Li Changzhi, Zhang Danwei, Zhang Xiaotong, Wu Shihui, Gao Xiang
Department of Chemistry, Fudan University, Shanghai, 200433, PR China.
Org Biomol Chem. 2004 Dec 7;2(23):3464-9. doi: 10.1039/b411862f. Epub 2004 Oct 20.
[60]Fullerene reacted with various beta-dicarbonyl compounds in the presence of Mn(OAc)3*2H2O to generate dihydrofuran-fused [60]fullerene derivatives or 1,4-bisadducts. Dihydrofuran-fused [60]fullerene derivatives 2 could be formed by treatment of alpha-unsubstituted beta-diketones 1a-e or beta-ketoesters 1f and 1g with [60]fullerene in refluxing chlorobenzene in the presence of Mn(III). Solvent-participated unsymmetrical 1,4-bisadducts 3 were obtained through the reaction of [60]fullerene with dimethyl malonate 1h or alpha-substituted beta-dicarbonyl compounds 1i-1n in toluene. A possible reaction mechanism for the formation of different fullerene derivatives is proposed.
[60]富勒烯在三水合醋酸锰（Mn(OAc)₃·2H₂O）存在下与各种β - 二羰基化合物反应，生成二氢呋喃稠合的[60]富勒烯衍生物或1,4 - 双加合物。通过在回流的氯苯中，在锰（III）存在下，用[60]富勒烯处理α - 未取代的β - 二酮1a - e或β - 酮酯1f和1g，可以形成二氢呋喃稠合的[60]富勒烯衍生物2。通过[60]富勒烯与丙二酸二甲酯1h或α - 取代的β - 二羰基化合物1i - 1n在甲苯中的反应，得到溶剂参与的不对称1,4 - 双加合物3。提出了形成不同富勒烯衍生物的可能反应机理。
