Selective preparation of oxygen-rich [60]fullerene derivatives by   stepwise addition of tert-butylperoxy radical and further   functionalization of the fullerene mixed peroxides

doi:10.1021/jo049974q

CORC > 北京大学 > 化学与分子工程学院

	Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides
	Huang, SH ; Xiao, Z ; Wang, FD ; Gan, LB ; Zhang, X ; Hu, XQ ; Zhang, SW ; Lu, MJ ; Pan, QQ ; Xu, L
刊名	journal of organic chemistry
	2004
关键词	T-BUTYL HYDROPEROXIDE HOMOLYTIC DECOMPOSITIONS UNSYMMETRICAL C60ME5O3H METAL-COMPLEXES C-60 CHEMISTRY < OXIDATION BUCKMINSTERFULLERENE ISOMER 60> FULLERENE
DOI	10.1021/jo049974q
英文摘要	tert-Butylperoxy radicals add to C-60 selectively to form multi-adducts C-60(O)(m)((OOBu)-Bu-t), (m = 0, n = 2, 4, 6; m = 1, n = 0, 2, 4, 6) in moderate yields under various conditions. Visible light irradiation favors epoxide formation. High concentration of tert-butylperoxy radicals mainly produces the hexa-homoadduct C-60((OOBu)-Bu-t)(6) 6; low concentration and long reaction time favor the epoxy-containing C-60(O)((OOBu)-Bu-t)(4) 7. The reaction can be stopped at the bis-adducts with limited TBHP. A stepwise addition mechanism is discussed involving mono-, allyl-, and cyclopentadienyl C-60 radical intermediates. m-CPBA reacts with the 1,4-bis-adduct to form C-60(O)((OOBu)-Bu-t)(2) and C-60(O)(3)((OOBu)-Bu-t)(2). The C-O bond of the epoxy ring in 7 can be cleaved with HNO3 and CF3COOH. Nucleophilic addition of NaOMe to 7 follows the S(N)1 and extended S(N)2' mechanism, from which four products are isolated with the general formula C-60(O)(a)(OH)(b)(OMe)(c)((OOBu)-Bu-t)(d). Visible light irradiation of the hexa-adduct 6 results in partial cleavage of both the C-O and O-O bonds of peroxide moieties and formation of the cage-opened compound C-60(O)(O)(2)((OOBu)-Bu-t)(4). All the fullerene derivatives are characterized by spectroscopic data. A single-crystal structure has been obtained for an isomer Of C-60(O)(OH)(2)(OMe)(4)((OOBu)-Bu-t)(2).; Chemistry, Organic; SCI(E); EI; PubMed; 60; ARTICLE; 7; 2442-2453; 69
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/199613]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Huang, SH,Xiao, Z,Wang, FD,et al. Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides[J]. journal of organic chemistry,2004.
APA	Huang, SH.,Xiao, Z.,Wang, FD.,Gan, LB.,Zhang, X.,...&Xu, L.(2004).Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides.journal of organic chemistry.
MLA	Huang, SH,et al."Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides".journal of organic chemistry (2004).