Manganese(III) acetate-mediated free radical reactions of [60]fullerene with beta-dicarbonyl compounds

[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.     

烯醇硅醚对[60]富勒烯的亲核加成反应

在空气气氛和非极性溶剂(甲苯)中1-(4'-甲氧基苯基)-1-三甲基硅氧基乙烯与[60]富勒烯反应得到了非预计的环丙基骈[60]富勒烯衍生物(5).在无氧和极性非质子性溶剂(THF)中进行上述反应,得到了1,2-取代[60]富勒烯亲核加成产物(3)。对反应的机理作了合理的阐述。     

Face-to-face C6F5-[60]fullerene interaction for ordering fullerene molecules and application to thin-film organic photovoltaics

Treatment of [60]fullerene with potassium methylnaphthalenide and excess C(6)F(5)CH(2)Br afforded 1,4-bis(pentafluorobenzyl)[60]fullerene, the study of which showed that there is a face-to-face interaction between [60]fullerene and a perfluoro aromatic ring, allowing the molecule to be utilized for high-performance organic photovoltaic devices.     

A scalable synthesis of methano[60]fullerene and congeners by the oxidative cyclopropanation reaction of silylmethylfullerene

1,2-Dihydromethano[60]fullerene and its congeners have attracted much interest, but they have been synthesized only in very low yields because of several insurmountable problems. A new three-stage synthesis involving addition of a silylmethylmagnesium chloride to [60]- and [70]fullerene and oxidation of the anionic intermediate with CuCl(2) afforded the methano[60]- and methano[70]fullerenes in 90% and 70% overall yield, respectively. The reaction with 1,4-diorgano[60]fullerene also proceeded smoothly to give a diastereomerically pure 56-π-electron fullerene that has a higher LUMO level than the parent fullerene and gave a higher open-circuit voltage and better power conversion efficiency when fabricated into an organic photovoltaic device.     

Reaction of [60]fullerene with free radicals generated from active methylene compounds by manganese(III) acetate dihydrate

The reaction of [60]fullerene with dimethyl malonate and diethyl malonate in the presence of manganese(III) acetate dihydrate (Mn(OAc)3.2H2O) for 20 min afforded singly bonded [60]fullerene dimers 1a and 1b in a 1,4-addition pattern. When the reaction time was extended to 1 h, 1,4-bisadducts 2a and 2b were obtained. Unsymmetrical 1,4-adduct 5 and C2 symmetrical 1,16-bisadduct 6 were obtained when diethyl bromomalonate was used as the active methylene compound. Reaction of [60]fullerene with malononitrile and ethyl cyanoacetate with the aid of Mn(OAc)3.2H2O produced methanofullerenes 7 and 8. It is proposed that all these products were formed the addition of free radicals from the active methylene compounds generated by Mn(OAc)3.2H2O.     

Dimethyl azo(bisisobutyrate) and C(60) produce 1,4- and 1, 16-Di(2-carbomethoxy-2-propyl)-1,x-dihydro

Thermal decomposition of dimethyl azo(bisisobutyrate) in a solution containing C(60) produced 1,4- and 1, 16-di(2-carbomethoxy-2-propyl)-1,x-dihydro[60]fullerenes in yields of 21% and 27%, respectively, based on reacted C(60). The structure of this first 1,16-dialkyl-1,16-dihydro[60]fullerene was assigned from (13)C 2D INADEQUATE NMR spectra. The 1,16-isomer has first and second electrochemical reduction potentials shifted positively by 0. 18 V relative to those of the 1,4-isomer. From the close similarity of all spectral, chromatographic, and electrochemical data, the previously unassigned isomer of 1,x-di(2-cyano-2-propyl)-1, x-dihydro[60]fullerene, which was obtained from azo(bisisobutyronitrile) and C(60), is also a 1,16-isomer.     

Novel multicomponent reaction of [60]fullerene: the first example of 1,4-dipolar cycloaddition reaction in fullerene chemistry

The novel multicomponent reaction of [60]fullerene with dimethyl acetylenedicarboxylate and isoquinoline, quinoline or substituted quinolines was investigated. This type of reaction presents the first example of a 1,4-dipolar cycloaddition reaction in fullerene chemistry.     

Reactions of [60]Fullerene with Di(azidomethyl) benzenes

Alargenumberofadditionsto[6O]fullerenehavebeeninvestigated.However,mostoftheworkhaveconcentratedontheformationofthemono-additionproductS0f[60]fullerene'-Thedevelopment0fselechveroutestomultipleadductShascurrentlybecomethefrontierinthechendstryof[60]fuIlerene'~'.FollowingtheaPplicahonoftether-directedremotefunctionalizati0ntotheregi0specificformati0nofthedi-andtriadductSof[60]fullerene,F.Diederichetal6alsodescribed'awayforthedirectdifunctionalizationof[60]fullerenebasedonacyclizationreachono…     

One-pot sequential synthesis of acetoxylated [60]fullerene derivatives

[reaction: see text] The reaction of [60]fullerene with 4-substituted phenylhydrazine hydrochlorides in refluxing chlorobenzene under aerobic conditions afforded 1-(4-substituted phenyl)-1,2-dihydro[60]fullerenes, which could be subsequently oxidized to 1-acetoxyl-4-aryl-1,4-dihydro[60]fullerenes by manganese(III) acetate dihydrate in one pot. The transformation of ArC(60)-H to ArC(60)-OAc has been realized with Mn(OAc)(3).2H(2)O for the first time.     

Regioselective synthesis of [60]fullerene eta 5-indenide R3C60- and eta 5-cyclopentadienide R5C60- bearing different R groups

Treatment of a 1,7-diorgano[60]fullerene with Grignard reagents or organocopper reagents affords a [60]fullerene indenide or a [60]fullerene cyclopentadienide regioselectively in good to excellent yields. These reactions gave an insight into the reaction mechanism of the organocopper penta-addition reaction of [60]fullerene, giving [60]fullerene cyclopentadienide in quantitative yield.     

Regioselective synthesis of 1,4-di(organo)[60]fullerenes through DMF-assisted monoaddition of silylmethyl Grignard reagents and subsequent alkylation reaction

Monoaddition of Grignard reagents, in particular tri(organo)silylmethylmagnesium chlorides, to [60]fullerene took place smoothly in the presence of dimethylformamide to produce (organo)(hydro)[60]fullerenes, C60R(1)H, in good yield (up to 93% isolated yield). The hydrofullerene was then deprotonated to generate the corresponding anion, C60R(-), which was then alkylated to obtain 58pi-electron di(organo)[60]fullerenes, C60R(1)R(2), in good to high yield (up to 93% overall yield). The two-step methodology provides a wide variety of 1,4-di(organo)[60] fullerenes bearing the same or different organic addends on the [60] fullerene core. By changing the addends, one can control the chemical and physical properties of the compounds at the molecular and bulk levels.     

Design and synthesis of multi-component 18 pi annulenic fluorofullerene ensembles suitable for donor-acceptor applications

A series of trannulene (all-trans annulene) derivatives of [60]fullerene have been prepared by reacting C(60)F(18) with methanetricarboxylate esters that incorporate a range of photoactive functions. All the compounds have the intense emerald-green colour of fullerene trannulenes, characterised by strong bands at ca. 612 and 667 nm. Single crystal X-ray studies show that the packing varies with the nature of the addend, attributable to differing steric effects. UV/vis absorption spectra display transitions of the respective fullerene and addend models, indicating absence of electronic interactions between them in the ground state. These now provide an extensive series for testing photoactive (light-harvesting) properties, with the exceptional properties of having strong visible light absorption. Their exceptional stability is attributed to the 18[small pi] aromatic circuit, inability to undergo nucleophilic substitution without disrupting this circuit, and a curved cage region that is shielded to reagents by the three bulky addends.     

Unexpected interconversion reaction of 1,4-diaminofullerenes

A facile substitution of amine groups attached to the fullerene cage occurs when 1,4-diaminofullerenes C60[NR2]2 are allowed to react with excess of another amine R'2NH; this reaction proceeds rapidly at room temperature without any additional initiators.     

[60]富勒烯衍生物的对称性、碳笼结构与13C NMR谱

本文全面综述了多种[60]富勒烯衍生物的结构,阐述了(13)~C NMR谱在[60]富勒烯衍生物结构表征中的应用,重点讨论了不同对称性[60]富勒烯衍生物的(13)~C NMR谱图特征.通过[60]富勒烯部分(13)~C共振线的化学位移、数目和相对强度,可以确定[60]富勒烯衍生物的对称结构和加成方式.对于C_s、C_(2v)和C_(3v)对称性的[60]富勒烯衍生物,镜面上的碳原子的相对化学位移很大程度上取决于他们距加成位置的距离.因此,(13)~C NMR谱在碳笼具体结构的确定中具有不可替代的作用.     

[60]富勒烯衍生物的对称性、碳笼结构与C NMR谱

本文全面综述了多种[60]富勒烯衍生物的结构,阐述了(13)~C NMR谱在[60]富勒烯衍生物结构表征中的应用,重点讨论了不同对称性[60]富勒烯衍生物的(13)~C NMR谱图特征.通过[60]富勒烯部分(13)~C共振线的化学位移、数目和相对强度,可以确定[60]富勒烯衍生物的对称结构和加成方式.对于C_s、C_(2v)和C_(3v)对称性的[60]富勒烯衍生物,镜面上的碳原子的相对化学位移很大程度上取决于他们距加成位置的距离.因此,(13)~C NMR谱在碳笼具体结构的确定中具有不可替代的作用.     

Polymeric fullerene hydrides. Birch reduction of [60] fullerene polymers from solution-based photopolymerization and free radical polymerization reactions

Fullerene polymers represent a new class of carbon materials for potential hydrogen storage applications. Poly[60]fullerene polymers were obtained by covalently linking [60]fullerene molecules in photochemical reactions. [60]Fullerene polymers were also prepared in free radical reactions of [60]fullerene with radical initiator benzoyl peroxide. The polymeric [60]fullerene materials were hydrogenated under Birch reduction conditions. The hydrides, which contain ≈3.5% (wt/wt) of hydrogen, were characterized by use of gel permeation chromatography, NMR, FT-IR, and elemental analysis. The results are compared with those of monomeric [60]fullerene hydrides.     

Efficient preparation of monoadducts of [60] fullerene and anthracenes by solution chemistry and their thermolytic decomposition in the solid state

The efficient preparation of monoadducts of [60]fullerene and seven anthracenes (anthracene, 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 2,3,6,7-tetramethylanthracene, and 2,6-di-tert-butylanthracene) by cycloaddition in solution is described. The seven mono-adducts of [60]fullerene and the anthracenes were characterized spectroscopically and were obtained in good yields as crystalline solids. The monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 2-methylanthracene and 9,10-dimethylanthracene crystallized directly from the reaction mixture. The thermolytic decomposition at 180 degrees C of the crystalline monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 9-methylanthracene and 9,10-dimethylanthracene all gave rise to the specific formation of a roughly 1:1 mixture of [60]fullerene and the corresponding antipodal bisadducts ("trans-1"-bisadducts) of [60]fullerene and the anthracenes. In contrast, the crystalline monoadducts of [60]fullerene and the anthracene derivatives 2-methylanthracene, 2,3,6,7-tetramethylanthracene and 2,6-di-tert-butylanthracene all decomposed to [60]fullerene and anthracenes (without detectable formation of bisadducts) upon heating in the solid state to temperatures of 180 to 240 degrees C. The formation of the antipodal bisadducts from thermolytic decomposition of crystalline samples of the monoadducts was rationalized by topochemical control.     

Absorption spectrophotometric study of supramolecular complexation of [60]- and [70]fullerenes with 24,26-dimethoxy-25,27-dihydroxy calix[4]arene

Supramolecular interactions of 24,26-dimethoxy-25,27-dihydroxy calix[4]arene (1) with [60]- and [70]fullerenes have been studied in only chloroform and in a ternary solvent mixture comprising of chloroform, ethyl alcohol and toluene by UV-vis absorption spectrophotometric method. The experimental results are explained using the model that takes into account the interaction between electronic subsystems of 1 and fullerene. The most interesting feature is the preference of [60]fullerene over [70]fullerene for 1 in ternary solvent mixture as revealed by higher value of formation constant of [60]fullerene/1 complex. The selectivity towards [60]fullerene opens up the way toward self-assembling systems and new separation and purification methods for fullerenes.     

The first synthesis of a methano[60]fullerene with an electron-donating group at the methano-bridge carbon: synthesis and reaction of aminomethano[60]fullerene

[reaction: see text] Aminomethano[60]fullerene was synthesized for the first time as a trifluoromethanesulfonic acid salt by applying the Curtius rearrangement of azidocarbonylmethano[60]fullerene as the key reaction. Aminomethano[60]fullerene thus obtained was found to be able to react with various acyl chlorides to afford the corresponding amides.     

Selective addition to [60]fullerene of two different radicals generated from Mn(III)-based radical reaction

Reaction of [60]fullerene in toluene with diethyl methylmalonate (3a), diethyl ethylmalonate (3b), diethyl bromomalonate (3c), triethyl methanetricarboxylate (3d) and ethyl cyanoacetate (3e) in the presence of manganese(III) acetate dihydrate afforded benzyl-substituted unsymmetrical 1,4-adducts 4a-4e. Dibenzylated 1,4-adduct 5 and methanofullerene 6 were also obtained in the case of 3d and 3e, respectively. A possible reaction mechanism for the formation of the 1,4-adducts 4a-4e is proposed.