. Ege and P. Arnold
Organisch-Chemisches Institut der Universitat
69 Heidelberg, Im Neuenheimer Feld 7 (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
Angew. Chem. internat. Edit. / Vol. 13 (1974) / No. 3
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