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

共 55 条

[1] SYNTHESIS AND CHARACTERIZATION OF DIETHYNYLMETHANOBUCKMINSTERFULLERENE, A BUILDING-BLOCK FOR MACROCYCLIC AND POLYMERIC CARBON ALLOTROPES [J].

AN, YZ ;

RUBIN, Y ;

SCHALLER, C ;

MCELVANY, SW .

JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (11) :2927-2929

[2]

ANDERSON HL, 1994, ANGEW CHEM INT EDIT, V33, P1628, DOI 10.1002/anie.199416281

[3] CONJUGATED PORPHYRIN LADDERS [J].

ANDERSON, HL .

INORGANIC CHEMISTRY, 1994, 33 (05) :972-981

[4] FULLERENE-ACETYLENE HYBRIDS - ON THE WAY TO SYNTHETIC MOLECULAR CARBON ALLOTROPES [J].

ANDERSON, HL ;

FAUST, R ;

RUBIN, Y ;

DIEDERICH, F .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (13) :1366-1368

[5] TETRAETHYNYLETHENES - FULLY CROSS-CONJUGATED PI-ELECTRON CHROMOPHORES AND MOLECULAR SCAFFOLDS FOR ALL-CARBON NETWORKS AND CARBON-RICH NANOMATERIALS [J].

ANTHONY, J ;

BOLDI, AM ;

RUBIN, Y ;

HOBI, M ;

GRAMLICH, V ;

KNOBLER, CB ;

SEILER, P ;

DIEDERICH, F .

HELVETICA CHIMICA ACTA, 1995, 78 (01) :13-45

[6] SYNTHESIS OF ALKYNYL(PHENYL)IODONIUM TRIFLATES AND THEIR REACTION WITH DIETHYL 2-AMINOMALONATE [J].

BACHI, MD ;

BARNER, N ;

CRITTELL, CM ;

STANG, PJ ;

WILLIAMSON, BL .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (12) :3912-3915

[7] REACTION OF BUCKMINSTERFULLERENE WITH ORTHO-QUINODIMETHANE - A NEW ACCESS TO STABLE C60 DERIVATIVES [J].

BELIK, P ;

GUGEL, A ;

SPICKERMANN, J ;

MULLEN, K .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1993, 32 (01) :78-80

[8] CYCLOPROPYLATION OF FULLERENES [J].

BINGEL, C .

CHEMISCHE BERICHTE-RECUEIL, 1993, 126 (08) :1957-1959

[9]

COREY EJ, 1972, TETRAHEDRON LETT, P3769

[10] COMPLETELY SPIROCYCLOPROPANATED MACROCYCLIC OLIGODIACETYLENES - THE FAMILY OF EXPLODING [N]ROTANES [J].

DEMEIJERE, A ;

KOZHUSHKOV, S ;

HAUMANN, T ;

BOESE, R ;

PULS, C ;

COONEY, MJ ;

SCOTT, LT .

CHEMISTRY-A EUROPEAN JOURNAL, 1995, 1 (02) :124-131

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