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Macrocyclically Fixed Diarylhexatrienes.

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of novel organic materials with specific properties by incorporating classical structural building blocks into macrocyclic
systems, and we now report on the configurationally and
conformationally stiffened cyclopolyenes 1 and 2.
Fig. 2. Molecular structure obtained from CHARMMiQUANTA simulations
for the azoniacyclophane 1 with five water molecules in the cavity; hydrogen
bridges in the cavity are indicated by dotted lines.
2
1
a: R =H ; b:R=CH,
outside of the cavity, on the other hand, are stabilized by an
average of four bridges per molecule.
Received: June 25, 1990 [Z 4035 IE]
German version: Angew. Chem. 102 (1990) 1194
111 See, e.g., W. P. Jencks: Catalysts in Chemistry and Enzymology, McGraw-
Hill, New York 1969.
[2] Cf. K. Odashima, K. Koga in P. M. Kuhn, S. M. Rosenfeld (Eds.): Cyclophanes. Vol. 2, Academic Press, New York 1983, pp. 629-677.
[3] a) H.-J. Schneider, R. Kramer, S. Simova, U. Schneider, J. Am. Chem. Sot.
I10 (1988) 6442; b) H.-J. Schneider, T. Blatter Angew. Chem. 100 (1988)
1211; Angew. Chem. Int. Ed. Engl. 27 (1988) 1163; c) H.-J. Schneider, T.
Blatter, S. Simova, I. Theis J. Chem. Soc. Chem. Commun. 1989, 580.
[4] Cf. a) S. K. Burley, G. A. Petsko, Adv. Protein Chem. 39 (1988) 125; b) J.
Sunner, K. Nishizawa, P. Kebarle, J. Phys. Chem. 85 (1981) 1814; c) C. A.
Deakyne, M. Meot-Ner, J. Am. Chem. SOC.107 (1985) 474; d) M. A. Petti,
T. J. Shepodd, R. E. Barrans, Jr., D. A. Dougherty, zbid. 110 (1988) 6825;
e ) D. A. Stauffer, D. A. Dougherty, Tetrahedron Lett. 29 (1988) 6039, and
references cited therein.
cm']: H,O 1.45 (D,O 1.26).
[51 Examples of average polarizabilities
CHCI, 9.5, benzene 10.5 (Handbook of Chemistry and Physics, E66-E75,
67th edit., CRC Press, Boca Raton, FL, USA 1986/1987).
[6] a)Cf. H.-J. Schneider, I. Theis, Angew. Chem. 101 (1989) 757; Angew.
Chem. Int. Ed. Engl. 28 (1989) 753; and references cited therein; b) H.-J.
Schneider, T. Schiestei, P. Zimmermann, unpublished results.
[7] Such an effect had already been postulated for cyclodextrin complexes:
a) D. W. Griffith, M. L. Bender, Adv. Catal. 23 (1973) 209; b) W. Saenger,
Angew. Chem. 92 (1980) 343; Angew. Chem. I n t . Ed. Engl. 19 (1980) 344.
c) Diederich et al. have on many occasions emphasized the role of cohesive
forces in the formation of apoiar complexes: D. B. Smithrud, F. Diederich,
J. Am. Chem. Soc. 112 (1990) 339, and references cited therein.
[8] See, for example C. L. Brooks, M. Karplus, Methods, Enrymot. 127 (1986)
369.
Although the McMurry reaction has found wide application,12] so far it has rarely been employed for the directed
cyclodimerization of dicarbonyl compounds in one ~tep.1~1
The one-pot synthesis of the hydrocarbons 1 and 2, which
proceeds in comparatively good yields (1 a: 36 YOafter optimized coupling of5a14])makes this method attractive for the
synthesis of macrocycles.
In order to work out optimal reaction conditions, but also
for comparative purposes, we first prepared the "open
chain" triene 4 a from 3a.
4
3
The cyclization to 1 or 2 was best achieved under moderate
dilution conditions; we assume that the principle of rigid
groups plays a role thereby. The synthetic concept is widely
applicable. Thus, in addition to 1 a and 4a, the macrocycles
1 b (20%), 2a (20%), and 2 b (4% yield), as well as the triene
4b could be prepared.
TiC14/Zn
," -11.4-dioxane
R
Macrocyclically Fixed Diarylhexatrienes**
W
5
By Fritz Vogtle* and Carlo Thilgen
Open-chain and cyclic polyenes have been the subject of
intensive research in organic chemistry for many years.'']
1,6-diphenyl-l,3,5-hexatriene
(DPH), for example, is a commonly used fluorescence indicator in investigations concerning the arrangement of molecules in vesicle and cell membranes, in liquid crystal phases, and in polymer films. Our
studies in this context are currently directed to the synthesis
['I
[**I
Prof. Dr. F. Vogtle, Dip].-Chem. C. Thilgen
Institut fur Organische Chemie und Biochemie der Universitat
Gerhard-Domagk-Strasse 1, D-5300 Bonn 1 (FRG)
This work was supported by the Volkswagen-Stiftung. We thank Prof. Dr.
E. Steckhan, Universitat Bonn, for measuring and evaluating the cyclovoltammograms, and Dipl. Chem. P . M . Windscheif, Universitat Bonn,
for carrying out calculations.
1162
0 VCH
Verlagsgesellschafr mbH, 0-6940 Weinheim, 1990
The yellowish, sparingly soluble microcrystals of the cycloalkene 1, which precipitated in analytically pure form on
recrystallization from pyridine, melt in an evacuated tube
at 385-388°C (decomp). Besides the peaks for M a
[m/z = 468.2817(calcd); 468.2814(obs), base peak] and M z a
[m/z = 2341, the mass spectrum of 1a also exhibits peaks of
graduated intensity for all the dehydrogenation products
down to mlz = 456, which corresponds to the especially
stable hexa-m-phenylene[6a1 (same carbon framework). The
'H-NMR spectrum (200 MHz, CDBr,) shows the following
signals: 6 = 1.93 (m, 8H; CH,), 2.51 (m, 8 H ; CH,), 2.60 (m,
8 H ; CH,), 7.20-7.38 (m, 6H; Ar-CH), 7.57 (s, 4 H ; vinylCH), 8.08 (s, 2H; Ar-CH). A striking feature is the down-
0570-0833~90/1010-1162$3.50+ .2S/O
Angew. Chem. Int. Ed. Engl. 29 (1990) No. 10
field shift of the olefinic and aromatic protons oriented to the
center of the molecule, as has also been observed for hexa-mphenylene[6a1and kekulene.[6b]
The fully aromatized hydrocarbon 6 containing two naphthalene units could be detected for the first time after treatment of the cyclopolyene 2a with 2,3-dichloro-5,6-dicyanop-benzoquinone (DDQ) [MS: m / z = 556.2185 ( M e obs),
556.2191 ( M a calcd); 278 ( M z e ) ] .
2a
DDQ
6
1 a contains two diphenylhexatriene units with a fixed geometry, in which the double bonds are (1E, 32,5E)-configurated, and the free rotation of the benzene rings is suppressed. In the “open-chain’’ triene 4a, however, there is still
the possibility of (E)/(Z)-isomerization with regard to the
exocyclic double bond.
The diarylhexatrienes 1 , 2 and 4 allow the consequences of
configurational and confirmational fixation of the respective
chromophore on the electronic excitation to be investigated
by UVjVIS spectroscopy. The maxima of the absorption
bands of the trienes 4a, b are unstructured, and hypochromic
in comparison to those of DPH and DNH (1,6-di[2-naphthyl]-l,3,5-hexatriene), and in each case they exhibit a
bathochromic shift of 14-16 nm.I7”.b1
The red shift due to the more extended chromophore in
the dinaphthylhexatriene 4 b already manifests itself in its
deeper yellow tone when compared to that of the diphenylhexatriene 4a, whose bright yellow platelet-shaped crystals
get a green tinge by the blue fluorescence in incident light
(Fig. 1).
Whereas Zechmeister et a1.[81found a hypsochromic shift
of only 1-2 nm for the longest wavelength absorption maximum of (3Z)-DPH in comparison to its all-(a-isomer, the
corresponding difference between the “open-chain’’ all-(E)triene 4a and its cyclic counterpart 1 a with the fixed double
(3Z)-configuration amounts to 23 nm.17=IIn the case of (E)and (Z)-stilbene the difference of 15.5 nm is attributed to a
hindrance of the conjugation in the no longer planar (3-isomer.[lo1 In l a , a rotation of the benzene rings out of the
plane of conjugation may contribute to the observed shift.
The absence of an absorption band at even longer wavelength in the UVjVIS spectra of l a and 2 a confirms the
assumption that the macrocycles contain two isolated
diphenylhexatriene systems instead of a single chromophore
extended over the whole ring.[”]
The most outstanding difference between the spectra of
1 a, 2 a and those of the “open chain” analogues 4 a, b is the
occurrence of an additional band in the former at 1 = 273
and 286 nm respectively. From a theoretical viewpoint, this
is due to the absence of a symmetry center[”] and has proven
to be characteristic of the presence of a (3-double bond
within a polyene chain. The “cis-peaks” of the macrocycles
1 and 2 are striking, not only by their high extinction coefficient but also by the sole fact of their occurrence, since l a
shows an inversion center in the energetically most favorable
conformation, as is predicted by calculation^.^' 31 This obserAngew. Chem. Inl. Ed. Engl. 29 (1990) No. 10
0 VCH
210 250
300
350
LOO
150
hlnrnl
500
-
550
600
650
Fig. 1. Absorption (A) and emission (E) spectra (in 1,Cdioxane. T = 292 K,
excitation at 380-400 nm) of the diarylhexatrienes 4 a (-)
and 4 b (*)
and of the cyclopolyenes l a (---) and 2 a (...). E in relative units.
vation also suggests a division of the molecules into two
separate chromophores.
Whereas the emission maxima” of the diphenylhexatrienes DPH, 4 a and l a are located at almost the same d
(blue spectral region), a pronounced bathochromic shift
characterizes the transition to the dinaphthylhexatriene 4 b
(blue-green) and further to the cyclic dinaphthylpolyene 2 a
(green). The difference between absorption and emission
maxima is significantly larger in the case of the cyclic compounds l a and 2a than in the case of the “open chain”
analogues 4 a, b17”* (Fig. 1).
Diphenylpolyenes form cations in sufficiently concentrat16] Those of 4a, b, 1 a and 2a (in 96 %
ed sulfuric
H2S04)are deep-colored, and in each case their absorption
spectra exhibit two intense bands.[7b1From the fact that the
solutions of the cyclic ions no longer show bands of the
hydrocarbons 1 a or 2a it may be assumed that both chromophoric units of the molecules are protonated.
Deep-blue/violet solutions of anions were obtained on
treatment of the diphenylpolyenes 1 a and 4a with sodium
metal in T H E The structural variety observed for the anions
of 1,n-diphenylpolyenes [ I 7 ] should be strongly reduced in
the case of the species described here by the additional
clamping. Cyclovoltammetric measurements in pyridine afforded the first reduction potentials of the polyenes 1 a and
4a, which are superimposed to the reduction of the base
electrolyte: they have nearly the same value for “open chain”
(4a) and cyclic triene
Unlike l a , 4a displays a
quasi-reversible behavior: at potential scanning rates of
2 100 mVs-’ the reoxidation of its radical anion can be observed, indicating that the chemical stability of 4a00 is significantly higher than that of l a o e .
Hydrocarbon rings of the type described here-particularly when substituted with eight solubilizing long-chain
residues R-provide means for further manipulations of
light absorption and emission.
Verlagsgesellschaft mbH. 0-6940 Weinheim,1990
Received: May 30, 1990 [Z 3991 IE]
German version: Angew. Chem. 102 (1990) 1176
S 3.50+.2S/O
OS70-0833~90/1010-1163
1163
{I] H. A. Staab: Einfuhrung in die tbeorelische organische Chemie, Verlag
Chemie, Weinheim 1964; B. M. Krasovitskii, B. M. Bolotin: Organic Luminescent Materials, VCH, Weinheim 1988.
[2] Review: J. E. McMurry, Cbem. Rev. 89 (1989) 1513.
[3] a) D. Tanner, 0.Wennerstrom, E. Vogel, TetrahedronLett. 23 (1982) 1221;
b) K. Yamamoto, S. Kuroda, M. Shibutami, Y Yoneyama, J. Ojimo, S.
Fujita, E. Ejiri, K. Yamigihara, J. Chem. SOC.Perkin Trans. f 1988, 395;
c) E. Vogel, I. Grigat, M. Kiicher, J. Lex, Angew. Chem. fOf (1989) 1687;
Angew. Chem. Int. Ed. Engl. 28 (1989) 1653, and references cited therein;
cf. also: d) J. E. McMurry, G. J. Haley, J. R. Matz, J. C. Clardy, G. Van
Duyne, R. Gfeiter, W. Schafer, D. H. White, J. Am. Cbem. SOC.108(1986)
2932; e) H. F. Griitrmacher, E. Neumann, F. Ebmeyer, K. Albrecht, P.
Schelenz, Cbem. Ber. 122 (1989) 2291.
[4] M. Bennett, N. B. Sunshine, G. F. Woods, J. Org. Cbem. 28 (1963) 2514.
IS] As described by: a) T. Mukaiyama, T. Sato, J. Hanna, Cbem. Left. 1973,
1041; b) D. Lenoir, Synthesis 1977, 553.
161 a) H. A. Staab, F. Binnig, Chem. Ber. 100 (1967) 293; b) F. Diederich,
H. A. Staab, Angew. Chem. 90(1978) 383; Angew. Chem. Int. Ed. Engl. 17
(1978) 372.
[7] a) Am.. (absorption) [nm]: 1a 344,2a 360,4a 367,4b 395, in 1,4-dioxane;
DPH 351, in n-hexane[8]; DNH 381, in THF[9]; b)&,., [~ m *m o l - ~4] 0:
46000,4b 59000, in 1,rl-dioxane; DPH ca. 78000, in n-hexane[8]; DNH
95000, inTHF[9];c)A~,..(emission) [nm]: la448,3a490,4n447,4b470,
in 1.4-dioxane; DPH 450, in n-heptane[l4]; d) A,, (absorption) [nm] of
the cations of 1a 443,492 (deep orange), 2a 445,482 (red-brown), 4 8 419,
475 (orange), 4 b 447, 504 (red).
[8] K. Lunde, L. Zechmeister, J. Am. Chem. SOC.76 (1954) 2308.
[9] K. Mandal, T. N. Misra, Bull. Chem. SOC.Jpn. 49 (1976) 975.
[lo] A. Smakula, A. Wassermann, 2. Phys. Cbem. Abf. A f55 (1931) 353.
[11] Cf. J. Dale, Acfa Chem. Scand. if (1957) 971; cf. also [6a].
1121 a) L. Zechmeister, A. L. LeRosen, W. A. Schroeder, A. Polgar, L. Pauling,
J. Am. Chem. Soc. 65 (1943) 1940; b) R. S. Mulliken, 1 Chem. Pbys. 7
(1939) 203.
[13] MM2(86)/MMP2 calculations (on HP 9000/825S SRX) afforded o-strain
energiesof 130(la), 52((3E)-4a),and 59kJmol-1((32)-4a;notisolated);
semiempirical calculations with SCF-MNDO [MNDO 89 Version 2.3 (w.
Thiel, Wuppertal 1989), on CONVEX C220 in the scope of the special
research project SFB 334 (closed shell, singlet, RHF)] afforded SCF bond
enthalpies of 469 (la) and 279 kJmol-' (4a), respectively.
1141 A. N. Nikitina, M. D. Galanin, G. S. Ter-Sarkisyan, B. M. Mikhailov,
Opt. Spektrosk. 6 (1959) 354; Opt. Spectrosc. (Engl. Transl.) 6 (1959) 226.
[IS] R. Kuhn, A. Winterstein, Helv. Chim. Acta If (1928) 87.
[16] S. Dahne, F. Schob, J. Prakr. Chem. 3f5 (1973) 810.
[I71 R. Scbenk, W. Huber, P. Schade, K. Miillen, Chem. Ber. f2f (1988) 2201.
1181 EYd = 2.1 V versus normal hydrogen electrode (NHE), pyridine,
Bu,NBF, (0.1 M) as supporting electrolyte, T = 293 K, scanning rate
100 mVs-', potentials measured versus Ag/AgNO, (0.1 M in CH,CN),
ferrocene calibration (converted to NHE). This potential is correlated with
the value of - 1.85 V found for DPH (versus SCE; d -1.61 V versus
NHE; 96% aqueous 1,Cdioxane): G. J. Hoijtink, J. Van Schooten, E.
De Boer, W. I. Aalbesberg, Recl. Trav. Chim. Pays-Bas 72 (1954) 895.
Stable Azirinimines? A Structural Corrigendum**
By Klaus Banert,* Elisabeth Reissaus, Hans-Jorg Deiseroth,
Claus Peter Kluge, and Eva-Maria Peters
toluenesulfonyl) with cyanide ions into the chain-lengthened
product 2.[11They obtained instead a product with melting
point 130-131 "C in 15% yield, which is said to have the
surprising structure 3a. This novel azirinimine was said to be
converted into the geometrical isomer 3b (m.p. 180- 182 "C)
upon treatment with bases (NaHCO, in aqueous acetone).
As evidence in support of the structures the authors quote
spectroscopic data and secondary reactions of 3 a: reaction
of 3a with sodium methoxide in methanol is reported to give
mainly 3 b and, in a side reaction, 4. The product 3 b is likewise described as being formed from 4 under the same reaction conditions, while layer-chromatographic work-up is reported to lead to 5.
R-OTs
1
MeOH
MeONa
R=
30.b
M e 0 NH
I1
I
ROmN=C-C-CONH2
4
CONH,
CHZ-
Tso-l/o\
0 NH
II
II
RO-NH-C-C-CONHZ
5
The report['' on the synthesis and reactions of the first
azirinimines [2*31 is contrary to the hitherto known chemistry
of the 2H-a~irines.[~]
The strained heterocycles 3a, b are said
to be surprisingly stable, which is in sharp contrast to the
instability which is postulated for the azirinones 6"l and has
been demonstrated in the case of the methyleneazirines 7.16]
Usually, 2H-azirines show a "C-NMR signal for C-3 in the
range 6 = 157- 173;[41 in the case of 7 this signal is shifted
downfield (6 = 185-188), which points to the participation
of a dipolar resonance form.[61The 13C-NMR spectra"] of
3a (C3: 6 = 133.5) and 3 b (C3: 6 = 127.2) therefore appear
to be hardly reconcilable with azirinimine structures. Furthermore, one would also expect the signals for C2 to appear
at much lower field (3a: 6 = 112.3; 3 b : 6 = 106.8) if one
compares the data quoted in the literature for aziridinimines.['] In the present communication we present corrected
structures for the substances 3a, b, 4 and 5.
Dedicated to Professor Wolfgang Kirmse
on the occasion of his 60th birthday
U.: Meyer zu Reckendorf and N. Schultz recently reported
on abortive attempts to convert the sulfonate 1 (Ts = p [*I Dr. K. Banert, E. Reissaus
Fachbereich 8, Organische Chemie I1
der Universitat-Gesamthochschule
Adolf-Reichwein-Strasse,D-5900 Siegen (FRG)
Prof. Dr. H.-J. Deiserothl'], C. P. Kluge[']
Fachbereich 8, Anorganische Chemie I1
der Universitat-Gesamthohschule
Adolf-Reichwein-Strasse, D-5900 Siegen (FRG)
E.-M. Peters[+]
Max-Planck-Institut fur Festkorperforschung
Heisenbergstrasse 1, D-7000 Stuttgart 80 (FRG)
['I X-ray structure analysis.
[**I This work was supported by the Deutsche Forschungsgemeinschaft. We
thank Prof. Dr. H. Quast (Wiiaburg) for stimulating discussions.
1164
0 VCH VerlagsgesellschaftmbH, 0-6940 Weinheim, 1990
In the case of the model compound 8[*l it is not a threemembered ring, but the anisotropic effect of the cyano
which gives rise to an upfield shift of the oxime
signal in the 13C-NMR spectrum. The 13C-NMR and the
"N-NMR data of 8 resemble those of the reputed azirinimines (Table 1) to which the structures 9 and 11 should
accordingly be assigned. In order to confirm this, 11 was
sodium hydroxide
synthesized independently from 10!'ol
and lt1'l in dimethyl sulfoxide (DMSO) (16 h, 50°C, yield
91 %).1121 When 1 was allowed to react-as described in the
literature[''-with potassium cyanide and tetrabutylammo-
0570-0833/90/fOfO-lf64$3.50+ ,2510
Angew. Chem. h t . Ed. Engl. 29 (1990) No. 10
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