Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Eguchi, Shoji; Ohno, Masatomi; Kojima, Satoshi; Koide, Naoya; Yashiro, Arihiro; Shirakawa, Yuri; Ishida, Hiroshi

doi:10.1080/10641229608001553

Cited by 23 publications

(21 citation statements)

References 111 publications

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“…The unique structure and properties of the newly discovered fullerene [C 60 ], its availability in macroscopic quantities of ultrahigh purity, and its possible applications have created immense interest in the preparation of newer derivatives. − The functionalization of fullerene has been developed rapidly, and a large number of C 60 derivatives have been synthesized. − Many of these derivatives have promising applications in nonlinear optics, optoelectronics, and biological sciences. A significant difference in the optical absorption spectra of the functionalized fullerenes reflect the change in their electronic structure from that of the parent fullerene. − Consequently, the photophysical and photochemical properties of the functionalized fullerenes too are expected to be affected significantly.…”

Section: Introductionmentioning

confidence: 99%

Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

et al. 1997

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Photophysical and photochemical properties of the singlet and triplet excited states of monochloropentaphenylfullerene [C60(C6H5)5Cl, MCPPF] have been characterized in two different solvents, benzene and benzonitrile, using two complementary transient absorption techniques, namely picosecond laser flash photolysis and nanosecond electron pulse radiolysis. Singlet−singlet and triplet−triplet absorption spectra have been recorded. The quantum yield of triplet formation (φT = 0.45 ± 0.05) and the intrinsic lifetime of the triplet (τ = 100 ± 10 μs) have been determined. Apart from the intrinsic decay of the triplet to the singlet ground state, another two processes, namely T−T annihilation and quenching by the ground state, make important contribution towards the overal triplet decay rate. Weak charge transfer (CT) complexes are formed between MCPPF and the electron-rich amines diphenylamine (DPA) and triphenylamine (TPA) in benzonitrile solution. On laser excitation, the CT complex undergoes charge separation, but the radical ions undergo very fast geminate recombination to form the triplet state of MCPPF.

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Section: Introductionmentioning

confidence: 99%

Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

et al. 1997

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“…Cycloadditions have proved to be the most generally useful method yet devised for attaching organofunctional groups to fullerenes. 1 In these processes the cage often behaves as the electron deficient component, so that alkenes bearing electronwithdrawing groups serve as useful models for reactions. Recently Zhang and Lu 2 described a novel [3 + 2] annulation technique for preparing cyclopentenes, based on the phosphinecatalysed cycloadditions of buta-2,3-dienoates and but-2-ynoates to electron-deficient alkenes.…”

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Phosphine-catalysed cycloaddition of buta-2,3-dienoates and but-2-ynoates to [60]fullerene

O'donovan¹,

Hitchcock²,

Meidine³

et al. 1997

Chem. Commun.

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“…1 Introduction of heterocycles on the C 60 surface has been performed satisfactorily by such methodologies for developing new materials based on combination of the interesting properties of these two ring systems. 2 The 1,3-dipolar cycloaddition has been applied as a reliable method for constructing five-membered fulleroheterocycles. 1,2 On the other hand, six-membered fulleroheterocycles have been so far achieved by hetero Diels-Alder reaction; for example, 2-aza-1,3-diene was applied for synthesis of d-lactam-fused C 60 .…”

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“…2 The 1,3-dipolar cycloaddition has been applied as a reliable method for constructing five-membered fulleroheterocycles. 1,2 On the other hand, six-membered fulleroheterocycles have been so far achieved by hetero Diels-Alder reaction; for example, 2-aza-1,3-diene was applied for synthesis of d-lactam-fused C 60 . 3 In relevance to the reasonable use of o-quinodimethane to prepare a cycloirreversible cycloadduct in fullerene chemistry, 4 its oxa and thia heterologs were demonstrated to give fullerochroman and -thiochroman derivatives (Scheme 1: X=O, S).…”

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confidence: 99%

Synthesis of Fullerotetrahydroquinolines by Cycloaddition Reaction of C₆₀ with Aza-ortho-xylylenes

Ohno¹,

Sato²,

Eguchi³

1999

Synlett

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This paper reports on the successful synthesis of fullerotetrahydroquinolines by using in situ generated aza-ortho-xylylenes using a Diels-Alder reaction.Various types of [2+3] and [2+4] cycloadditions have been exploited for the purpose of the exohedral functionalization of fullerenes. 1 Introduction of heterocycles on the C 60 surface has been performed satisfactorily by such methodologies for developing new materials based on combination of the interesting properties of these two ring systems. 2 The 1,3-dipolar cycloaddition has been applied as a reliable method for constructing five-membered fulleroheterocycles. 1,2 On the other hand, six-membered fulleroheterocycles have been so far achieved by hetero Diels-Alder reaction; for example, 2-aza-1,3-diene was applied for synthesis of d-lactam-fused C 60 . 3 In relevance to the reasonable use of o-quinodimethane to prepare a cycloirreversible cycloadduct in fullerene chemistry, 4 its oxa and thia heterologs were demonstrated to give fullerochroman and -thiochroman derivatives (Scheme 1: X=O, S). 5 In this series, we now wish to report a successful aza version (Scheme 1: X=NR) by using in situ generated aza-ortho-xylylenes with electron-withdrawing and electron-donating substituents and even no substituent on an imino group. The last case exemplified the first intermolecular Diels-Alder reaction of this heterodiene. Scheme 1Thermal decarboxylation of a 3,1-benzoxazin-2-one ring was documented recently to effect the generation of azaortho-xylylenes 6 and then employed for the present reaction with C 60 . The parent 1,4-dihydro-2H-3,1-benzoxazin-2-one 3 is available easily from the reaction of o-aminobenzyl alcohol 1 with phosgene. 7 Because of high toxicity of the latter reagent, we simply considered that it could be replaced with carbonyldiimidazole (Im 2 CO). 8 However, attempted cyclocondensation of 1 with this popular alternative gave no expected product. A complementary two-step conversion was rather effective (Scheme 2); 9 acylation of 1 with ethyl chloroformate in the presence of pyridine and, without purification of carbamate 2, following cyclization with DBU in refluxing toluene gave 3 in 88% overall yield. 10 According to the established procedure, 3 was converted to N-substituted 3,1-benzoxazin-2-ones 4a-e with NaH and appropriate halides. 6 Scheme 2The desired cycloaddition, typically with N-ethoxycarbonylated aza-ortho-xylylene 5a, was conducted by heating a solution of C 60 and 4a (1.5 equiv.) in 1,2,4-trichlorobenzene at reflux temperature under a nitrogen atmosphere. The color change of the solution from purple to dark brown showed the formation of new products together with TLC analysis (R f =0.6, silica gel/toluene). After refluxing for 4.5 h, the cycloadduct was isolated by flash chromatography on a silica gel column (hexane/toluene=1/1) to give 1,2,3.4-tetrahydroquinoline-fused C 60 6a in 46% yield (69% yield based on consumed C 60 ) (Scheme 3). The structural determination was based on spectral inspections. The usual evidence required for a 1:1...

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Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Cited by 23 publications

References 111 publications

Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Phosphine-catalysed cycloaddition of buta-2,3-dienoates and but-2-ynoates to [60]fullerene

Synthesis of Fullerotetrahydroquinolines by Cycloaddition Reaction of C₆₀ with Aza-ortho-xylylenes

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Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Cited by 23 publications

References 111 publications

Photophysical Properties of C60(C6H5)5Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Photophysical Properties of C60(C6H5)5Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Phosphine-catalysed cycloaddition of buta-2,3-dienoates and but-2-ynoates to [60]fullerene

Synthesis of Fullerotetrahydroquinolines by Cycloaddition Reaction of C60 with Aza-ortho-xylylenes

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Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Photophysical Properties of C₆₀(C₆H₅)₅Cl: A Laser Flash Photolysis and Pulse Radiolysis Study

Synthesis of Fullerotetrahydroquinolines by Cycloaddition Reaction of C₆₀ with Aza-ortho-xylylenes