Bucky-bowls. A general approach to benzocorannulenes: Synthesis of mono- , di- and tri-benzocorannulenes

Article abstract of DOI:10.1039/a908852k

We outline a conceptually simple and general route to bowl-shaped benzocorannulenes based on readily assembled PAHs which on flash vacuum pyrolysis result in the sequential formation of a five- and six-membered ring; following this approach, syntheses of

Full text of DOI:10.1039/a908852k

Bucky-bowls. A general approach to benzocorannulenes: synthesis of mono-,
di- and tri-benzocorannulenes
Goverdhan Mehta* and P. V. V. Srirama Sarma
Department of Organic Chemistry, Indian Institute of Science, Bangalore, 560 012 India.
E-mail: diroff@admin.iisc.ernet.in
Received (in Cambridge, UK) 8th November 1999, Accepted 16th November 1999
We outline a conceptually simple and general route to bowl-
shaped benzocorannulenes based on readily assembled
PAHs which on flash vacuum pyrolysis result in the
sequential formation of a five- and six-membered ring;
following this approach, syntheses of mono-, di- and tri-
benzocorannulenes have been achieved.
As a part of our continuing interest in the synthesis of C60
fullerene (bucky-ball) and its fragments (bucky-bowls),1,2 we
became interested in developing a synthetic approach to
Scheme 1 Reagents and conditions: i, NBS, AIBN, CCl4, 73%; ii,
pentabenzocorannulene 1 en route (see transannular bridging
(Bu4N)2Cr2O7, CHCl3, 76%.
indicated in 1) to the ‘deep-bowl’ 2, C40H10.3 Bowl-shaped 1
and 2 represent 2/3 of the carbon content of C60 with eleven and
procedure.4 The methyl group in 7 was oxidised to the required
sixteen rings, respectively, constituting a dominant cross-
aldehyde 9 in two steps via the intermediate bromide 8 (Scheme
section on the fullerene surface. Both 1 and 2 evoke consider-
1). The aldehyde functionality in 9 was then elaborated to 10–12
able synthetic interest and are formidable objectives. As a
having active functionalities, which on thermal activation under
prelude to efforts towards 1 and 2, we have developed a new and
FVP conditions were expected to result in the projected two-
fold cyclization. Indeed, FVP of 10–12 furnished 3, albeit in
low yields characteristic of such reactions (Scheme 2).2
Benzocorannulene 3 was readily identified through its spectral
characteristics (UV, 2D NMR, mass).5,6
Our approach to dibenzocorannulene 4 originated from
5-methylbenzo[c]phenanthrene 13, in turn readily accessible
from commercial 2-methylnaphthalene.7 Naphthoannulation on
13 through the intermediacy of the Wittig salt 14 and
photocyclization of the resulting stilbene derivative 15 led to
13-methyldibenzo[c,p]chrysene 16 (Scheme 3). The methyl
general synthetic route to benzoannulated corannulenes in
which an appropriately constructed aromatic array upon flash
vacuum pyrolysis (FVP) undergoes two-fold C–C bond forma-
tion involving cyclodehydrogenation to generate a five-mem-
bered ring, followed by insertion of vinylidene carbene or
equivalent species to form a six-membered ring. Herein, we
report the synthesis of mono-, di- and tri-benzocorannulenes
3–5.
Our approach to benzocorannulene 3 emanated from 13-
methylbenzo[g]chrysene 7, readily available from 9-methyl-
phenanthrene 6 through a tactical modification of the reported
Scheme 2 Reagents and conditions: i, CBr4, PPh3, Zn, CH2Cl2, 85%; ii,
ClCH2PPh3Cl, ButOK, 0.5 h, 68%; iii, ClCH2PPh3Cl, ButOK, 2 h, 60%; iv,
FVP, 1150 °C, 5–7%; v, FVP, 1150 °C, 2–3%; vi, FVP, 1150 °C, 1–2%.
Chem. Commun., 2000, 19–20
This journal is © The Royal Society of Chemistry 2000
19

furnished the desired tribenzocorannulene 5, which was spec-
troscopically characterised (Scheme 4).5,6
In short, we have accomplished the syntheses of bowl-shaped
benzocorannulenes 3–5 from appropriate polycyclic aromatics
employing FVP as the key step, in which a five- and a six-
membered rings are sequentially formed. The precursor poly-
cyclic platforms were assembled from simple aromatic starting
materials through an iterative sequence involving Wittig
olefination and photocyclization steps. Notwithstanding the low
yields in the final FVP step, which is not uncommon for such
cyclizations,1,2 this work demonstrates the generality of our
approach and sets the stage for the synthesis of 1 and 2.
We thank JNCASR for financial support and the SIF facility
at I.I.Sc for high field NMR data. One of us (P. V. V. S. S.)
thanks CSIR for a research fellowship. We thank Professor L. T.
Scott for generously providing copies of spectra for comparison
purposes.
Notes and references
Scheme 3 Reagents and conditions: i, NBS 99%; ii, PPh3, C6H6, 79%; iii,
p-MeC6H4CHO, Cs2CO3, PriOH, 80%; iv, hv, I2, C6H6, propylene oxide,
65%; v, NBS, CCl4, 44%; vi, (Bu4N)2Cr2O7, CHCl3, 77%; vii, CBr4, PPh3,
Zn, CH2Cl2, 85%; viii, FVP, 1150 °C, 5–7%.
1 Reviews: (a) R. Faust, Angew. Chem., Int. Ed. Engl., 1995, 34, 1429; (b)
L. T. Scott, Pure Appl. Chem., 1996, 68, 291; (c) G. Mehta and H. S. P.
Rao, in Advances in Strain in Organic Chemistry, ed. B. Halton, JAI,
London, 1997, vol. 6; (d) G. Mehta and H. S. P. Rao, Tetrahedron, 1998,
53, 13 325; (e) L. T. Scott, Pure Appl. Chem., 1999, 71, 209.
2 G. Mehta, S. R. Shah and K. Ravikumar, J. Chem. Soc., Chem. Commun.,
1993, 1006; G. Mehta and K. Venkateswara Rao, Synlett, 1995, 319; G.
Mehta, K. Venkateswara Rao and K. Ravikumar, J. Chem. Soc., Perkin
Trans. 1, 1995, 1787; G. Mehta, G. V. R. Sharma, M. A. Krishna Kumar,
T. V. Vedavyasa and E. D. Jemmis, J. Chem. Soc., Perkin Trans. 1, 1995,
2529; G. Mehta, G. Panda, R. D. Yadav and K. Ravikumar, Indian J.
Chem., Sect. B, 1997, 36, 301; G. Mehta and G. Panda, Tetrahedron Lett.,
1997, 38, 2145; G. Mehta and G. Panda, Chem. Commun., 1997, 2081; G.
Mehta, G. Panda, S. R. Shah and A. C. Kunwar, J. Chem. Soc., Perkin
Trans. 1, 1997, 2269; G. Mehta, G. Panda and P. V. V. S. Sarma,
Tetrahedron Lett., 1998, 39, 5835.
group in 16 was oxidised to the aldehyde 17 and in the light of
the relatively more efficient conversion 10?3 was further
transformed to the hexacyclic gem-dibromoalkene 18, the
desired FVP precursor. On thermal activation 18 underwent the
expected double cyclization to furnish the new dibenzocor-
annulene 4 and was fully characterised on the basis of incisive
spectral analyses5 (Scheme 3).
Interestingly, 5-methylbenzo[c]phenanthrene 13 and the
Wittig salt 14 derived from it also served as the precursor for the
synthesis of tribenzocorannulene 5. Wittig coupling between 14
and 4-methylnaphthaldehyde gave 19 which on photocycliza-
tion led to the naphtho[1,2-f]picene derivative 20 (Scheme 4).
The methyl group in 20 was again elaborated to the aldehyde 21
and further to the FVP precursor 22. As planned, FVP on 22
3 G. N. Sastry, E. D. Jemmis, G. Mehta and S. R. Shah, J. Chem. Soc.,
Perkin Trans. 2, 1993, 1867.
4 W. H. Laarhoven, Th. J. H. M. Cuppen and R. J. F. Nivard, Tetrahedron,
1970, 26, 4865.
5 All new compounds reported here were fully characterised on the basis of
their spectral (UV, IR, 2D 1H and 13C NMR, MS) and analytical data.
Selected data for 3: mp 253 °C; lmax(MeOH)/nm 305, 275, 260 and 240;
dH(300 MHz; CDCl3), 8.68 (2H, dd, J 6 and 3.3), 8.26 (2H, d, J 8.7), 7.95
(2H, d, J 8.7), 7.84 (4H, ABq, J 8.7), 7.76 (2H, dd, J 5.7 and 3.3); dC(75
MHz; CDCl3) 137.6 (qC), 135.4 (qC), 134.6 (qC), 133.1 (qC), 130.8
(qC), 130.5 (qC), 128.9 (qC), 127.5 (CH), 127.3 (CH), 127.1 (CH), 126.9
(CH), 125.1 (CH) and 124.3 (CH); m/z 300 (M+). For 4: mp > 250 °C
(decomp.); lmax(MeOH)/nm 319, 272, 257 (sh), 242 (sh); dH(300 MHz;
CDCl3) 9.41 (2H, d, J 8.4), 8.83 (2H, d, J 7.5), 8.35 (2H, d J 8.7), 8.01
(2H, d, J 8.4), 7.91 (2H, s), 7.88–7.77 (4H, m); dC(75 MHz; CDCl3) 136.7
(qC), 134.2 (qC), 134.0 (qC), 133.9 (qC), 133.7 (qC), 130.2 (qC), 128.5
(qC), 127.8 (CH), 127.5 (CH), 127.1 (CH), 127.0 (CH), 126.5 (CH),
125.5 (CH), 124.5 (qC), 123.9 (CH); m/z 350 (M+). For 5: lmax(MeOH)/
nm 347, 334, 279, 252; dH(400 MHz; CDCl3) 9.41 (2H, d, J 8), 8.86 (2H,
d, J 7.2) 8.73 (2H, dd, J 6.4 and 3.6), 8.45 (4H, ABq, J 8.4), 7.87 (2H, d,
J 8), 7.83 (2H, d, J 9.2), 7.79 (2H, dd, J 6 and 3.2); m/z 400 (M+).
6 Mono- 3 and tri-benzocorannulene 5 reported here have been prepared
previously by Scott et al. [ref. 1(b), (e)] following entirely different
routes. See also: B. McMahon, B.S. Thesis, Boston College, 1997; C. C.
McComas, B.S. Thesis, Boston College, 1996. Since the details of this
work are not published, we have provided here the spectral data and also
compared the spectra of our synthetic compounds with theirs. Dibenzo-
corannulene 4 has been prepared for the first time.
Scheme 4 Reagents and conditions: i, 4-methylnaphthaldehyde, Cs2CO3,
PriOH; ii, hv, I2, C6H6, propylene oxide, 50% (2 steps); iii, NBS, CCl4, 45%;
iv, (Bu4N)2Cr2O7, CHCl3, 70%; v, CBr4, PPh3, Zn, CH2Cl2, 55%; vi, FVP,
1150 °C, 1–2%.
7 D. L. Nagel, R. Kupper, K. Antonson and L. Wallcave, J. Org. Chem.,
1977, 42, 1977.
Communication a908852k
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Chem. Commun., 2000, 19–20