150493-27-9Relevant articles and documents
Synthesis and reactions of 2,2-[60]fullerenoalkanoyl chlorides
Tada, Tomoyuki,Ishida, Yasuhiro,Saigo, Kazuhiko
, p. 1633 - 1639 (2006)
2,2-[60]Fullerenoalkanoyl chlorides (1a-d) were easily and securely prepared from the corresponding 2,2-[60]fullerenoalkanoic acids (2a-d) by the reaction with thionyl chloride in an unusual mixed solvent, CH 2Cl2/dioxane. The characterization of 1a-d by 1H and 13C NMR, FT-IR, and MALDI-TOF-MASS was conducted for the first time. The 2,2-[60]fullerenoalkanoyl chlorides thus obtained were readily converted to the corresponding amides and esters in moderate to excellent yields by the condensation with amines and alcohols, respectively. Upon applying the condensation, [60]fullerene-biomolecule hybrids were easily prepared.
72. Improved Purification of C60 and Formation of ?- and ?-Homoaromatic Methano-Bridged Fullerenes by Reaction with Alkyl Diazoacetates
Isaacs, Lyle,Wehrsig, Arno,Diederich, Francois
, p. 1231 - 1250 (1993)
A rapid and inexpensive method for the large-scale purification of C60 is the simple filtration of the toluene-soluble extract of commercial fullerene soot through a short plug of charcoat/silica gel with toluene as the eluent.Reactions of C60 with ethyl and tert-butyl diazotates in refluxing toluene lead to the formation of the (alkoxycarbonyl)methylene-bridged isomers 1a-3a and 1b-3b, respectively, which can be equilibrated, upon further heating, into the single compounds 1a and 1b, respectively.Isomers 1a/b possess the methano bridge at the 6-6 ring junction, whereas structures 2a/b and 3a/b are bridged at the 6-5 junction.A dramatic influence of local and ?-ring current anisotropic effects of the fullerene sphere on the NMR chemical shifts of the methine protons in the bridge is observed: the chemical shifts of the protons located over a pentagon ring in 2a/b and over a hexagon ring in 3a/b differ by Δδ = 3.47 and 3.45 ppm, respectively.The analysis of the 13C-NMR chemical shifts of the bridgehead C-atoms and the 1J(C,H) coupling constants for the methano-bridge atoms reveals conclusively that the 6-5-ring-bridged structures 2a/2b and 3a/3b are ?-homoaromatic ('open' transannular bond) and the 6-6-ring-bridged structures 1a/b are ?-homoaromatic ('closed' transannular bond).The electronic absorption spectra show that ?-homoconjugation in 2a/b and 3a/b represents a much smaller electronic perturbation of the original C60 chromophore than ?-homoconjugation in 1a/b.The results of this study demonstrate an impressive linkage between the chemistry of methano-bridged annulenes and methano-bridged fullerenes.
Synthesis of methano[60]fullerene derivatives: The fluoride ion-mediated reaction of [60]fullerene with silylated nucleophiles
Hino, Tetsuo,Kinbara, Kazushi,Saigo, Kazuhiko
, p. 5065 - 5067 (2001)
A new reaction of [60]fullerene with silylated nucleophiles is described. The cyclopropanation of [60]fullerene with silylated nucleophiles, such as silyl ketene acetals, silyl ketene thioacetals, and silyl enol ethers, derived from α-halo carbonyl compounds, smoothly proceeded in the presence of KF/18-crown-6 to give the corresponding methano[60]fullerene derivatives in moderate to good yields.
A Superior Synthesis of -Methanofullerenes: The Reaction of Sulfonium Ylides with C60
Wang, Yihan,Cao, Jingrong,Schuster, David I.,Wilson, Stephen R.
, p. 6843 - 6846 (1995)
The addition-elimination reaction of stabilized sulfonium ylides 1a-f to C60 provides a new high yield route to -methanofullerenes.The rates of reaction differ with the nucleophilicity of the ylides.
Catalytic [2+1]-cycloaddition of ethyl diazoacetate to fullerene [60]
Tuktarov,Akhmetov,Kamalov,Khalilov,Pudas,Ibragimov,Dzhemilev
, p. 1168 - 1174 (2009)
Cyclopropanation of C60-fullerene was performed with ethyl diazoacetate in the presence of Pd(PPh3)4 catalyst. A probable reaction mechanism is suggested.
Dirhodium(II) Tetraacetate-Mediated Decomposition of Ethyldiazoacetate and Ethyldiazomalonate in the Presence of Fullerene. A New Procedure for the Selective Synthesis of [6-6]-Closed Methanofullerenes
Pellicciari, Roberto,Annibali, Danilo,Costantino, Gabriele,Marinozzi, Maura,Natalini, Benedetto
, p. 1196 - 1198 (1997)
The reaction of C60 fullerene with carboalkoxycarbenoids generated by Rh2(OAc)4-catalyzed decomposition of α-diazoester precursors is reported. This reaction is the first example of a transition metal catalyzed carbenoid reaction with fullerene and represents a significative improvement in terms of reaction conditions, selectivity of the products obtained, and yields over previously reported methods.
176. Structures and Chemistry of Methanofullerenes: A Versatile Route into N--Substituted Amino Acids
Isaacs, Lyle,Diederich, Francois
, p. 2454 - 2464 (1993)
The reaction of C60 with oxadiazole 13 afforded the dimethoxymethanofullerene 7 in 32 percent yields as a 6-6-ring-bridged isomer with a closed transannular bond.A literature survey showed that all 6-6-ring-bridged methanofullerenes are ?-homoaromatic with a closed transannular bond (6-6-closed) and all 6-5-ring-bridged are ?-homoaromatic with an open transannular bond (6-5-open).The preference for 6-6-closed and 6-5-open structures is not due to substituent effects but is best explained with the conservation in these isomers of the favorable bonding seen in C60 with higher double- bond character at 6-6-bonds and higher single-bond character at 6-5-bonds.Reaction of C60 with diazo diester 15 gave the fullerene diester 14 which was hydrolyzed with BBr3 in benzene to the methanofullerenecarboxylic acid 10, a versatile synthon for the preparation of amphiphilic fullerene derivatives.Treatment of 10 with alcohols and amino acid esters under DCC coupling conditions afforded the esters 5 and 17 and the amino-acid derivatives 11 and 12, respectively.
Electroreductive retro-cyclopropanation reactions of nitrophenyl-methanofullerene derivatives
Herranz, M. Angeles,Beulen, Marcel W. J.,Rivera, Jose A.,Echegoyen, Luis,Diaz, Marta C.,Illescas, Beatriz M.,Martin, Nazario
, p. 2048 - 2053 (2002)
Spiromethanofullerenes 5, 8 and 10 containing a nitrophenyl substituent attached to the methano adduct, were synthesized via the diazomethane route or via the Bingel reaction. The electrochemistry and electrolysis of these compounds were investigated in THF. Reductive electrolysis leads to the removal of the addend, formation of [60]fullerene, and to the formation of bis-adducts from the mono-adducts. The extent of the retro-cyclopropanation reaction varied as a function of the structural and electronic differences between the compounds. Electron spin resonance studies (ESR) allowed the observation of spin localization on the fullerene core or on the nitrobenzene moiety upon successive reductions.
C602- chemistry: C60 adducts bearing two ester, carbonyl, or alcohol groups
Allard, Emmanuel,Delaunay, Jacques,Cousseau, Jack
, p. 2239 - 2242 (2003)
(Matrix presented) Reactions of activated halo compounds XCH2-A (X = Br, I; A = ester, ketone) with C602- anion give rise to C60(CH2-A)2 adducts (major products) along with unexpected metha
Quantitative spectroscopic studies of the photoexcited state properties of methano- and pyrrolidino-[60]fullerene derivatives
Ma,Bunker,Guduru,Zhang,Sun
, p. 5626 - 5632 (1997)
UV/vis absorption and fluorescence spectra and fluorescence quantum yields and lifetimes of a series of methano- and pyrrolidino-[60]fullerene derivatives in different solvents are studied systematically. The absorption and fluorescence properties of the
