Fullerenes as a tert-Butylperoxy Radical Trap, Metal Catalyzed Reaction of tert-Butyl Hydroperoxide with Fullerenes, and Formation of the First Fullerene Mixed Peroxides C60(O)(OOtBu)4 and C70(OOtBu)10

Gan, Liangbing; Huang, Shaohua; Zhang, Xiang; Zhang, Aixin; Cheng, Bo; Cheng, Hao; Li, Xiaolei; Shang, Gao

doi:10.1021/ja027714p

Cited by 181 publications

(74 citation statements)

References 17 publications

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“…Nevertheless, the radical reaction [4] of [60] fullerene (C 60 ) promoted by metal salts is relatively scarce. Very limited works have reported the radical reaction of C 60 in the presence of metal salts such as those of ruthenium [5], iron [5,6], manganese [7][8][9][10][11][12][13][14][15][16], copper [12], and lead [16,17]. We were the first to report the free radical reaction of C 60 promoted by Mn(OAc) 3 ·2H 2 O [8].…”

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confidence: 99%

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

Zhu

Wang

2010

Chin. Sci. Bull.

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The manganese(III) acetate-mediated radical reaction of [60]fullerene (C 60 ) with three carboxylic acids, that is, bromoacetic acid, 3-chloropropionic acid, and 1-naphthylacetic acid, was investigated. The reaction of C 60 with bromoacetic acid in the presence of 4-(dimethylamino)pyridine afforded the anticipated C 60 -fused lactone, while the reaction with 3-chloropropionic acid unexpectedly led to the formation of a novel C 60 -fused lactone with the loss of one molecule of HCl. Interestingly, the reaction with 1-naphthylacetic acid under similar conditions gave both C 60 -fused lactone and 1,4-adduct, yet each of them could be selectively obtained by controlling reaction conditions. It was also observed that the C 60 -fused lactone bearing a bulky naphthyl group existed as two isomers.[60]fullerene, manganese(III) acetate, carboxylic acids, C 60 -fused lactones Citation: Li F B, Zhu S E, Wang G W. Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid. Since the availability of fullerenes in a macroscopic amount, various types of reactions for the functionalization of fullerenes have been discovered [1-3]. Nevertheless, the radical reaction [4] of [60] fullerene (C 60 ) promoted by metal salts is relatively scarce. Very limited works have reported the radical reaction of C 60 in the presence of metal salts such as those of ruthenium [5], iron [5,6], manganese [7-16], copper [12], and lead [16,17]. We were the first to report the free radical reaction of C 60 promoted by Mn(OAc) 3 ·2H 2 O [8]. It was found that the reaction of C 60 with carboxylic acids, carboxylic anhydrides, or malonic acids mediated by Mn(OAc) 3 ·2H 2 O could afford the rare C 60 -fused lactones [15,16]. The obtained C 60 -fused lactones undergo further transformation [15,18] to give fullerene hemiacetals, fullerene hemiketals, C 60 -fused dihydrofurans, fullerenols, and reductive ring-opening *Corresponding author (email: gwang@ustc.edu.cn)products 1,2-C 60 H(CHRCOOH). Hence, it is demanding to prepare more C 60 -fused lactones [19,20] with specific structures for further functionalization. In our recent work, we have chosen eleven cheap and easily available carboxylic acids as the reactants for the synthesis of C 60 -fused lactones [15,16]. Other carboxylic acids were also investigated for the lactonization of C 60 , and new aspects for the reaction were discovered. Herein we disclose these interesting results obtained from the Mn(OAc) 3 ·2H 2 O-mediated reaction of C 60 with bromoacetic acid, 3-chloropropionic acid, or 1-naphthylacetic acid.

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confidence: 99%

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

Zhu

Wang

2010

Chin. Sci. Bull.

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“…1 were hydrocarbons with a fairly strong C-H bond (cf. benzene, 8 which is much less active in proton donation). In this connection, it seems likely that the lifetime of peroxide radicals RO 2 • in benzene is much longer than in the solvents containing active hydrogen; therefore, reaction (1) in benzene is much more probable.…”

Section: P -Productsmentioning

confidence: 99%

Effect of the medium on the reactivity of fullerene N60 with respect to the peroxide radicals RO2 ·. Chemiluminescence in the C60—AIBN—O2—C2H5Ph—PhH system

Булгаков

Ponomareva

2009

Russ Chem Bull

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Chemiluminescence (CL), HLPC, and volumetry were used to demonstrate that fullerene С 60 exerts no inhibiting effect on the liquid phase chain oxidation of hydrocarbons. Peroxide radicals RO 2 • do not add to С 60 in hydrocarbons with active C-H bond, because the reaction is suppressed by the competing addition of RO 2• to the hydrocarbon. The addition of RO 2 • radicals to С 60 does occur in benzene (a solvent with strong C-H bonds) in the presence of low concentrations of the hydrocarbon oxidized. Fullerene С 60 is found to exhibit a new type of liquid phase CL, which is presumably generated upon thermal decomposition of fullerene peroxides formed by adding peroxy radicals to fullerene in the C 60 -AIBN-O 2 -C 2 H 5 Ph-PhH system. The CL spectrum exhibits long wavelength maxima at 645 and 685 nm. The supposed CL emitters are keto derivatives of fullerene С 60 .There are two main reasons which make investigations of the reactivity of fullerene С 60 to the peroxide radicals RO 2 • topical. First, RO 2 • radicals are key intermediates of numerous chemical and biochemical oxidation process es. Second, there are contradictory data 1-7 (we have dis cussed them in quite detail earlier 1 ) on the ability of ful lerene to act as inhibitor by reaction (1) in thermal oxida tive degradation of polymers 2-4 and in reactions involved in the metabolism of viruses and pathogenic bacteria. 5-7 RO 2 • + C 60 P(1) P -productsHowever, our chemiluminescence (CL) and HPLC study 1 revealed no inhibiting effect of С 60 fullerene on AIBN initiated liquid phase oxidation of various hydro carbons including ethylbenzene (EB), dodecane, and cy clohexane and oleic acid. It was concluded 1 that С 60 does not react with RO 2 • radicals. However, more recently it was found 8 that peroxide radicals (Bu t O 2 • generated upon catalytic decomposition of Bu t OOН) add to С 60 yielding a complex fullerene peroxide (Bu t OO) x C 60 (O) (x = 4) con taining one epoxide oxygen. It is important that the sol vents used in Ref. 1 were hydrocarbons with a fairly strong C-H bond (cf. benzene, 8 which is much less active in proton donation). In this connection, it seems likely that the lifetime of peroxide radicals RO 2 • in benzene is much longer than in the solvents containing active hydrogen; therefore, reaction (1) in benzene is much more probable. The aim of this work is to explore the effect of the medium on the reactivity of fullerene toward RO 2 • radicals by com paring some parameters of two pairs of redox systems, С 60 -AIBN-O 2 -C 2 H 5 Ph-DBA (DBA is 9,10 di bromoanthracene) and AIBN-O 2 -C 2 H 5 Ph-DBA, С 60 -AIBN-O 2 -C 2 H 5 Ph-PhH and AIBN-O 2 --C 2 H 5 Ph-PhH. In addition, we tried to detect CL in the system С 60 -AIBN-O 2 -C 2 H 5 Ph-PhH. ExperimentalCommercially available fullerite was used, its purity (С 60 , 99.8%) was assessed by HPLC and elemental analysis. Benzene and EB (both "chemically pure" grade) were used as received, AIBN and DBA ("pure" grade) were recrystallized as described in Ref. 9. Solutions of С 60 were prepared by disso...

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“…Since fullerene has been reported as a radical sponge which has high efficiency in capturing free radicals [15], the free radical reaction between C 60 and various compounds has been extensively investigated [16][17][18]. In previous researches, it has been reported that 2 mass% C 60 could increase the onset degradation temperature (T onset ) and the maximum degradation temperature (T max ) of PP by 20 and 62°C, respectively [19,20].…”

Section: Introductionmentioning

confidence: 99%

Improving flame-retardant efficiency by incorporation of fullerene in styrene–butadiene–styrene block copolymer/aluminum hydroxide composites

Zhou

Ran

et al. 2016

J Therm Anal Calorim

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The effects of fullerene (C 60 ) and aluminum hydroxide (ATH)/C 60 combination on the thermal stability, flame retardancy and mechanical properties of styrenebutadiene-styrene block copolymer (SBS) were investigated. Adding small amount (0.5-2 mass%) of C 60 into SBS matrix raised the initial decomposition temperature of the composites slightly, while C 60 alone had little influence on the flame-retardant behavior. In SBS/ATH/C 60 system, however, the addition of C 60 significantly improved the UL-94 vertical combustion grade and limiting oxygen index. The total content of the flame retardant in SBS/ ATH/C 60 system (56 mass%) was lower than that in SBS/ ATH system (60 mass%) when UL-94 reached V0 level. Consequently, the adverse effects on the mechanical properties due to the high level of flame-retardant loading reduced. Meanwhile, the data obtained from cone calorimetric test indicated that C 60 can not only reduce the heat release rate, but also raise the char residue of SBS/ATH composites.

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Fullerenes as a tert-Butylperoxy Radical Trap, Metal Catalyzed Reaction of tert-Butyl Hydroperoxide with Fullerenes, and Formation of the First Fullerene Mixed Peroxides C₆₀(O)(OO^tBu)₄ and C₇₀(OO^tBu)₁₀

Cited by 181 publications

References 17 publications

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

Effect of the medium on the reactivity of fullerene N60 with respect to the peroxide radicals RO2 ·. Chemiluminescence in the C60—AIBN—O2—C2H5Ph—PhH system

Improving flame-retardant efficiency by incorporation of fullerene in styrene–butadiene–styrene block copolymer/aluminum hydroxide composites

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