An unusual reaction of triphenylphosphine with dichlorodinitrobenzofuroxan

A novel phosphorylation reaction of dichlorodinitrobenzofuroxan by triphenylphosphine has been studied. An unusual course of the reaction with the participation of benzofuroxan nitro groups as reactive centers has been established. It is shown that as final product of the reaction, a stable diphenolate diphosphabetaine with strong participation of the mesomeric ketoylide structure is formed. The structure of the product has been confirmed by X-ray diffraction

A versatile route to substituted 1,4-diazine-fused [60]fullerenes

Torres-Garcia G, Luftmann H, Wolff C, Mattay J. A versatile route to substituted 1,4-diazine-fused [60]fullerenes. The Journal of Organic Chemistry. 1997;62(9):2752-2756.An alternative route to [5,6]fullereno-C-60-I-h-[1,9-d]-2'-hydroxycyclohexanone (4a) is presented based on the [4 + 2] cycloaddition of 2,3-bis(trimethylsiloxy)butadiene (3) and [60]fullerene. The oxidation of the primary monoadduct with bromine yield the new [5,6]fullereno-C-60-I-h-[1,9-d]-1',2'-cyclohexanedione (5) which can be isolated as the dimethoxime derivative (9). The diketone 5 constitutes a versatile reactant for the synthesis of different substituted [5,6]fullereno-C-60-I-h-[1,9-b]-1',2',3',4'-tetrahydrophenazines (6a-d). The isolation, characterization, controlled-temperature H-1 NMR measurements as well as UV-vis and fluorescence studies of these new heterocycles are presented

Functionalization of [60]fullerene by photoinduced electron transfer (PET): Syntheses of 1-substituted 1,2-dihydro [60]fullerenes

Siedschlag C, Luftmann H, Wolff C, Mattay J. Functionalization of [60]fullerene by photoinduced electron transfer (PET): Syntheses of 1-substituted 1,2-dihydro [60]fullerenes. Tetrahedron. 1997;53(10):3587-3592.[60]Fullerene is irradiated in the presence of the electron transfer sensitizer 9,10-dicyanoanthracene (DCA) under cosensitization with biphenyl. The generated radical cation C-60(.+) reacts with H-donors such as tert-butylmethyl ether, propionaldehyde and alcohols to give 1:1-adducts, the 1-substituted 1,2-dihydro[60]fullerenes. (C) 1997 Elsevier Science Ltd

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

[60]fullerene radical cation: Reactions and mechanism

Siedschlag C, Luftmann H, Wolff C, Mattay J. [60]fullerene radical cation: Reactions and mechanism. TETRAHEDRON. 1999;55(25):7805-7818.C-60 was irradiated in the presence of several electron transfer photosensitizers. Upon addition of H-donors such as N,N-dimethylformamide, 1,3-dioxolane, phenylacetaldehyde, methyl formate, tert-butanol, propionic acid, glycol and methoxyethanol 1-substituted 1,2-dihydro[60]fullerenes 1-3 and 5-11 and in one case a 1,2,3,4-tetrahydro[60]fullerene, 4, were formed. A mechanistic pathway involving C-60(.+) is proposed