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Beltlike Aromatic Hydrocarbons by Metathesis Reaction with Tetradehydrodianthracene.

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temperature with occasional agitation. The supernatant was separated by ultrafiltration (Centricon, Amicon, cut-off 30 kDa, 6 h at 15 "C). The nanotubes were
then washed with water (0.6 mL), and the separation was repeated. In a control
experiment (to check for adsorption of DNA onto the membrane filter), DNA
solution was added to the ultrafiltration tube in the absence of nanotuhes, and the
separation and washing steps carried out as before. DNA concentrations were
determined from the absorption at 260 nm. The recovery of DNA in the control
experiment was >87%. A second set of experiments was carried out with 0.1 M
NaCIO, to wash the tubes, and then melting curves for the desorbed DNA were
determined by UV.
Molecular rnodelmg: A bifunctional Pt adduct was constructed on one strand of a
B-DNA model with the HyperChem program [19] and restrained energy minimization, followed by docking of the ammine ligands in an appropriate geometry. This
produced a model of the bifunctional adduct similar to those obtained with Newton- Raphson energy minimization and a force field developed for PtiDNA interactions [20]. Iodine atoms were then added to the 5-positions of each cytidine base.
Beltlike Aromatic Hydrocarbons by Metathesis
Reaction with Tetradehydrodianthracene""
Stefan Kammermeier, Peter G. Jones, and
Rainer Herges*
One of the main motivations for the synthesis of cyclophanes
is the preparation and investigation of compounds in which the
n-electron system is spherically deformed by the introduction of
bridging ligands (Scheme 1, left) .[IJ Fully conjugated belt- and
Received: December 3, 1996
Revised version: May 23, 1997 [Z9850IE]
German version: Angen. Chem. 1997,109, 2291 -2294
- immobilization
- nanotubes - oligonucleotides
Keywords: electron microscopy
recognition
*
molecular
Scheme 1. Spherically deformed
conjugated system (right)
[l] K. M. Millan, A. J. Spurmanis, S. R. Mikkelsen, Electroanalysis 1992,4, 929932.
[2] P. Pantano, W. G. Kuhr, Electroanalysis 1995, 7, 405-416.
[3] H. J. Dai, E. W. Wong, C M. Lieber, Science 1996, 272, 523-526.
[4] S. Iijima, Nature 1991, 354, 56-58.
[5] T. W Ebbesen, P. M. Ajayan, Nature 1992, 358, 220-222.
[6] S. C. Tsang, J. J. Davis, M. L. H. Green, H. A. 0. Hill, Y C. Leung, P. J. Sadler
J: Chem. SOC.Chem. Commun. 1995, 1803-1804,
[7] R. M Lago, S . C. Tsang, K. L. Lu, Y K. Chen, M. L. H. Green, J: Chem. SOC.
Chem Comm. 1995, 135551356,
[XI S. C. Tsang, Y K. Chen, P. J. F. Harris, M. L. H. Green, Nature 1994, 372,
159-162.
[9] G. C. K. Roberts, N M R of Macromolecules. a Practical Approach, Oxford
University Press, Oxford, 1993.
[lo] J. Reedijk, Chem. Commun. 1996, 801-806.
[ l l ] K. J. Barnham, S. J. Berners-Price, T. A. Frenkiel, U. Frey, P. J. Sadler,
Angew Chem. 1995, 107, 2040-2043; Angew. Chem. I n t . Ed. Engl. 1995, 34,
1874- 1877.
[12] S. J. Berners-Price, K. J. Barnham, U. Frey, P. J. Sadler, Chem. Eur. J: 1996,
2. 1283-1291.
[13] R. J. H. Clark, E. E. Hester, Sperrroscopy of Biological Systems, Wiley,
Chichester, 1986.
[14] R. Henderson, Q.Rev. Eiophys. 1995,28, 171-193.
[15] Y S Melnikova, N. Kumazawa, K. Yoshikawa, Biochem. Biophys. Res. Commun. 1995,214, 1040-1044.
j16] S. J. S. Kerrison, P. J. Sadler, J: Chem. SOC.Chem Commun. 1977, 861-863.
[17] S. 1. Berners-Price, U. Frey, J. D.Ranford, P. J. Sadler, J. Am. Chem. Soc.
1993,115, 8649-8659.
[18] J. Stonehouse, G. L. Shaw, J. Keeler, E. D. Laue, J. Magn. Reson. Ser. A 1994,
174-184.
[19] HyperChem, Release 2 for Windows, Autodesk, Sausalito, California, USA.
[20] T. W. Hambley, Inorg. Chem. 1991, 30, 937-942.
R
systems in a cyclophane (left) and in a beltlike
tubelike structures can be viewed as an extreme example of such
a deformation (Scheme 1, right)."] The p orbitals in these structures are perpendicular to the surface of a cylinder and their
inner lobes point towards the axis of the cylinder. To date,
three such systems have been prepared by conventional synthesis and isolated as stable compound^.^^
Formally, the nanotubes generated by vaporization of carbon[@and chemical
vapor deposition (CVD)['] also belong to this class of compounds.
Our approach to the synthesis of molecular belts and tubes is
based on the ring enlargement metathesis[*] of tetradehydrodianthracene 1 (TDDA).[91Scheme 2 illustrates the molecular unit
construction system employed. a) Bianthraquinodimethanes
are obtained starting from TDDA 1 and noncyclic a l k e n e ~ ; ~ ~ ]
b) cyclophanelike, bridged bianthraquinodimethanes are available from TDDA and cyclic a l k e n e ~ ; [c)~ ]tubelike anthracene9,10-bisylidenes, which are connected by quinoid double
bonds, can be constructed by dimerizing metathe~is;'~]
and
d) bianthraquinodimethanes bridged by conjugated chains are
formed from [ n l a n n ~ l e n e sThe
. ~ ~double
~
bonds in the bridge of
these beltlike conjugated systems should again be able to undergo metathesis with TDDA. This should provide access to larger
conjugated systems composed of anthracenylidene units connected by quinoid double bonds and diene units in an alternating sequence. We now report on the synthesis of the smallest of
these beltlike, fully conjugated systems which has 20 carbon
atoms in its perimeter (n = 0, Scheme 2d).
In principle, cyclobutadiene, the smallest [nlannulene, would
be suitable for the synthesis of the conjugated, bridged bianthraquinodimethane. Cyclobutadiene can be generated in
situ["J and also undergoes [2 + 2]~ycloadditions;~' however,
-
[*I Prof. Dr. R. Herges, Dr. S. Kammermeier
Institut fur Organische Chemie der Technischen Universitat
Hagenring 30, D-38106 Braunschweig (Germany)
Fax: Int. code +(531)391-5266
e-mail : r. herges@tu-bs.de
Prof. Dr. P. G. Jones
Institut fur Anorganische und Analytische Chemie der Technischen Universit& Braunschweig
[**I This work was supported by the Deutsche Forschungsgemeinschaft and by the
Fonds der Chemischen Industrie (scholarship for S. K.).
2200
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Angew. Chem. I n t . Ed. Engl. 1997,36, No. 20
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Figure 1 X-ray crystal structure of 5
n
n
filter,[151room temperature, 1 h) directly leads to
cyclophane 6 (“Kammermeierphane 2”“ 31),
which has the molecular formula C,,H,,
(Scheme 4).
Scheme 2. Molecular unit construction system for the synthesis of molecular belts
and tubes.
we chose the more comfortable detour via a-pyrone and 1,2-diazine. Both dienes react with TDDA 1 in boiling toluene yielding the Diels-Alder adducts 2[”] and 3, which eliminate CO,
and N,,respectively (Scheme 3). Electrocyclic ring opening reIn
sults in the desired product 5 (“Kammermeierphane
contrast to 3, adduct 2 can be isolated and characterized.
the bridging
According to the X-ray analysis (Figure
ethene unit in 5 is syn with respect to the two quinoid double
bonds. The Cs-symmetricalstructure is also in agreement with a
thermochemically allowed electrocyclic ring opening of 4.
1
5
/
Scheme 4 Synthesis of 6 by metathesis of 1 with 5
4
110°C
-N/
“
i
I
--+
Ill
a) 36%
5
b) 80%
3
Scheme 3 Synthesis of ‘ Kammermeierphane 1” 5 by reaction of 1 with a) m-pyrone and b) 1,2-diazine
The sterically easily accessible double bond in the bridging
part of 5 can serve as the reaction partner in a second metathesis
reaction with TDDA 1. Photochemically induced metathesis of
1 with 5 (benzene, 15OW high-pressure mercury lamp, quartz
Angew Chem
In! Ed Ettgl 1997,36,No. 20
0 WILEY-VCH
Compound 6 is composed of two bianthraquinodimethane
units, which are connected by C-C bonds such that a fully
conjugated beltlike system is formed. The structure of 6 can be
viewed as a subunit of a (5,5)-armchair nanotube.[16’According
to AM1 calculations[171and simple considerations based on
space-filling models, the 1,3-butadiene units in the bridge must
have s-trans configuration (C,,,) . The s-cis/s-trans (C,) and s-cis1
s-cis (C2Jconfigurations are not possible for steric reasons and
would be highly strained. The NMR spectra confirm the C2,,symmetrical structure. Because the structure itself prevents rotation about the single bonds, 6 has a rigid conformation. According to AM1 calculations the cavity of the approximately
rectangular tube has dimensions of 7.9 x 4.8 A. Figure 2 shows
the calculated van der Waals surface of 6. Based on the strategy
illustrated in Scheme 2, it should be possible to synthesize larger
belt- and tubelike n systems.
Experimental Section
2 : A solution of 1 (100 mg, 0.284 mmol) and a-pyrone (82 mg, 0.852 mmol) in
toluene (60 mL) was heated at reflux for 30 h. During the reaction two portions of
a-pyrone were added (82 mg each). The solvent was removed in vacuo and the
residue was purified by chromatography with hexane/ethyl acetate 2/1 on silica gel
Verlag GmbH, D-69451 Weinheim, 1997
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2201
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a) F. Vogtle, Cyclophane Chemistry, Wiley, Chichester, 1993, b) F. Diederich,
Cyclophanes, The Royal Society of Chemistry, London, 1991; c) G. J. Bodwell,
Angew. Chem. 1996, 108, 2221-2224, Angeus. Chem. Ini. Ed. Engl. 1996, 35,
2085 - 2088.
I For a review of beltlike but not fully conjugated molecules see a) A. Schroder,
H.-B. Mekelburger, F. Vogtle, Top. Curr. Chem., 1994,172,178-201 ; for more
recent work see b) H. Meier, K. Miiller, Angew. Chem. 1995, 107, 1598- 1600;
Angen,. Chem. Inr. Ed. Engl. 1995,34,1437-1438; c) M. G. Banwell, D. C. R.
Hockless, J. M. Walter, Chem. Commun. 1996,1469-1470; d) S . Breidenbach,
S. Ohren, E Vogtle. Chem. Eur. J 1996,2, 832-837.
S. Kammermeier, R. Herges, Angen,. Chem. 1996, 108, 470-472; Angew.
Chem. Ini. Ed. Engl. 1996, 35,417-419.
S. Kammermeier, P. G. Jones, R. Herges, Angew. Chem 1996, 108, 28342836; Angen. Chem. Int. Ed. Engl. 1996,35,2669-2671.
T. Kawase, H. R. Darabi, M. Oda, Angen. Chem. 1996, 108, 2803-2805;
Figure 2. AM1-calculated van der Waals surface of "Kammermeierphane 2" 6
Angew. Chem Int. Ed. Engl. 1996,35, 2664-2666.
(C60H36).
I a) S. Iijima, Nature 1991,354, 56-58; b) S. Iijima, T. Ichihashi, Y Ando, ibid.
1992,356, 776-778; c) for a review see: R. S. Ruoff, ibid. 1994,372, 731 -732.
I K. Hernadi, A. Fonseca, J. B. Nagy, D. Bernaerts, J. Riga, A. Lucas, Synth.
Met. 1996, 77, 31 -43.
(R,= 0.37). Compound 2 was obtained as a colorless solid. Yield: 90 mg (71 X).
a) G. Schroder, J. F. M. Oth, Tetrahedron Lett. 1966,4083-4088; Reviews: b)
M.p.229"C(decomp); 'HNMR(400 MHz, CDCI,):6 =7.72(m, 1 H;CH,arom.),
G. Mehta, J. Chem. Educ. 1982,59, 313-316, c) G. Kaupp, Methoden Org.
7.58 (m, 1 H; CH, arom.), 7.17 (m, 6H; CH, arom. and CH=CH), 6.90 (m.10H;
Chem (Houben Weyl) 4th ed. 1952- , Vol. IV/5a, pp. 298-299; d) H. Quast, P.
CH, arom.), 5.95 (dd, J = 4.3 Hz, J = 2.9 Hz, 1 H; CH, saturated), 4.39 (dd,
Eckert, Angew. Chem. 1976,88, 150-151, Angew. Chem. Int. Ed. Engl. 1976,
J = 5.1 Hz, J = 2.7 Hz, 1 H; CH, saturated); 13C NMR (100.6 MHz, CDCI,):
15, 168-169; e) B. A. R. C. Bulusu, P. R. Spur, R. Pinkos, C. Grund, W.-D.
6 = 174.16 (C=O), 150.76 (CJ, 150.76 (CJ, 147.95 (CJ, 147.29 (CJ, 147.26 (CJ,
Fessner, D. Hunkler, H. Fritz, W. R. Roth, H. Prinzbach, Chimia 1987, 41,
146.95 (CJ, 144.38 (CJ, 143.56 (CJ, 143.09 (CJ, 142.87 (Cq), 133.43 (CH=CH),
32-36.
132.23 (CH=CH), 126.79 (CH, arom.), 126.51 (CH, arom.), 126.38 (CH, arom.),
a) R. L. Viavattene, F. D. Greene, L. D. Cheung, R. Majeste, L M. Trefonas,
126.38(CH, arom.), 126.38 (CH, arom.), 126.12 (CH, arom.), 125.98(CH, arom.),
J Am. Chem. Soc. 1974,96,4342-4343; b) R. Herges, H. Neumann, Liebigs
125.21 (CH, arom.), 125.21 (CH, arom.), 125.07 (CH, arom.), 124.78 (CH, arom.),
Ann. 1995,1283-1289; c) R. Herges, H. Neurnann, F. Hampel, Angew. Chem.
124.71 (CH, arom.), 124.10 (CH, arom.), 123.93(CH, arom.), 123 56 (CH, arom.),
1994, 106, 1024-1026, Angew. Chem. In?. Ed. Engl. 1994,33,993-995; d) S .
123.56(CH, arom.), 79.04 (CH, saturated), 66.12 (Cq, saturated), 61.78 (CJ, 49.46
Kammermeier, H. Neumann, F. Hampel, R. Herges, Liebig.7 Ann. 1996,1795(CH, saturated); IR (KBr): C = 3061,3037 cm-' (m,C-H,arom), 1754 (s,C=O),
1800.
1634 (w. C=C, olef.),1451 (s, C=C, arom.), 1361 (m), 1181 (m), 1019 (m), 768 (s,
a) G. F. Emerson, L. Watts, R. Pettit, J Am. Chem. SOC.1965,87,131-133; b)
C-H, arom.); UV/Vis (CH,CI,): 1,,, ( 6 ) = 230 (20100), 272 (1700, sh), 280 nm
R. P. Dodge, V. Schomacher, Nature 1960, 186, 798-799.
CO,]; C,H
(1200, sh); MS (70 eV): m / z (%): 448 (47) [M'], 404 (100) [M'
a) L. Watts, J. D. Fitzpatrick, R. Pettit, J Am Chem. SOC.1966, 88, 623-624;
analysis (C3,H2,,02): calcd C 88.36, H 4.50; found C 88.06, H 4.90.
b) J. C. Barborak, L. Watts, R. Pettit, ibid. 1%6, 88, 1328-1329.
5 (Kammermeierphane 1): Method a from Scheme 3: Thermolysis of 2: A solution
This proves the high reactivity of TDDA 1in [4 + 2]cycloadditions. Under these
of 2 (106 mg, 0.237 mmol) in xylene (50 mL) was heated at reflux for 16 h. After
conditions reactions of n-pyrone with even very reactive dienophiles like maleic
removal of the solvent in vacuo the residue was purified by chromatography on
anhydride do not proceed with more than 50% yield: E. Pfaff, H. Plieninger,
silica gel with hexane/dichloromethane 2/1. 5 was obtained as a colorless solid.
Chem. Ber. 1982, 115, 1967-1981, and references therein.
Yield: 54 mg (51 %). M.p. 242°C; 'H NMR (400 MHz, CDCI,): 6 =7.58 (m, 2 H ;
Named after one of the authors, Stefan Kammermeier.
CH,arom.),7.47(m,2H;CH,arom.),7.19(m,2H;CH,arom),7.07(m,6H,CH,Crystal structure analysis o f 5 : 5.CHC13,C,,H,,CI,, M , = 523.85, monoclinarom.), 6.96(m,4H; CH, arom.), 6.45 (m.2H; HC=C), 5.86(m, 2 H ; HC=C); 13C
ic, space group P2,/n, a =799.2(1), b = 2137.7(3), c =1477.4(2) pm, =
NMR (100.6 MHz, CDCI,): 6 = 142.20 (CJ, 140.56 (CJ, 140.12(Cq), 139.96(CJ,
90.06(1)", V = 2.5242 nm3, 2 = 4, p..,., = 1.378 Mgm-', F(OO0) = 1080,
136.59 (CJ, 136.00 (CJ, 130.00 (CH, arom.), 126.84 (CH, arom.), 126.71 (CH,
~(Mo,.) = 0.39 mm-', T = -100"C.Acolorlessplate0.5x0.5x0.3mmwas
arom ), 126.53 (CH, arom.), 126.42 (CH, arom.), 125.75(CH, arom.), 125.19 (CH,
mounted in inert oil and brought into a stream of cold gas in the diffractometer
arom.), 125.19 (CH, arom.), 124.56 (CH, arom.), 121.44 (CH, arom.); IR (KBr):
(Siemens, P4). 4772 Reflections were registered up to 29 = 50" by o-scans, of
= 3061, 3035, 3013 cm-' (m, C-H, arom, olef.), 1633 (m, C=C, olef.), 1450 (s,
which 4438 were independent (R,,, = 0.023). The structure was solved with
C=C, arom.), 768 (s, C-H, arom.); UV/Vis (CH,CI,): i
,
,
,
( 6 ) = 230 (41000 ),
direct methods and refined anisotropically versus F z (program SHELXL-93,
272 nm (20400, sh); MS (70 eV): m / z ( O h ) : 404 (100) [M']. 200 (10); C,H analysis
G. M. Sheldrick, Universitat Gottingen). Hydrogen atoms were considered
(C3,Hz0):calcd C 95.02, H 4.98; found C 94.81, H 5.04.
using a riding model. The final w,R(F2)value was 0.129 for all reflections, with
Method b from Scheme 3: Diels-Alder reaction of 1 with 1,2-diazine: A solution of
conventional R(F) = 0.050; S = 0.95, max. A p = 592 enrn-,. Crystallograph1 (100 mg,0.284 mmol) and 1,2-diazine (350 mg, 4.38 mmol) in toluene (70 mL) was
ic data (excluding structure factors) for the structures reported in this paper
heated at reflux for 20 h. After removal of the solvent in vacuo the residue was
have been deposited with the Cambridge Crystallographic Data Centre as
purified by chromatography on silica gel with hexane/dichlormethane 211
supplementary publication no. CCDC-100360. Copies of the data can be ob( R , = 0.26). 5 was obtained as a colorless solid. Yield: 92 mg (80%).
tained free of charge on application to The Director, CCDC, 12 Union Road,
Cambridge CBZlEZ, UK (fax: Int. code +(1223)336-033; e-mail: de6 (Kammermeierphane 2): A solution of 5 (40 mg, 0.010 mmol) and 1 (53 mg,
posit(?chemcrys.cam.ac.uk).
0.015 mmol) in benzene (120 mL) was irradiated in a quartz reactor for 3 h. The
The n-n* transition of TDDA lies at 280 nm. With a Pyrex filter the irradation
solvent was removed in vacuo and the residue was purified by chromatography on
time is much longer due to absorption of light with wavelengths <300 nm.
silica gel with hexane/dichloromethane 2/1 (R, = 0.08). After further purification
Two other compounds that have been synthesized in our laboratory following
by HPLC (PSS-SDV gel 100 A, 10 mm, CHCI,) the product was recrystallized from
the same construction principle correspond to sections of (4,4)nanotubes, see
toluene. 6 was obtained as a lemon-yellow solid. Yield: 7 mg (10%). M.p. 380°C
refs.[3,4] For a review on the nomenclature, properties, and synthesis of
(decomp); 'HNMR (400MHz, CDCI,): 6 =7.79 (m. 8 H ; CH, arom.), 7.54 (m.
nanotubes see: M. S. Dresselhaus, G. Dresselhaus, P. C. Eklund, Science of
4H;CH,arom.), 7.27 (m,4H; CH,arom.), 7.16(m, 16H; CH,arom.), 6.82(s,4H;
Fullerenes and Carbon Nanotubes, Academic Press, San Diego, 1996.
CH, olef.); I3C NMR (100.6 MHq CS,/C,D, l0jl): 6 =140.55 (CJ, 139.96 (CJ,
M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. P. Stewart, J. Am. Chem. SOC.
139.45 (CJ, 138.56 (C,), 136.17 (Cq), 135.70 (CJ, 128.72 (CHR=CR,), 128.67
1985, 107, 3902-3909.
(CH, arom.), 127.55(CH,arom.), 127,16(CH,arom.),126.20(CH,arom.), 125.57
(CH, arom.), 124.91 (CH, arom.), 123.39 (CH, arom.), 122.98 (CH, arom.); IR
(KBr): C = 3090, 3060, 3028 cm-' (m, C-H, arom, olef.), 1644 (m, C=C, olef.),
1451 (s, C=C, arom.), 769 (s, C-H, arom.); UV/Vis (CH,CI,): %,,,( E ) = 230
(56000), 246 (SSOOO), 316 (27000). 358 nm (60000); MS (70 eV): m / z ( O h ) : 756
(100) [M+]; HRMS: calcd for C,,H,,: 756.2817, found: 756.2815.
~
Received: April 14, 1997 [Z10338IE]
German version: Angew. Chem. 1997, 109,2317-2319
Keywords: cycloadditions
chemistry
2202
- cyclophanes - metatheses
*
photo-
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