CYCLOADDITIONS .47. CYCLOADDITION OF 1,8-DEHYDRONAPHTHALENE TO [60]FULLERENE IN BENZENE SOLUTION - A NEW FUNCTIONALIZATION OF C-60 BY IN-SITU GENERATED 6B,1OA-DIHYDROFLUORANTHENE

AVERDUNG J, Mattay J. CYCLOADDITIONS .47. CYCLOADDITION OF 1,8-DEHYDRONAPHTHALENE TO [60]FULLERENE IN BENZENE SOLUTION - A NEW FUNCTIONALIZATION OF C-60 BY IN-SITU GENERATED 6B,1OA-DIHYDROFLUORANTHENE. Tetrahedron Letters. 1994;35(36):6661-6664.The reaction of C-60 with in situ generated 6b,10a-dihydrofluoranthene 3 affords the stable [4+2]cycloadduct 1,2-(7,10-etheno-6b,7,8,9,10, 10a-hexahydrofluorantheno)-[60]fullerene 4. A similar incorporation of the solvent is observed in the reaction of 1,8-dehydronaphthatene 2 with C-60 in toluene

Exohedral functionalization of [60]fullerene by [3+2] cycloadditions: Syntheses and chemical properties of triazolino-[60]fullerenes and 1,2-(3,4-dihydro-2H-pyrrolo)-[60]fullerenes

Averdung J, Mattay J. Exohedral functionalization of [60]fullerene by [3+2] cycloadditions: Syntheses and chemical properties of triazolino-[60]fullerenes and 1,2-(3,4-dihydro-2H-pyrrolo)-[60]fullerenes. Tetrahedron. 1996;52(15):5407-5420.The reaction of C-60 with aryl azides 5 in dichlorobenzene at room temperature leads to isolable triazolinofullerene derivatives 6a and 6b. Photolysis of 6 selectively yields the aziridinofullerenes 7, In contrast to the photolysis the thermolysis affords the azafulleroids 8 as main product next to C-60 In addition the first photochemically induced rearrangement of azafulleroids (1,6-aza-bridged isomers) to aziridinofullerenes (1,2-aza-bridged isomers) is described. Beside aziridines 7 the photochemical reactions of azides 5 with C-60 predominantly yield one novel C-s symmetrical bisadduct, respectively. Furthermore the syntheses of symmetrical 1,2-(3.4-dihydro-2H-pyrrolo)-[60]fullerenes 12a-c by [3+2] cycloaddition of nitrile ylides ii are reported. Copyright (C) 1996 Published by Elsevier Science Lt

Syntheses of aziridino-[60]fullerenes via photochemically induced conversions of 1,2,3-triazolino-[60]fullerenes and azafulleroids

Averdung J, Mattay J. Syntheses of aziridino-[60]fullerenes via photochemically induced conversions of 1,2,3-triazolino-[60]fullerenes and azafulleroids. JOURNAL OF INFORMATION RECORDING. 1996;22(5-6):577-580.The reaction of C-60 with aryl azides 1 in dichlorobenzene at room temperature leads to isolable triazolinofullerene derivatives 2a and 2b. Photolysis of 2 selectively yields the aziridinofullerenes 4. In contrast to the photolysis the thermolysis affords the azafulleroids 3 as main product next to C-60. In addition the first photochemcially induced rearrangement of azafulleroids (1,6-aza-bridged isomers) to aziridinofullerenes (1,2-aza-bridged isomers) is described. Beside aziridines 4 the photochemical reactions of azides 1 with C-60 predominantly yield one novel C-s symmetrical bisadduct, respectively

Syntheses of urethano-, amido- and sulfonamido[60]fullerenes by nucleophilic substitutions with 1,2-(2,3-dihydro-1H-azirino)-[60]fullerene

Averdung J, Wolff C, Mattay J. Syntheses of urethano-, amido- and sulfonamido[60]fullerenes by nucleophilic substitutions with 1,2-(2,3-dihydro-1H-azirino)-[60]fullerene. Tetrahedron Letters. 1996;37(27):4683-4684.C60NH 1 and the acyl and tosyl chlorides 2 or acetic anhydride 1 in I,2-dichlorobenzene solution and pyridine give the stable fulleroaziridine derivatives 3a-d and 5 by nucleophilic substitution. Copyright (C) 1996 Elsevier Science Lt

AZA-DIHYDRO[60]FULLERENE IN THE GAS-PHASE - A MASS-SPECTROMETRIC AND QUANTUMCHEMICAL STUDY

AVERDUNG J, LUFTMANN H, SCHLACHTER I, Mattay J. AZA-DIHYDRO[60]FULLERENE IN THE GAS-PHASE - A MASS-SPECTROMETRIC AND QUANTUMCHEMICAL STUDY. Tetrahedron. 1995;51(25):6977-6982.A new approach to produce heterofullerenes is described. Starting from a fullerene with an intact cage which is activated by suitable exohedral functionalization, the first aza-heterofullerene is generated in the gas phase under DCl mass-spectrometric conditions. On the basis of AMl-calculations the 1,2-closed structure is proposed to be the most stable one

CYCLOADDITIONS .48. ADDITION OF PHOTOCHEMICALLY GENERATED ACYLNITRENES TO C-60 - SYNTHESIS OF FULLEROAZIRIDINES AND THERMAL REARRANGEMENT TO FULLEROOXAZOLES

AVERDUNG J, Mattay J, JACOBI D, ABRAHAM W. CYCLOADDITIONS .48. ADDITION OF PHOTOCHEMICALLY GENERATED ACYLNITRENES TO C-60 - SYNTHESIS OF FULLEROAZIRIDINES AND THERMAL REARRANGEMENT TO FULLEROOXAZOLES. Tetrahedron. 1995;51(9):2543-2552.The reaction of C-60 to acylnitrenes 2, generated by photolysis of aroylazides 1 in dichloromethane, creates the stable fulleroaziridine derivatives 3a, 3b, 3c, and 3d. The rearrangement of the fulleroaziridines 3 by boiling in tetrachloroethane leads to the formation of the corresponding fullerooxazoles 4a, 4b, 4c, and 4d. The formation of a fullerooxazole 4b was also observed by irradiation of C-60 and 1b in benzene

1,2-[3,4-dihydro-2-(4-methoxyphenyl)-2H-pyrrolo][60]fullerene carbon disulfide

Ramm M, Luger P, Averdung J, Mattay J. 1,2-[3,4-dihydro-2-(4-methoxyphenyl)-2H-pyrrolo][60]fullerene carbon disulfide. Acta Crystallographica Section C Crystal Structure Communications. 1996;52(10):2590-2594.The title fullerene, C69H9NO.CS2, is a low-symmetry derivative of C-60 and does not show the known disorder of the unsubstituted fullerene molecule. Contrary to spectroscopic investigations, the C-s symmetry of the molecule is no longer present in the crystal. The two bridging atoms, C1 and C2, 'stand out' of the C-60 surface

Progress in fullerene chemistry: From exohedral functionalization to heterofullerenes

Averdung J, TorresGarcia G, Luftmann H, Schlachter I, Mattay J. Progress in fullerene chemistry: From exohedral functionalization to heterofullerenes. Fullerene Science and Technology. 1996;4(4):633-654.Various types of cycloaddition such as [2+1], [2+3], and Diels-Alder reactions have been investigated for the purpose of exohedral functionalization of [60]fullerene and also in few cases of [70]fullerene. Thermal and photochemical activation have been used and lead to a variety of new fullerene derivatives which may be further functionalizable. In addition, a new approach to aza-heterofullerenes has been developed starting from an exohedrally activated fullerene

SYNTHESIS OF 1,2-(2,3-DIHYDRO-1H-AZIRINO)-[60]FULLERENE, THE PARENT FULLEROAZIRIDINE

AVERDUNG J, LUFTMANN H, Mattay J, CLAUS KU, ABRAHAM W. SYNTHESIS OF 1,2-(2,3-DIHYDRO-1H-AZIRINO)-[60]FULLERENE, THE PARENT FULLEROAZIRIDINE. Tetrahedron Letters. 1995;36(17):2957-2958.The reaction of [60]fullerene with tert-butylazidoformate in 1,1,2,2-tetrachloroethane yields the stable fulleroaziridine 1. Elimination of the tert-butyloxycarbonyl (BOC)group generates the parent fulleroaziridine C60NH 2