Alkylation of Dihydrofullerenes

Abstract

The fulleride dianions C(60)(2-) and C(70)(2-) were generated by deprotonation of the corresponding hydrogenated fullerenes, 1,2-C(60)H(2) and 1,2-C(70)H(2). These anions were prepared in the presence of a variety of alkylating agents, and mono- or dialkylated products were obtained. Alkylation was not successful with sulfonate ester alkylating agents. Deprotonation of monoalkylated compounds, followed by second alkylation with a different alkylating agent, produced heterodialkylated compounds. The monoalkyated material was invariably the 1,2-isomers, while the dialkylated materials were generally 1,4-isomers, although some 1,2-isomer was observed in the C(70) context. The major product from alkylation of C(70)(2-) was the 7,23-isomer 13a, a structure where the alkylation took place near the equator of the fullerene cage, rather than at the more strained carbons near the poles.

Hydro‐aza‐(C59N)fullerenes: Formation Mechanism and Hydrogen Substitution

“…Ad istinct and unprecedented color change from orange-red to dark-green appeared on adding the base Bu 4 NOHt ot he startingm aterial 5a-8a.I nC 60 chemistry, ad eep-green color is characteristic of RC 60 À anions. [27,28] In particular,t he UV/Vis spectrumo fd eprotonated 5a-8a shows absorptionsb etween 600 and 1200 nm ( Figure 4). The generatedi ntermediates are air-sensitive, whichc ould be provenb yq uenching the solution with aerial oxygen,w hereupon the distinct absorptions between 600 nm and 1200 nm disappeared.…”

“…A distinct and unprecedented color change from orange‐red to dark‐green appeared on adding the base Bu 4 NOH to the starting material 5 a – 8 a . In C 60 chemistry, a deep‐green color is characteristic of RC 60 − anions . In particular, the UV/Vis spectrum of deprotonated 5 a – 8 a shows absorptions between 600 and 1200 nm (Figure ).…”

Recent Achievements in Organic Trithiocarbonates Synthesis

“…40,41 Tetra-n-butylammonium hydroxide is a versatile and efficient reagent which acts as a base-and phase-transfer catalyst in organic reactions. [41][42][43][44][45] Under neat aqueous conditions, Soleiman-Beigi and co-workers utilized this reagent as an efficient catalyst to synthesize symmetrical trithiocarbonates in high yields (Scheme 16). 46 In 2013, Movassagh and Alapour developed a useful and dependable protocol for the synthesis of symmetrical trithiocarbonates in a one-pot reaction by use of potassium phosphate in dimethylformamide, as an inexpensive and efficient reagent, (Scheme 17).…”

Functionalization of [60]fullerene through the anionic route

“…Another chemical process has been reported, in which C 60 2-anion is produced in benzonitrile medium by treating dihydrofullerene C 60 H 2 with tetrabutylammonium hydroxide [10].…”

“…Various alkyl bromides RBr were used (R=Ph 2 CH, PhCH 2 , HC≡C-CH 2 , CH 2 =CH-CH 2 ), and gave rise to the corresponding R(H)C 60 derivatives in fair to good yields (21% from propargyl bromide, 60% from diphenylmethyl bromide) after an immediate quenching of the reaction mixture by acetic acid [10].…”