Fullerene derivatives, methods of preparing them and their use

• US 5,739,376 A
• Filed: 10/20/1995
• Issued: 04/14/1998
• Est. Priority Date: 04/24/1993
• Status: Expired due to Term

• Current Assignee: Siemens Axiva GmbH & Co. KG (Siemens AG)
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Bingel, Carsten
• Primary Examiner(s): BARTS, SAMUEL A
• Application Number:
  US08/535,163
• Time in Patent Office: 907 Days
• Field of Search: 560/127, 560/51, 560/54, 560/39, 549/274, 549/454, 562/509, 562/459, 568/329, 540/467, 564/47
• US Class Current: 560/51
• CPC Class Codes: C07C 205/43 to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
• CPC Class Codes: C07C 2603/00 Systems containing at least three condensed rings
• CPC Class Codes: C07C 2604/00 Fullerenes, e.g. C60 buckminsterfullerene or C70
• CPC Class Codes: C07C 49/553 polycyclic
• CPC Class Codes: C07C 49/798 containing rings other than six-membered aromatic rings
• CPC Class Codes: C07C 49/82 containing hydroxy groups
• CPC Class Codes: C07C 69/00 Esters of carboxylic acids; Esters of carbonic or haloformic acids ortho esters, see the relevant groups, e.g. C07C43/32
• CPC Class Codes: C07F 9/4025 Esters of poly(thio)phosphonic acids
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.

Abstract

Fullerene derivatives, methods of preparing the same and methods of using the same, wherein the fullerene derivatives are of the formula I ##STR1##

Claims

1. A fullerene derivative of the formula I ##STR49## where the symbols and indices have the following meanings:

F;

is a fullerene radical of the formula C.sub.(20+2m) where m=20, 25, 28, 29;

E¹, E² ;

are identical or different and are each COOH, COOR, CONRR¹, CHO, COR, CN, P(O)(OR)₂ and SO₂ R, where R, R¹ are each a straight-chain or branched, aliphatic radical (C₁ to C₂₀) which may be unsubstituted or monosubstituted or polysubstituted by identical or different substituents, in which radical up to every third CH₂ unit can be replaced by O or NR⁴, where R⁴ is (C₁ -C₂₀)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 5 substituents R, OH, OR, COOR, OCOR, SO₃ H, SO₂ Cl, F, Cl, Br, NO₂ and CN or together are ##STR50## or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/Cl/Br, where R is as defined above, or are different from one another and are each NO₂, R³ or H, where R³ is an unsubstituted, monosubstituted or polysubstituted aliphatic radical (C₁ to C₂₀);

n;

is a natural number from 1 to 10+m where m=20, 25, 28, 29.

2. A fullerene derivative of the formula I as claimed in claim 1, where the symbols and indices have the following meanings:

F;

is a fullerene radical of the formula C.sub.(20+2m) where m=20, 25, 28, 29,

E¹, E² ;

are identical or different and are each COOR, COR, P(O)(OR)₂, COOH, CN, where R is a straight-chain or branched, aliphatic radical (C₁ to C₂₀) which may be unsubstituted or monosubstituted or polysubstituted by identical or different substituents, in which radical up to every third CH₂ unit can be replaced by O or NR⁴, where R⁴ =(C₁ -C₂₀)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 3 substituents R, OH, OR, COOR, OCOR, SO₃ H, SO₂ Cl, F, Cl, Br, NO₂ and CN, or together are ##STR51## or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/C1/Br,

n;

is a natural number from 1 to 12.

3. A fullerene derivative of the formula I as claimed in claim 1, where the symbols and indices have the following meanings:

R;

C₆₀, C₇₀

E1/E2;

CO₂ R¹ /CO₂ R² ;

CO₂ R¹ /COR² ;

CO₂ R¹ /CN;

COAr/R¹ or H;

COAr/R¹ or Cl;

##STR52## COR¹ /COR² ;

P(O)(OR¹)₂ /P(O)(OR²)₂ ;

COOH/COOH;

where R¹ and R² are identical or different and are each a straight-chain or branched alkyl radical (C₁ to C₂₀) which may be unsubstituted or monosubstituted or polysubstituted by identical or different substituents, in which radical every third CH₂ unit can be replaced by O or NR⁴, where R⁴ =(C₁ -C₂₀)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 3 substituents OH, OMe, CO₂ R¹, OOCR¹, SO₃ H, SO₂ Cl, F, Cl, Br, NO₂ and CN, and Ar is a phenyl radical which can likewise be substituted by from 1 to 3 substituents OH, OMe, Me, CO₂ R¹, OCOR¹, SO₃ H, SO₂ Cl, F, Cl, Br, NO₂ and CN or can be substituted by a straight-chain or branched aliphatic radical (C₁ -C₂₀), preferably C₁ -C₁₀, which may be unsubstituted or monosubstituted or disubstituted by identical or different substituents COOR⁵, CONHR⁵, CONR₂⁵, CONH₂, CONR⁶, COOH, OH or OCOR⁵, COOAr, COOCH₂ Ar, where R⁵ = ##STR53## C₁ -C₆ -alkyl, hydroxy- (C₁ -C₆)-alkyl, carboxy (C₁ -C₆)-alkyl or (C₁ -C₃)-alkylcarboxyl (C₁ -C₆)-alkyl;

R⁶ =C₁₁ -C₁₇ -alkylene in which up to every 3rd CH₂ unit can be replaced by O and which together with the amide nitrogen forms a C₁₂ -C₁₈ ring, and Ar is as defined above;

n;

is a natural number from 1 to 6.

4. A fullerene derivative of the formula I as claimed in claim 1, where the symbols and indices have the following meanings:

F;

C₆₀, C₇₀

E¹ /E² ;

CO₂ Alkyl¹ /CO₂ Alkyl¹ ;

CO₂ Alkyl¹ /COAlkyl² ;

COAr/Ar;

COAr;

Alkyl¹ ;

COAr/H

where Alkyl¹, Alkyl² are each a straight-chain or branched alkyl radical having from 1 to 10 carbon atoms in which up to every third CH₂ unit can be replaced by O, and Ar is a phenyl group which can be substituted by a straight-chain or branched aliphatic radical (C₁ -C₆) which may be unsubstituted or monosubstituted or disubstituted by identical or different substituents COOR⁵, CONHR⁵, CONR₂⁵, CONR⁶, COOH, OH or OCOR⁵, where R⁵ and R⁶ are as defined above,

n;

is 1 or 2.

5. A process for preparing fullerene derivatives as claimed in claim 1, which comprises reacting a fullerene of the formula C.sub.(20+2m) (m=a natural number) in an aprotic organic solvent with a CH acid component of the formula II ##STR54## where the symbols and indices have the following meanings F is a fullerene radical of the formula C.sub.(20+2m) where m=20, 25, 28, 29,

E¹ and E² are identical or different and are each COOH, COOR, CONRR¹, CHO, COR, CN, P(O)(OR)₂ and SO₂ R, where R, R¹ are each a straight-chain or branched aliphatic radical (C₁ to C₂₀) which may be unsubstituted or monosubstituted or polysubstituted by identical or different substituents, in which radical up to every third CH₂ unit can be replaced by O or NR⁴, where R⁴ is (C₁ -C₂₀)-alkyl or benzyl, or a benzyl radical or phenyl radical which can be unsubstituted or substituted by from 1 to 5 substituents R, OH, OR, COOR, OCOR, SO₃ H, SO₂ Cl, F, Cl, Br, NO₂ and CN or together are ##STR55## or are different from one another and are each COR, R or H, or are different from one another and are each COR/R or F/Cl/Br, or are different from one another and are each NO₂, R³ or H, where R³ can be an unsubstituted, monosubstituted or polysubstituted aliphatic radical (C₁ to C₂₀),

X is --Cl, --Br, --I, --OSO₂ Ar, OSO₂ CF₃, OSO₂ C₄ F₉, and alkali metal hydrides, alkali metal hydroxides, alkoxides, amides, amines or guanidines in a temperature range from -78°

C. to 180°

C.