Fullerene acetylene hybrids: Towards a novel class of molecular carbon allotropes

被引：90

作者：

Timmerman, P ^{[1
]}

Anderson, HL ^{[1
]}

Faust, R ^{[1
]}

Nierengarten, JF ^{[1
]}

Habicher, T ^{[1
]}

Seiler, P ^{[1
]}

Diederich, F ^{[1
]}

机构：

[1] ETH ZENTRUM,ORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND

来源：

TETRAHEDRON | 1996年 / 52卷 / 14期

基金：

英国工程与自然科学研究理事会;

关键词：

D O I：

10.1016/0040-4020(96)00102-0

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis and complete characterization of 17 new fullerene-acetylene covalent derivatives is described. Reaction of 3-bromo-1,5-bis(trimethylsilyl)penta-1,4-diyne (5) with C-60 gave bis-protected diethynylmethanofullerene 4 in 56% yield. Unsymmetrically bis-protected diethynylmethanofullerene 6 was synthesized in 53% yield from tosylhydrazone 7 and C-60 Proto-desilylation of 4 and 6 gave the corresponding free alkynes 3 and 8 in 83% and 69% yield, respectively. partial deprotection of 4 afforded mono-protected fullerene 9 in 35% yield. Oxidative hetero-coupling reactions of 3 and 8 under Hay conditions with various monosubstituted acetylenes gave the butadiynylmethanofullerenes 10-13 in yields varying from 25-49%. Home-coupling of 8 produced dumbbell-shaped fullerene 14, the first dimeric fullerene that could be fully characterized. The X-ray crystal structure analysis of 14 revealed little or no electronic interaction between the two fullerene spheres. Addition of lithium trimethylsilylacetylide to C-60 gave access to 1-substituted-2-(trimethylsilylethynyl)fullerenes. The acidity of hydrofullerene 16, synthesized in 58% yield, was studied as a function of base and solvent. Reaction of lithiated fullerene 17 with various electrophiles is discussed. Alcohol 25 was prepared in 57% yield by reaction of 17 with formaldehyde. Under strongly basic conditions, 25 eliminates formaldehyde to give 16 in quantitative yield Oxidation of 25 afforded aldehyde 27 in 53% yield, a rather unstable compound that is easily converted to hydrofullerene 16. Conversion of 25 to the corresponding tosylate could be performed in 40% yield. (C) 1996 Elsevier Science Ltd

引用

页码：4925 / 4947

页数：23

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