Synthesis of fullerenes

SWCNT is synthesized by almost the same method as that- for the synthesis of MWCNT. Remarkable difference lies in the fact that metallic catalyst is indispensable to the synthesis of fullerenes. The metal compounds used as the catalyst are listed in Table 2 [8]. 

Dipolar cycloaddition in the synthesis of fullerene Ceo derivatives containing heterocyclic fragments 98KGS291. 

H. Isobe, H. Mashima, H. Yorimitsu, and E. Nakamura, Synthesis of fullerene glycoconjugates through sulfide connection in aqueous media, Org. Lett., 5 (2003) 4461 1463. 

Pantarotto D, Bianco A, Pellarini F, Tossi A, Giangaspero A, Zelezetsky I, Briand J-P, Prato M (2002) Solid-phase synthesis of fullerene-peptides. J. Am. Chem. Soc. 124 12543-12549. 

Braun T, Buvari-Barcza A, Barcza L, Konkoly-Thege I, Fodor M, Migali B (1994) Mechanochemistry a novel approach to the synthesis of fullerene compounds. Water soluble Buckminster fullerene - gamma- cyclodextrin inclusion complexes via solid-solid reaction. Solid State Chem. 74 47-51. 

Example Fullerene soots as obtained by the Huffman-Kratschmer synthesis of fullerenes can be characterized by positive- as well as negative-ion LDI. [115] The LDI-TOF spectrum of such a sample exhibits fullerene molecular ion signals well beyond m/z 3000 among these, Ceo and 070" are clearly preferred (Fig. 10.11). Furthermore, such samples provide experimental carbon-only isotopic patterns over a wide mass range (Chap. 3.2.1). 

Other methods that use 55 anions as precursor for the synthesis of fullerene-derivatives usually involve chemical formation of the anion. Alkylation of 55 has been accomplished, e.g. by reduction with propanethiol and potassium carbonate in DMF [91,92], sodium methanethiolate in acetonitrile [93], the naphthalene radical anion in benzonitrile[94], potassium naphthalide [95] or simply with zinc [96]. 

Scheme 10.15 Synthesis of fullerene appended macrocycles 69 and 70 and the [1 2 3] hexakisadduct 72. (i) 10 equiv. 3-bromo-l,5-bis(trimethylsilyl)-1,4-pentadiyne (75), 10 equiv. DBU (ii) Bu2NF(Si02) (iii) 200 equiv. Cu(OAc)2, molecular sieves (iv) 60 equiv. CH2N2 (v) hv.

McKinnon JT, Bell WL, Barkley RM (1992) Combustion synthesis of fullerenes. Combust Flame 88 102-112... 

Goel A, Hebgen P, Vander Sande JB et al (2002) Combustion synthesis of fullerenes and fullerenic nanostructures. Carbon 40 177-182... 

Zhang S, Lukoyanova O, Echegoyen L (2006) Synthesis of fullerene adducts with terpyridyl-or pyridylpyrrolidine groups in trans-1 positions. Chem Eur J 12 2846-2853... 

Shortly after realization of preparative syntheses of fullerenes their high chemical activity was proved and fullerene hydrides were obtained (Goldshleger and Moravskii 1997). The methods of synthesis of fullerene hydrides have been intensively developing because these hydrides are considered to be the base compounds for the development of fullerene chemistry, possess a potential for the use as hydrogen accumulators. The... 

The synthesized fullerene hydrides vary both in the composition and in the isomeric structures. The number of possible isomers of the C60H2n fullerene hydrides varies over a wide range from 23 for C60H2 to >1015 for C60H30 (Balasubramanian 1991). In the synthesis, the mixtures are formed with a limited number of isomers due to thermodynamic and kinetic limitations. However, the synthesis of fullerene hydrides of high purity is still impossible due to the above mentioned peculiarities. The best samples correspond to the isomeric mixtures containing 1-5% of the hydrides of different formula. 

Among the reactions applied in the synthesis of fullerene derivatives cycloaddition reactions such as [2 + 1]-, [2 + 2]-, [3 + 2] and [4 + 2] cycloadditions play a dominant role. In these reactions ring-fused fullerene derivatives are obtained, at least with incorporation of heteroatoms such as oxygen, nitrogen, or silicon. In this section photochemical reactions leading to cycloalkyl ring-fused fullerene adducts will be presented. Photocycloaddition reactions leading to C6o-fused heterocycles will be discussed later. 

The thermal Diels-Alder reaction ([4 + 2] cycloaddition) is widespread in the synthesis of fullerene derivatives. In contrast, only a few examples of the photochemical Diels-Alder reaction in solution or in the solid state are known. The first example is described by Tomioka and coworkers [249], Irradiation of ketone 73 and C6o at 10°C with a high pressure mercury lamp through a Pyrex filter led to the formation of 61-hydroxy-61-phenyl-l,9-(methano[l,2]benzenomethano) fullerene 75 (Scheme 29). This compound is unusually unstable and yields the monoalky 1-1,2-dihydrofullerene 76 either by silica gel chromatography or upon heating. 

Regioselective Synthesis of Fullerene Derivatives and Separation of Isomers of the Higher Fullerenes... 

In this section we present the use of the retro-cyclopropanation reactions for the synthesis of fullerene derivatives which are not available by other routes, and for the isolation of isomers and enantiomers of the higher fullerenes. 

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