Alkali-Metal Trichloroacetates for Dichloromethylenation of Fullerenes: Nucleophilic Addition-Substitution Route

作者：Apenova Marina G; Akhmetov Vladimir A; Belov Nikita M; Goryunkov Alexey A^*; Ioffe Ilya N; Lukonina Natalia S; Markov Vitaliy Yu; Sidorov Lev N

来源：Chemistry-An Asian Journal, 2014, 9(3): 915-923.

DOI：10.1002/asia.201301413

• alkylation
• fullerenes
• mass spectrometry
• NMR spectroscopy
• reaction mechanisms

The first experimental evidence that fullerenes react with alkali-metal trichloroacetates through a nucleophilic addition-substitution route, yielding dichloromethylenefullerenes as the final products, is reported. The intermediates, C-60(CCl3)(-) and C-70(CCl3)(-) anions, have been isolated in their protonated forms as ortho-C-60(CCl3)H, as well as three ortho and one para isomer of C-70(CCl3)H. The structures were unambiguously determined by means of H-1, C-13, and H-1-C-13 HMBC NMR spectroscopy along with UV/Vis spectroscopy. The observed regiochemistry was analyzed with the aid of quantum chemical calculations. Conversion of the protonated compounds into the [6,6]-closed C-60/70(CCl2) cycloadducts under basic conditions can be effected only for the ortho isomers, whereas para-C-70(CCl3)H decomposes back into pristine C-70.

• 出版日期2014-3