SCHEME 1. Outline Synthesis of Tri-n-alkylmellitic
Triimides from Mellitic Acid via Mitsunobu Alkylation
An Expedient Synthesis of Mellitic Triimides
Kathryn G. Rose, Dina A. Jaber,
Chenaimwoyo A. Gondo, and Darren G. Hamilton*
Department of Chemistry, Mount Holyoke College,
50 College Street, South Hadley, Massachusetts 01075
ReceiVed January 23, 2008
for lack of an effective preparative route, while other heavily
crowded benzene systems have found important roles in new
functional materials.3
We reported a viable, though limited, synthesis of tri-n-
alkylmellitic triimides in 2001:1 a small number of such
derivatives were subsequently employed in the preparation of
a class of donor–acceptor organized mesophases4 and in an
electrochemical study.5 Aside from one other isolated, and
unusual, example,6 this synthetic approach represented the only
published means to prepare mellitic triimide derivatives.7 Here,
we introduce a strikingly simple and far more general preparative
approach, the versatility of which is revealed in the preparation
of a range of susbtituted mellitic triimides 1.
Heating of the solid ammonium salts obtained from treatment
of mellitic acid with 3 equiv of a primary amine yields
trisubstituted mellitic triimides via dehydration and imide
ring closure. This surprisingly simple synthetic approach is
amenable to incorporation of alkyl, aryl, and amino acid ester
substituents, thereby opening broad access to a family of
C3-symmetric organic electron acceptors.
Triimides 1 containing the benzenehexacarbonyl core are
attractive supramolecular building blocks by virtue of their
relatively unusual planar 3-fold symmetic structure and powerful
electron-accepting ability.1 In these regards, they are closely
related to, but distinct from, the ubiquitous diimide acceptors
based on benzene, naphthalene, and perylene aromatic platforms
that have found extensive application in myriad supramolecular
designs.2 They also represent a class of hexasubstituted benzene
derivatives which have received little attention, at least in part
Our previously reported synthesis (Scheme 1) involved initial
conversion of mellitic acid 2 to the crude unsubstituted triimide
core 4 via thermal decomposition of the hexaammonium salt
3.1 Mitsunobu alkylation of crude 4 provided substituted
derivatives (R ) n-butyl, n-octyl, n-decyl, n-tetradecyl), but
overall yields with respect to starting material were low, and
lengthy chromatography was typically required to isolate the
desired triimides from a variety of unwanted byproducts. The
(3) (a) Rochefort, A.; Bayard, E.; Hadj-Messaoud, S. AdV. Mater. 2007, 19,
1992–1995. (b) Traber, B.; Wolff, J. J.; Rominger, F.; Oeser, T.; Gleiter, R.;
Goebel, M.; Wortmann, R. Chem. Eur. J. 2004, 10, 1227–1238. (c) Tulevski,
G. S.; Bushey, M. L.; Kosky, J. L.; Ruter, S. J. T.; Nuckolls, C. Angew. Chem.,
Int. Ed. 2004, 43, 1836–1839. (d) Bushey, M. L.; Nguyen, T.-Q.; Zhang, W.;
Horoszewski, D.; Nuckolls, C. Angew. Chem., Int. Ed. 2004, 43, 5446–5453.
(e) Gearba, R. I.; Lehmann, M.; Levin, J.; Ivanov, D. A.; Koch, M. H. J.; Barberá,
J.; Debije, M. G.; Piris, J.; Geerts, Y. H. AdV. Mater. 2003, 15, 1614–1618. (f)
Bushey, M. L.; Nguyen, T.-Q.; Nuckolls, C. J. Am. Chem. Soc. 2003, 125, 8264–
8269. (g) Ma, S.; Ni, B. J. Org. Chem. 2002, 67, 8280–8283.
(4) Park, L. Y.; Hamilton, D. G.; McGehee, E. A.; McMenimen, K. A. J. Am.
Chem. Soc. 2003, 125, 10586–10590.
(1) McMenimen, K. A.; Hamilton, D. G. J. Am. Chem. Soc. 2001, 123, 6453–
6454.
(2) These classes of aromatic diimides have proven, and continue to prove,
to be versatile and valuable building blocks for new applications in molecular
recognition and as components of functional materials. For selected examples
from the past two years, see: (a) Bradford, V. J.; Iverson, B. L. J. Am. Chem.
Soc. 2008, 130, 1517–1524. (b) Sakai, N.; Sisson, A. L.; Bhosale, S.; Furstenberg,
A.; Banerji, N.; Vauthey, E.; Matile, S. Org. Biomol. Chem. 2007, 5, 2560–
2563. (c) Pascu, S. I.; Naumann, C.; Kaiser, G.; Bond, A. D.; Sanders, J. K. M.;
Jarrosson, T. J. Chem. Soc., Dalton Trans. 2007, 3874–3884. (d) Clark, A. E.;
Qin, C.; Li, A. D. Q. J. Am. Chem. Soc. 2007, 129, 7586–7595. (e) Chu, Y.;
Sorey, S.; Hoffman, D. W.; Iverson, B. L. J. Am. Chem. Soc. 2007, 129, 1304–
1311. (f) Che, Y.; Datar, A.; Balakrishnan, K.; Zang, L. J. Am. Chem. Soc. 2007,
129, 7234–7235. (g) Wang, W.; Wang, L.; Palmer, B. J.; Exarhos, G. J.; Li,
A. D. Q. J. Am. Chem. Soc. 2006, 128, 11150–11159. (h) Reczek, J. J.; Villazor,
K. R.; Lynch, V.; Swager, T. M.; Iverson, B. L. J. Am. Chem. Soc. 2006, 128,
7995–8002. (i) Pengo, P.; Pantos, G. D.; Otto, S.; Sanders, J. K. M. J. Org.
Chem. 2006, 71, 7063–7066. (j) Kato, S.; Matsumoto, T.; Ideta, K.; Shimasaki,
T.; Goto, K.; Shinmyozu, T. J. Org. Chem. 2006, 71, 4723–4733. (k) Johnstone,
K. D.; Bampos, N.; Sanders, J. K. M.; Gunter, M. J. New J. Chem. 2006, 30,
861–867. (l) Bhosale, S.; Sisson, A. L.; Talukdar, P.; Furstenberg, A.; Banerji,
N.; Vauthey, E.; Bollot, G.; Mareda, J.; Roger, C.; Wurthner, F.; Sakai, N.;
Matile, S. Science 2006, 313, 84–86. (m) Balakrishnan, K.; Datar, A.; Naddo,
T.; Huang, J.; Oitker, R.; Yen, M.; Zhao, J.; Zang, L. J. Am. Chem. Soc. 2006,
128, 7390–7398.
(5) Carroll, J. B.; Gray, M.; McMenimen, K. A.; Hamilton, D. G.; Rotello,
V. M. Org. Lett. 2003, 5, 3177–3180.
(6) Augustin, M.; Jeschke, P. Z. Chem. 1987, 27, 257–258.
(7) Mellitic triimides have been reported as components of network
polymers. Clemenson, P. I.; Pandiman, D.; Pearson, J. T.; Lavery, A. J. Polym.
Eng. Sci. 1997, 37, 966–977.
(8) Some of this chemistry was explored in parallel with that reported in
ref 1.
(9) (a) Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 28, 539–556.
(b) Agenet, N.; Gandon, V.; Vollhardt, K. P. C.; Malacria, M.; Aubert, C. J. Am.
Chem. Soc. 2007, 129, 8860–8871.
(10) For example, treatment of tetramethyl pyromellitate with 2 equiv of
n-butylamine in DMF at 140 °C for 16 h gave a 35% yield of N,N′-di-n-
butylpyromellitimide.
3950 J. Org. Chem. 2008, 73, 3950–3953
10.1021/jo800185v CCC: $40.75 2008 American Chemical Society
Published on Web 04/11/2008