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Competitive Retro-Cycloaddition Reaction in Fullerene Dimers Connected Through Pyrrolidinopyrazolino Rings

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Competitive Retro-Cycloaddition Reaction in Fullerene Dimers Connected Through Pyrrolidinopyrazolino Rings pubs.acs.org/joc Competitive Retro-Cycloaddition Reaction in Fullerene Dimers Connected through Pyrrolidinopyrazolino Rings Juan Luis Delgado,†,‡ Sı´lvia Osuna,§ Pierre-Antoine Bouit,‡ Roberto Martı´nez-Alvarez,† Eva Espı´ldora,† Miquel Sola,* ,§ and Nazario Martı´n*,†,‡ †Departamento de Quı´mica Organica, Facultad de Ciencias Quı´micas, Universidad Complutense de Madrid, E-28040, Madrid, Spain, ‡IMDEA-Nanociencia, Facultad de Ciencias, Modulo C-IX, 3a planta, Ciudad Universitaria de Cantoblanco, E-29049 Madrid, Spain, and §Institut de Quı´mica Computacional and Departament de Quı´mica, Universitat de Girona, E-17071 Girona, Catalonia, Spain [email protected]; [email protected] Received July 31, 2009 Competitive retro-cycloaddition in [60]- and [70]fullerene homodimers (1a,1c) as well as [60]/[70]heterodimer (1b), linked through 2-pyrazolinopyrrolidino bridges, has been studied by means of HPLC, mass spectrometry, and theoretical calculations at the density functional theory (DFT) level by using the two-layered ONIOM approach. The results of these investigations indicate that the retro-cycloaddition reaction of pyrrolidinofullerenes is favored compared to the retro- cycloaddition reaction of 2-pyrazolinofullerenes in compounds 1a-c. Evidence of the occurrence of this process have been observed both by HPLC and MS-MALDI, these findings being in good agreement with those predicted by theoretical calculations. Introduction variety of new reactions.4 Some of us have previously reported the thermally induced transition metal catalyzed Since fullerenes1 and other molecular carbon nanostruc- tures2 were discovered, a remarkable effort has been devoted 3 (3) (a) Hirsch A. The Chemistry of Fullerenes; Wiley-VCH: Weinheim, to their chemical modification. Moreover, owing to their Germany, 2005. (b) Fullerenes: From Synthesis to Optoelectronic Properties; exceptional electronic and geometrical characteristics, full- Guldi, D. M., Martín, N., Eds.; Kluwer Academic Publishers: Dordrecht, The erenes represent an exceptional scenario for testing a wide Netherlands, 2002. (c) Taylor, R. Lecture Notes on Fullerene Chemistry: A Handbook for Chemists; Imperial College Press: London, UK, 1999. (d) Langa, F.; Nierengarten, J.-F. Eds. Fullerenes. Principles and Applications; RSC: (1) Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Cambridge, UK, 2007 Nature 1985, 318, 162. (4) (a) Martı´n, N. Chem Commun. 2006, 2093. (b) Martı´n, N.; Altable, (2) (a) For a recent review, see: Delgado, J. L.; Herranz, M. A.; Martı´n, M.; Filippone, S.; Martı´n-Domenech, A. Synlett 2007, 3077. N. J. Mater. Chem. 2008, 18, 1417. (b) Carbon Nanotubes and Related (5) (a) Martı´n, N.; Altable, M.; Filippone, S.; Martı´n-Domenech, A.; Structures: New Materials for the Twenty-First Century; Harris, P., Ed.; Echegoyen, L.; Cardona, C. M. Angew. Chem., Int. Ed. 2006, 45, 110. (b) Cambridge University Press: Cambridge, UK, 2001. (c) Reich, S.; Thomsen, Lukoyanova, O.; Cardona, C. M.; Echegoyen, L.; Altable, M.; Filippone, S.; C.; Maultzsch, J. Carbon Nanotubes: Basic Concepts and Physical Properties; Martı´n Domenech, A.; Martı´n, N. Angew. Chem., Int. Ed. 2006, 45, 7430. (c) VCH: Weinheim, Germany, 2004. (d) Acc. Chem. Res. 2002, 35 (Special Issue), For a retro-cycloaddition on SWCNTs, see: Bruneti, F. G.; Herrero, M. A.; Munoz,~ 1997. (e) Akasaka,T.; Nagase, S. Eds. Endofullerenes: A New Family of Carbon J. M.; Giordani, S.; Diaz-Ortiz, A.; Filippone, S.; Ruaro, G.; Meneghetti, M.; Clusters; Kluver Academic Publishers: Dordrecht, The Netherlands, 2002. Prato, M.; Vazquez, E. J. Am. Chem. Soc. 2007, 129, 14580. 8174 J. Org. Chem. 2009, 74, 8174–8180 Published on Web 09/28/2009 DOI: 10.1021/jo901644b r 2009 American Chemical Society Delgado et al. JOCArticle quantitative retro-cycloaddition reaction of pyrrolidino- then a small amount (0.5 mL) of the reaction mixture was [3,4:1,2]fullerenes5 as well as isoxazolino[3,4:1,2]fullerenes,6 collected, diluted, and submitted to HPLC analysis (Table 1, and proved its convenience as a new and useful protec- o-DCB-24 h). The results of this experiment showed that 5 tion-deprotection protocol. Recently, this methodology pristine C60 was obtained in moderate yield (50%) under also has been applied to induce the retro-cycloaddition thermal treatment. Then, we carried out the same experiment process in 2-pyrazolino[3,4:1,2]fullerenes.7 The results of by adding a large excess (30 equiv) of maleic anhydride as an that study clearly indicated that C-substitution on the pyra- efficient dipolarophile in order to trap the in situ generated zole ring plays an important role on the course of the dipole (Table 1, MA-24 h). Analysis of this experiment by reaction, as l,3-diaryl-2-pyrazolino[60]fullerenes are ther- HPLC showed that pristine C60 was obtained in a better yield mally stable under these conditions and form C60 in very (66%) together with a new peak located at 11.25 min (toluene low yields. In contrast, 1-aryl-3-alkyl-2-pyrazolino deriva- 1 mL/min), which was identified by the detector of the HPLC tives are more vulnerable to these experimental conditions, as a fullerene-based compound. undergoing an efficient thermally induced transition metal To shed some light on the nature of this new fullerene- catalyzed retro-cycloaddition reaction. In a previous paper,8 based compound, we isolated a small amount of this new we have reported the preparation and photovoltaic applica- derivative by semipreparative HPLC chromatography and tions of a new family of fullerene-based compounds, namely, submitted this sample to MALDI MS analysis. The recorded soluble [60]- and [70]fullerene homodimers (1a, 1c) and the mass spectra, both in positive and in negative mode of [60]/[70]heterodimer (1b), linked through 2-pyrazolinopyr- detection, do not exhibit the corresponding molecular ion rolidino bridges (Figure 1). These dimers represent the first proposed for the trapping of the thermally generated azo- example of covalently bonded pyrrolidinopyrazolinofuller- methyne ylide by the maleic anhydride (compound 2, mo- ene dimers, despite the fact that pyrrolidinofullerenes9 and lecular weight 1134 Da). In contrast, a peak at m/z 1104 (M - pyrazolinofullerenes10 are well-known in fullerene chemistry 30 Da) and a fragment at m/z 1060 (1104 - 44 Da) were and have been extensively studied. In the present paper we observed both in the negative and in the positive modes of report on the competitive retro-cycloaddition reaction that detection. The structure of the proposed new derivative with takes place in these dimers (1a-c), by means of thermally a cyclic anhydride moiety supports the formation of both induced treatment in the presence of an excess of dipolar- fragments. Thus, an elimination of 30 Da (formaldehyde) ophile (maleic anhydride), as well as copper triflate and a subsequent loss of 44 Da (carbon dioxide) explain the (CuOTf2). The competitive retro-cycloaddition process that formation of these ions, thus indicating that the retro- takes place on these dimers has also been studied by mass cycloaddition of 1a takes place with trapping of the inter- spectrometry and the experimental findings are underpinned mediate dipole (see the SI). It is important to note that the by theoretical calculations at the density functional theory mass spectra of cyclic anhydrides are known to give small or (DFT) level, using the two-layered ONIOM approach. negligible molecular ion peaks but produce abundant peaks 11 Analysis of the experimental and theoretical results ob- due to CO2 elimination. The fragmentation pattern of tained by these three different approaches reveals that the this new derivative therefore can be considered as a proof retro-cycloaddition occurs preferentially on the pyrrolidino- of the proposed structure. This conclusion is, indeed, well fullerene moiety, due to the lower activation barrier and supported by our previous research findings: when per- the slightly more favorable reaction energy for the entire forming the retro-cycloaddition study with different 2-pyr- process. azolinofullerenes, we were not able to observe the trapped nitrile-imine species in any case.7 On the contrary, Results and Discussion dealing with fulleropyrrolidines, the retro-cycloaddition process is more favored, and efficient trapping of the ther- Thermal Treatment. To investigate the thermal stability of mally generated azomethine ylide has recently been des- these dimers, compound 1a has been submitted to the same cribed.12 experimental conditions previously reported for other full- - Then, we performed the same experiment but adding erene-fused pentagonal heterocyclic rings.5 7 Compound 1a copper triflate, a metal Lewis acid, in order to find out if a was first heated at reflux in o-DCB for 24 h (Figure 2), and possible coordination with the nitrogen atoms could activate the retro-cycloaddition reaction (Table 1, entry 3). The (6) (a) Martı´n, N.; Altable, M.; Filippone, S.; Martı´n-Domenech, A.; Martı´nez-Alvarez, R.; Suarez, M.; Plonska-Brzezinska, M. E.; Lukoyanova, results of this experiment showed that pristine C60 was O.; Echegoyen, L. J. Org. Chem. 2007, 72, 3840. (b) Da Ros, T.; Prato, M.; obtained in 58% yield, a value that resembles that obtained Novello, F.; Maggini, M.; De Amici, M.; De Micheli, C. Chem. Commun. 1997, 59. (c) Da Ros, T.; Prato, M.; Lucchini, V. J. Org. Chem. 2000, 65, 4289. with simple thermal treatment, being therefore, the influence (7) (a) Delgado, J. L.; Cardinali, F.; Espı´ldora, E.; Torres, M. R.; Langa, of copper triflate, scarce or negligible on the retro-cycloaddi- F.; Martı´n, N. Org. Lett. 2008, 10, 3705. (b) Delgado, J. L.; Oswald, F.; tion process. When the experiment was performed in the Cardinali, F.; Langa, F.; Martı´n, N. J. Org. Chem. 2008, 73, 3184. (8) Delgado, J. L.; Espı´ldora, E.; Liedtke, M.; Sperlich, A.; Rauh, D.; presence of maleic anhydride (30 equiv) and copper triflate Baumann, A.; Deibel, C.; Dyakonov, V.
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