Reactivity of fullerene epoxide: preparation of fullerene-fused thiirane, tetrahydrothiazolidin-2-one, and 1,3-dioxolane.
The epoxide moiety in the fullerene-mixed peroxide C60(O)(OOtBu)4 1 reacts readily with aryl isocyanates ArNCS (Ar = Ph, Naph) to form both the thiirane derivative C60(S)(OOtBu)4 and fullerene-fused tetrahydrothiazolidin-2-one. The reaction of 1 with trimethylsilyl isothiocyanate TMSNCS yields the isothiocyanate derivative C60(NCS)(OH)(OOtBu)4, the isothiocyanate and hydroxyl moieties of which could be converted to a fullerene-fused tetrahydrothiazolidin-2-one ring with alumina quantitatively. Treating 1 with BF3.Et2O yields the fullerene-fused [1,3,2]-dioxoborolane derivative C60(O2BOH)(OOtBu)4. In the presence of aldehyde or acetone, BF3.Et2O catalyzes the conversion of epoxide to fullerene-fused 1,3-dioxolane derivatives. The products are characterized by spectroscopic data. Two of the compounds are also characterized by single-crystal X-ray analysis.
Yang
Xiaobing
X
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Huang
Shaohua
S
Jia
Zhenshan
Z
Xiao
Zuo
Z
Jiang
Zhongping
Z
Zhang
Qianyan
Q
Gan
Liangbing
L
Zheng
Bo
B
Yuan
Gu
G
Zhang
Shiwei
S
D018360:Crystallography, X-Ray; D004148:Dioxolanes / Q000138:chemical synthesis* / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry*; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism; D013440:Sulfides / Q000138:chemical synthesis* / Q000737:chemistry; D053778:Thiazolidines / Q000138:chemical synthesis* / Q000737:chemistry
D004148:Dioxolanes; D004852:Epoxy Compounds; D037741:Fullerenes; D013440:Sulfides; D053778:Thiazolidines; C013523:ethylene sulfide; C010962:formal glycol