[2 + 2] Cycloadditions of fullerenes. Synthesis and characterization of C{sub 62}O{sub 3} and C{sub 72}O{sub 3}, the first fullerene anhydrides
- Univ. of California, Los Angeles, CA (United States)
[2 + 2] Cycloaddition of C{sub 60} with N,N,N{prime},N{prime}-tetraethylethynediamine (1a) and N,N-diethyl-2-ethylthioethyneamine (1b) gave the stable, 1,2-dihydrofullerene[60]-1,2-cyclobutenediamine 2a and thioenamine 2b, respectively, in good yield. Self-sensitized photooxygenation of 2a and 2b produced 1,2-dihydrofullerene[60]-1,2-diamide 3a and thioester amide 3b, from which 1,2-dihydrofullerene[60]-1,2-dicarboxylic acid anhydride (C{sub 62}O{sub 3}) was readily prepared. Similarly, C{sub 70} reacted with 1a (regiospecifically at the 1,9-bond) to give 1,9-dihydrofullerene[70]-1,9-cyclobutenediamine 5 or 1,9:61,62-biscyclobutenediamine 6 in good yields. In contrast to 2a, self-sensitized photooxygenation of 5 regenerated C{sub 70} and the oxidized ynamine. 1,9-Dihydrofullerene[70]-1,9-dicarboxylic acid anhydride (C{sub 72}O{sub 3}) was prepared from a tert-butylthioester amide 10 in one pot by reaction of N,N-diethyl-2-tert-butylthioethyneamine (1c) with C{sub 70} and photooxygenation of the resultant cycloadduct. 52 refs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 41830
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 117; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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