Chemistry of hydrocarbon compounds – Aromatic compound synthesis – By alkyl or aryl transfer between molecules – e.g.,...
Patent
1995-09-15
1998-06-09
Ivy, C. Warren
Chemistry of hydrocarbon compounds
Aromatic compound synthesis
By alkyl or aryl transfer between molecules, e.g.,...
546285, 560 20, 560255, 564308, 568306, 568632, 505460, 423445B, C07C 522
Patent
active
057637199
DESCRIPTION:
BRIEF SUMMARY
RELATED APPLICATIONS
This application claims priority to German Application No. P 43 01 458.5, filed Jan. 20, 1993, and to International Application No. PCT/EP93/03658, filed Dec. 22, 1993, both incorporated herein by reference.
Several publications are referenced in this application. These references describe the state of the art to which this invention pertains, and are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Fullerenes are cage-like carbon allotropes of the formula (C.sub.20+2m) (where m=a natural number). They contain twelve five-membered rings and any number, but at least two, six-membered rings of carbon atoms.
Although this class of compounds was not discovered until 1985 by Kroto and Smalley (Nature, 1985, 318, 162) and Kratschmer and Huffmann did not report the preparation of macroscopic amounts of C.sub.60 until 1990 (Nature, 1990, 347, 354), such compounds have very quickly attracted wide interest and within a very short time have become the subject of numerous research studies (see, for example, G. S. Hammond, V. J. Kuck (Editors), "Fullerenes", ACS Symposium Series 481, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research 1992, 25, 98-175).
The use of fullerenes as synthetic building blocks in organic chemistry is beset by great difficulties since, for example, the degree of substitution of fullerenes can be controlled only with difficulty during the formation of derivatives. C.sub.60 contains 30 double bonds which are in principle available as reaction centers. In addition, a very large number of positional isomers is possible as soon as even only two substituents are present on the fullerene base structure.
Further problems are provided by the low solubility of the fullerenes in all conventional solvents.
However, since there is the expectation of a high potential of this class of substances, for example in the fields of optoelectronics and research on active compounds, efforts have already been made to form derivatives, in particular of C.sub.60 (see, for example, H. Schwarz, Angew. Chemie. 1992, 104, 301 and F. Wudl et al. in "Fullerenes" G. S. Hammond, V. S. Kuck, eds. ACS Symp. Ser. 481, p. 161, Washington DC 1992 and Accounts of Chemical Research, 1992, 25, 157).
It is already known that fullerenes can be reacted with dienes to give Diels-Alder adducts ("Fullerenes ACS-Symposium Series No. 481, p. 164). The dienophilic reactivity of C.sub.60 has hitherto been observed only in the reaction with anthracene and furan and also cyclopentadiene. However, all these reactions have a broad product distribution. Furthermore, these products decompose again on heating into their starting compounds.
It is also known that fullerenes can be reacted with diazo compounds in a 1,3 dipolar cycloaddition (e.g. F. Wudl, Acc. Chem. Res., 1992, 25, 157).
It was desirable to synthesize derivatives of fullerenes which are thermally stable, contain the basic fullerene framework, and make possible further reactions at the derivatized position.
DESCRIPTION OF THE INVENTION
It has now been found that well-defined fullerene derivatives can be obtained by reacting fullerene with a compound of the formula ##STR3## or the formula ##STR4## with the aromatic ring system being bonded to the fullerene via a cycloaliphatic 6-membered ring.
The invention accordingly provides a fullerene derivative of the formula I, ##STR5## where the symbols and indices have the following meanings: F is a fullerene radical of the formula (C.sub.20+2m), where m is a number from 1 to 50 NR.sup.9 R.sup.10, NR.sup.9 H, CO.sub.2 R.sup.9, OCOR.sup.10, CN, COR.sup.10, Cl, Br, I, F, OR.sup.11, CONH.sub.2, C.sub.1 -C.sub.20 alkyl which can be substituted by Cl, I, Br and F, C.sub.3 -C.sub.8 -cycloalkyl, aryl, heteroaryl, where R.sup.9 to R.sup.11 are each H, C.sub.1 -C.sub.20 -alkyl which can be substituted by F, Cl, Br or I, pyridinyl or phenyl which in turn can be substituted by F, Cl, Br, I, nitro, amino, C.sub.1 -C.sub.20 -alkylamino, C.sub.6 -C.sub.14 -arylamino, C.sub.1 -C.sub.20 -alkoxy o
REFERENCES:
Wudl, F. Acc. Chem. Res. 1992, 25, pp. 157-161.
G. S. Hammond et al., "Fullerenes", ACS Symposium Series 481, Chapter 11: Survey of Chemical Reactivity of C60' Electrophile and Dieno-polar-ophile Par Excellence American Chemical Society, Washington, D.C., 1992, pp. 161-175.
Chemical Reviews, vol. 70, No. 4, published in 1970 I. L. Klundt "Benzocyclobutene and its derivatives" pp. 471-487.
Belik Pavel
Gugel Andreas
Mullen Klaus
Dahlen Garth M.
Hoechst AG
Ivy C. Warren
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