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Naphtho[2 3-d] [1 2 3]oxadiazole.

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Chem. Soc. Chem. Comniun. 1990, 432; H. L. Anderson, C. A. Hunter,
M. N. Meak, J. K. M. Sanders, J. Am. Chem. Soc. 112 (1990) 5780; b) metallomacrocycles, such as uranium-containing chelates, which form complexes with pyridines: A. R. van Doorn, M. Bos, S. Harkema, J. van
Eerden, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 56 (1991) 2371;
c) numerous multidentate Lewis acids that bind two molecules of the same
kind. see, e.g.: B. Bachand, J. D. Wuest. Organometallics 10 (1991) 2015.
and references cited therein; d) Note added by the editorial staff See also
the communication by E Hawthorne et al. in this issue, in which a host
compound analogous to a [12]crown-4 with four Hg atoms is reported: X.
Yang, C. B. Knobler, M. F. Hawthorne, Angew. Chem. 103 (1991) 1519;
Angew. Chem. Inr. Ed. Engl. 30 (1991) 1507.
[4] In the preceding communication we describe the synthesis of the host
compound 1 as well as its ability to bind potassium salts, KX (X = F. CI,
Br, 1, SCN. CN, OCH,) selectively: M. T. Reetz, C. M. Niemeyer. K .
Harms, Angew. Chem. 103 (1991) 1515; Angew. Chem. Int. Ed. Engl. 30
(1991) 1472.
[S] The "B NMR spectrum (CD,CI,, BF,-ether as external standard) of 2
shows one signal at 6 = 9.0, a reliable indication of the presence of a
compound with tetracoordinated boron (41. The 'Hand I3C NMR spectra
exhibit chemical shifts characteristic of cation inclusion [4].
16) Crystallographic data for 2 toluene (C,,H,,BNO,, M, = 689.6): triclinic, space group P1,a = 1093.8(1), b = 1392.3(1), c = 1447.7(2) pm, c( =
101.16(1), /l = 109.52(1), 7 = 104.29(1)". Z = 2 , Q . . , . ~ = 1.193 gcrn--',
~(CU,,)= 6.42 cm-'. Measurement carried out on an Enraf-Nonius
= 1.54184 A, graphite monoCAD4 diffractometer (Cn,, radiation, i.
chromator, T = 190 K); 4666 measured reflections, 4404 of which are
independent (R,,, = 0.0185), 4081 with F > 4a(F) were regarded as observed. Solution by direct methods and refinement with the Siemens
SHELXTL-PLUS(VMS) program package, R = 0.0641, R, = 0.0797
(w = l/u'(F)); all non-hydrogen atoms refined anisotropically; N- and
0-bonded H atoms localized; the others "riding" with groupwise common
isotropic temperature factors. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum
Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH,
W-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository
number CSD-320298, the names of the authors. and the journal citation.
171 In order to generate the space-filling representation, the X-ray data were
processed on a Silicon graphics computer using the Sybyl program.
[8] See, e.g.: D. J. Cram, K. N. Trueblood. Top. Curr. Chern. 98 (1981) 43; I.
Goldberg in S. Patai, Z. Rappoport (Eds.): Crown Ethers and Analogs,
Wiley, Chichester, England 1989, p. 359.
[9] In a typical experiment, 0.1 mmol of host 1 and 0.1 mmol of an amine were
placed in 1 mL of dry CD,CI, at room temperature and treated with
0.2 mmol of each alcohol. The analysis was carried out by I3C NMR
spectroscopy at room temperature. When 1.3, or 5 mmol of the methanol/
ethanol pair was used, no change in the selectivity was observed. The
selectivities thereby obtained (Table 1) provide no information concerning
the absolute magnitudes of the binding constants, which are the subject of
a more detailed investigation.
1101 The equilibrium constants for the reaction of boranes and amines to form
borane/amine adducts were measured by Brown et al. and interpreted on
the basis of front strain: H. C. Brown, R. B. Johannesen, J. Am. Chem.
SOC.75 (1953) 16; H. C. Brown, Rec. Chem. Prog. 14 (1953) 83; Related
studies have recently been reported by Yamamoto et al. on this kind of
molecular recognition in the complexation of ethers and carbonyl compounds by bulky aluminum compounds: K. Marnoka, S. Nahahara, H.
Yamamoto. J. Am. Chem. Sor. 112(1990) 6115; K. Maruokoa, S. Nagahara. H. Yamamoto, Terruhedron Let[. 31 (1990) 5475.
[ll] The host was prepared in the same way as 2 [4].
1121 An indication of the weaker complexation is the fact that rapid exchange
processes are detectable by NMR spectroscopy for the ammonium components at room temperature. In this case the competition experiments were
therefore carried out at - 40°C.
[13] Crystallographicdata forl(C,,H,,BNO,, M, = 567S):monoclinic, space
group P2/n, a = 1535.9(3). b = 994.4(2). c = 2067.8(4) pm, /l = 105.55(3)",
Z = 4,
= 1.239 gcm-3. ~(CU,,)= 6.82 cm-'. Measurement carried
out on an Enraf-Nonius CAD4 diffractometer (Cu,, radiation, 2. =
1.54184 A, graphite monochromator, T = 190 K); 4290 measured reflections, 3830 of which were independent (& = 0.0660); 2605 with F >
4a(F) were regarded as observed. Solution by direct methods and refinement in Siemens SHELXTL-PLUS(VMS) program system, R = 0.0686,
R, = 0.0613 (w = l/u2(F)),all non-hydrogen atoms relined anisotropically; N-bonded H atoms localized; the others were refined using the riding
model with gronpwise common isotropic temperature factors. Further
details of the crystal structure determination are available on request from
the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, W-7514 Eggenstein-Leopoldshafen 2,
on quoting the depository number CSD-320335, the names of the authors,
and the journal citation.
[14] For example, host 1 can bind water and benzylamine in the same way as
2. Furthermore, preliminary experiments show that hosts form 1 : 1 inclusion complexes with amines and even ammonia.
1476
VCH ~ ~ e r l u g s ~ e . ~mbH,
~ l l sW-6940
~ h ~ ~ Weinheim,
~
1991
Naphtho[2,3-4 [1,2,3]oxadiazole**
By Achim Blocher and Klaus-Peter Zeller *
Dedicated to Professor Michael Hanack
on the occasion of his 60th birthday
The early history of "diazoanhydrides", obtained on diazotization of a-amino /?-keto esters and of o-aminophenols,
is marked by controversy over the constitution of these compounds.['] Much evidence initially favored the presence of
1,2,3-oxadiazoles of type 1 and 2, respectively. In the end,
however, the application of spectroscopic methods settled
this structural discussion in favor of the isomeric ct-diazo
carbonyl compounds 3 and the o-quionone diazides 4, respectiveIy.[21
1
2
3
E = COOEt
R a ; 2
4
Only recently were Schulz and Schweigf3.41 able to detect
the formation of an equilibrium[5]between the parent compound, the o-quinone diazide 5, and its valence isomer, the
benzo[l,2,3]oxadiazole 6, in the gas phase and in nonpolar
solvents and thus provide the first experimental evidence for
the existence of this five-membered heterocycle.
- a"pr
0
5
6
The o-quinone diazide 8, expected on deprotonation of the
diazonium tetrafluoroborate 7,contains the o-quinone bismethide substructure A together with the o-quinonoid structural element B. On going to naphtho[2,3-d][1,2,3]oxadiazole
(9), both of these energetically unfavorable structures should
give way to the more stable naphthalene system. Thus, the
cyclization to 9 should be particularly favored.
We have carried out the deprotonation of 7[61on basic
alumina and sublimed the product (which is slightly colored
owing to impurities) at about 10°C under vacuum. The white
to pale lemon yellow solid thereby obtained is stable for
several days in the dark at - 20°C. Its spectroscopic data
9
10
[*I Prof. Dr. K.-P. Zeller, Dipl.-Chem. A. Blocher
lnstitut fur Organische Chemie der Universitat
Auf der Morgenstelle, W-7400 Tubingen (FRG)
[**I This work was supported by the Fonds der Cbemischen Industrie
0570-0N33/91/l/fl-1476S 3.50+.25/0
Angew. Chem. Ini. Ed. Engl. 30 ( 1 9 9 1 ) No. 11
rule out both the o-quinone diazide structure 8 and the equally
conceivable a-carbonyl diazirine structure lo,['' but are consistent with 9. To the best of our knowledge, 9 is the first
1,2,3-oxadiazole to be isolated in pure form.
In the I R spectrum (KBr), the intense diazo and carbonyl
bands typical of o-quinone diazides are absent. If the KBr
disk is exposed to daylight for a few minutes and the IR
spectrum recorded again, intense bands appear at 2090
(v(C=N=N)) and 1627 cm-' (v(C=O)), indicative of the
photochemical ring opening 9 -+ 8. If the disk is kept in the
dark for 30 min at 20°C, the initial spectrum is obtained
once again.
The 'H and 13C NMR spectra indicate that compound 9
is a 2.3-disubstituted naphthalene derivative; this structure is
supported in particular by the lowest-field I3C NMR signal
(6 = 148.7). which is at markedly higher field than that of a
carbonyl C atom of o-quinone diazides, which usually show
a chemical shift of 6 = 180.'8]
In the 70 eV mass spectrum (rn/z,rel. int.), the molecularion peak, M + (1 70, 10 %), is accompanied by intense peaks
corresponding to the fragment ions [ M - N,] (142, 100°/~)
and [ M - N, - CO]@(114, 14%).
Table 1 . Spectroscopic data for 9.
IR(KBr): F[cm-'] = 1626(m),1611 (m). 1594(m), 1503(m), 1464(s).1457(s).
1443 (in). 1376 (m),...
After direct irradiation of the KBr disk with sunlight (filtered through a glass
1696(s),1684(s).
window)for7min[a]: C[cm-'] = 2090(~),1718(~),1700(s).
1675 (m). 1627 (s). 1617 (m), 1601 (m). 1576 (m), 1565 (m). 1560 (m). 1499 (s),
1457 (s). . . .
'H NMR (200 MHz. CDCI,, - 20°C): d = 8.58 (s. 1 H : H-9). 8.04-8.01 (d.
1 H. J = X.3 Hz: H-5 or H-8). 7.97-7.94(d, 1 H. J = 8.5 Hz; H-5 or H-8). 7.91
(s, 1 H : H-4). 7.63-7.57 (t. l H , J = 7 . 6 H z ; H-6 or H-7). 7.51-7.45 (t. l H ,
J = 7.6 H r ; H-6 or H-7)
"C NMR (200 MHz, CDCI,, - 20'C): 6 = 148.7 (C-9a). 137.6 (C-3a). 135.7,
130.O(C-4a.8a), 129.4. 128.8, 128.0, 125.1 (C-5.6,7,8). 121.2(C-4), 103.8(C-9)
UV/VlS (n-heptane): E., (loga) = 358 (3.37), 31 1 (4.00). 298 (3.84). 286 (3.56).
239 (4.54). 213 (4.54) nm
UV/VlS (95% methanol/5% n-heptane) [b]: i,,,
(log&)= 547 (3.07). 335
(3.70). 317 (3.76). 298 (3.73). 246 (4.43). 213 (4.33). 198 (4.03). 192 (3.98) nm
[a] Photochemical valence isomerization to 8. [b] Formation ofan equilibrium
mixture between the valence isomers 8 and 9.
The UVjV1.S spectrum of 9 in n-heptane is similar in structure to that recorded for benzo[l,2,3]oxadiazole 6 in solution.l4l As expected, the positions of the bands are shifted to
longer wavelengths. The spectrum of 9 in polar methanol is
significantly different. We interpret this change as evidence
of partial ring opening to give 8, in analogy to the system
5 ~ 6 .The
I ~absorption
~
in the visible (I,,, = 547 nm, E,,, =
1200). in contrast to the short-wavelength absorptions, remains unchanged on going back to nonpolar n-heptane and
is therefore presumably due to a secondary product of the
ring-opened o-quinone diazide 8.
Photolysist9~
of a 4.7 x
molar solution of 9 in methanol affords, as main product, 2-(methoxycarbonyl)indene
(13) (59% yield).["' As indicated by the UVjVIS spectrum,
9 forms an equilibrium with its valence isomer 8 in methanol.
9 (MeOH),
8
3
a
C
=
O
11
12
Angew. Chem. Inl. Ed. Engl. 30 (1991) No. 11
In addition, as already noted, 8 can be formed photochemically from 9. We assume that the observed loss of N, and the
ring closure preceed as expected for a Wolff rearrangement"
of an o-quinone diazide, via the ketene 11 and the ester 12['']
as intermediates.
Experimental Procedure
9: A solution of 7 (100 mg, 0.388 mmol) in about 80 mL of methanol was
concentrated to about 3 m L at ca. 20°C and then transferred to a cooled
column (ca. 10°C) filled with 100 g of basic AI,03 (Woelm B. activity 1) and
immediately eluted (eluent: petroleum etherlethyl acetate 1:1). Concentration
of the eluate afforded 74 mg of crude product, which was dissolved in a small
amount of dichloromethane and transferred to a sublimation apparatus. The
sublimation was carried out in the dark (bath temperature ca. 10°C. cold finger
temperature - 7 0 ° C 0.01 Torr). Yield: 14.3 mg (22%). The product could be
stored in thedark at - 20°C for two days without any noticeable spectroscopic
changes. At ZO'C. 9 gradually turns brown. Above 77°C. it decomposes explosively.
Received: December 11, 1990 [Z4319 IE]
Publication delayed at the authors' request
German version: Angew. Chem. 103 (1991) 1489
CAS Registry numbers:
7. 136445-42-6; 9,70304-47-1 ; 13, 17332-04-6.
[l] For a short historical discussion of this intriguing controversy about the
constitution, see L. C. Behr in R. H. Wiley (Ed.): The ChemDtry ofHerrrocyclic Compounds, Vol. 17, Interscience Publishers, New York 1962.
p. 235.
[2] M. Regitz. Diuzoalkane, Thieme. Stuttgart 1977.
[3] R. Schulz, A. Schweig, Angew. Chem. 91 (1979) 737; Angew. Chem. I n / . Ed.
Engl. 18 (1979) 692.
141 R. Schulz, A. Schweig, Angew. Chem. 96 (1984) 494; Angew. Chem. Inr. Ed.
Engl. 23 (1984) 509.
[5] The valence isomerization 5 + 6 can be regarded as a pericyclic I .5-electrocyclization: R. Huisgen, Angew. Chem. 92 (1980) 979; Angew. Cheni. Int.
Ed. Engl. 19 (1980) 947.
[6] Synthesized by diazotization of 3-amino-2-hydroxynaphthalenein analogy to M. P. Doyle, W. J. Bryker, J. Org. Chem. 44 (1979) 1572. Recrystallization from acetoneln-pentane (2:l); yield 82% 7, m.p. 143-4'C (dec.).
IR (KBr): t = 2244cm-' (C=C=N).
[7] Several cr-carbonyl diazirines are obtainable by photochemical valence
isomerization of x-diazo carboxamides: R. A. Franich, G. Lowe. J. Parker,
J. Chem. Soc. Perkin Trans. 11972,2034; E. Voigt, H. Meier. Angew. Chem.
87 (1975) 109; Angew. Chem. I n t . Ed. Engl. /4 (1975) 103.
181 Cf., for example. R. Radeglia. J. Egler, A. Hauser, S. Simova. J. Schrdml.
Z. Chem. 24 (1984) 259.
191 Hanovia 450-W medium-pressure lamp, Pyrex filter.
[lo] Identified by comparison with authentic 13 (m.p. 80°C): J. Vebrel, R.
Carrie, Bull. Soc. Chim. Fr. 1982 116; I3C NMR: B. Eliasson. U. Edlund.
J. Chem. Soc. Perkin Trans. II 1981 403.
[ I l l H. Meier, K.-P. Zeller, Angew. Chem. 87(1975) 52; Angeiv. Chum. Int. Ed.
Engl. 14 (1975) 32.
[12] Both the ketene I 1 and the ester 12 display an interesting o-quinone bismethide structure. Matrix isolation and trapping experiments are planned
[{Fe(p-'S4')jz(p-S2)]: A Model Complex for
[Fe-S] Enzymes with a New Type of [2Fe-ZSI
Center""
By Dieter Sellmann,* Giinter Mahr, and Falk Knoch
Enzymes containing iron-sulfur centers are ubiquitous in
nature and are found, for example, in ferredoxins, hydro[*] Prof. Dr. D. Sellmann, Dip1.-Chem. G. Mahr, Dr. F. Knoch
["'I
13
0 VCH
Institut fur Anorganische Chemie I1 der Universitat
Egerlandstraae 1, W-8520 Erlangen (FRG)
'S,"- = 2,2'-(ethylenedithio)dibenzenethiolate.Transition Metal Complexes with Sulfur-Containing Ligands. Part 77. This work was supported
by the Deutsche Forschungsgemeinschaft. the Bundesministerium fur
Forschung und Technologie, and the Fonds der Chemischen Industrie.
Part 76: D. Sellmann, S. Funfgelder, F. Knoch. M. Moll, Z. Nuturforsch.
466 (1991). in press.
Verlugsgesellschafi mbH. W-6940 Weinheim, 1991
0570-083319ljllll-1477 $3.50+.25/0
1417
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