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WO1997000235A1 - Bisadducts asymetriques de fullerenes c70, procede de preparation et d'utilisation - Google Patents

Bisadducts asymetriques de fullerenes c70, procede de preparation et d'utilisation Download PDF

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Publication number
WO1997000235A1
WO1997000235A1 PCT/EP1996/002395 EP9602395W WO9700235A1 WO 1997000235 A1 WO1997000235 A1 WO 1997000235A1 EP 9602395 W EP9602395 W EP 9602395W WO 9700235 A1 WO9700235 A1 WO 9700235A1
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WO
WIPO (PCT)
Prior art keywords
substituted
alkyl
radical
coor
cooh
Prior art date
Application number
PCT/EP1996/002395
Other languages
German (de)
English (en)
Inventor
Carsten Bingel
Original Assignee
Hoechst Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Publication of WO1997000235A1 publication Critical patent/WO1997000235A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
    • C07J41/0055—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 the 17-beta position being substituted by an uninterrupted chain of at least three carbon atoms which may or may not be branched, e.g. cholane or cholestane derivatives, optionally cyclised, e.g. 17-beta-phenyl or 17-beta-furyl derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70

Definitions

  • Fullerenes are cage-shaped carbon allotropes of the general formula (C 20 + 2rJ ' w o at m is a natural number. They contain twelve five- and any number, but at least two six-membered rings made of carbon atoms. Although this class of compounds was only discovered in 1985 by Kroto and Smalley ( Nature, 1985, 318, 1 62), and Krätschmer and Huffman reported for the first time in 1990 on the representation of macroscopic amounts of C 60 (Nature 1990, 347, 354), such compounds quickly met with broad interest and became the subject within a very short time Numerous research projects (see e.g. GS Hammond, VJ Kuck (Editors), Fullerenes, American Chemical Society, Washington DC 1992 and Accounts of Chemical Research, March 1992 edition).
  • the invention therefore relates to fullerene C 70 bisadducts of the formula (I)
  • E 1 can with E 2 and E 3 with E 4
  • E 2 and E 4 are COX radicals, where X is H, OH, Cl, Br, OR 4 , NH 2 , NHR or NRR 1 , where R 4 defines either as R. C.
  • E 1 and E 3 are COR and E 2 and E 4 are R or H, F, Cl, Br;
  • E 1 and E 3 are NO 2 and E 2 and E 4 are R 5 or H, where R 5 represents an optionally mono- or polysubstituted aliphatic radical C 1 to C 20 ;
  • E 1 is different from E 3 and / or E 2 is different from E 4 .
  • E 1 , E 2 , E 3 , E 4 are either selected from the group consisting of COOH,
  • COOR, OCOR, SO 3 H, SO 2 CI, F, Cl, Br, NO 2 and CN may be substituted
  • E 1 can with E 2 and E 3 with E 4
  • E 2 and E 4 are COX radicals, where X is OH, Cl, OR 4 ,
  • R 4 is either defined as R or is selected from the following structures:
  • E 1 and E 3 are COR and E 2 and E 4 are R or H, F, Cl, Br;
  • E 1 is different from E 3 and / or E 2 is different from E 4 .
  • E 1 / E 2 and E 3 / E 4 are selected from the group consisting of the pairs
  • R 2 is phenyl, C., - C 20 - Is alkyl or benzyl, or R, R 1 is a benzyl or phenyl radical which is substituted by 1 to 3 substituents Me, OH, OMe, COOR, OCOR, SO 3 H, SO 2 CI, F, Cl, Br, NO 2 and CN may be substituted, and Ar is a C 6 -C 14 aryl radical, preferably a phenyl or benzyl radical, which may be substituted as described above
  • Q may be substituted with R 3 equal to C r C 6 alkyl, hydroxy (C r C 6 ) alkyl, carboxy (C r C 6 ) alkyl or (C r C3) alkyl carboxyl (C r C 6 ) -Alkyl; and with R 4 is C ⁇ -C ⁇ alkylene, in which up to every 3rd CH 2 unit can be replaced by O, which together with the amide nitrogen forms a C 1 2 -C 18 ring
  • R, R 1 and R 2 have the meaning given above or R is selected from the following structures:
  • E: 17 / cE2 and E: 3 / / c E4 are selected from the group consisting of the pairs CO 2 alkyl 1 / CO 2 alkyl 1 , COOH / COOH, CO 2 alkyl 1 / COAIkyl 2 , COAr / Ar, COAr / H, Ar / COX
  • X is OH, OR, NHR 1 or NR 1 R 2 , where R, R 1 and R 2 also have the abovementioned meaning of alkyl 1 , or R is selected from the following structures:
  • EVE 2 is different from E 3 / E 4 .
  • the compounds of the formula (I) are prepared by reacting a cyclopropanated C 70 monoadduct, which is accessible by known methods (see, for example, WO 94/25424 and P 44 33 245.9), by a second cyclopropanation which is carried out after the same procedure as in mono-adduct production is carried out.
  • cyclopropanation reagents commercially available substituted ⁇ -halo-CH-acidic compounds can be used, or the compounds used can be obtained by methods known to chemists, such as the halogenation of CH-acidic compounds or, for example, Friedel-Crafts acylation of substituted aromatics with halogenoacetyl halides or the reaction of an acid halide with a hydroxylamide or a hydroxyaromatic to an activated ester.
  • the compounds of the formula (I) which can be obtained can also be prepared in a well-defined manner by subsequent reactions, for example by saponifying an ester of the formula (I) to give the corresponding acid of the formula (I) or an activated ester of the formula (I) with an amine a corresponding amide of formula (I) is implemented.
  • the fullerene derivatives of the formula (I) according to the invention serve u. a. as starting products for the production of new, derivatized derivatives and can be used for the production of optoelectronic components.
  • FAB-MS 1212 (M ⁇ 50%), 1111 (10%), 1012 (15%), 840 (100%)
  • n [cm "1 ] 2977 (m), 1746 (s), 1444 (m); 1426 (m), 1369 (m),
  • Example 2 Analogously to Example 1, 50 mg (43 ⁇ mol) of 4- [4- (carbonylmethanofullerene-C 70 ) phenyl] butyric acid (4-nitrophenyl) ester with 10 mg (43 ⁇ mol) of bromomalonic acid diethyl ester and 6.5 mg ( 43 ⁇ mol) DBU implemented at room temperature. After a reaction time of 12 h, the reaction mixture was filtered and chromatographed (50 g SiO 2 , 0.063-0.1 mm) and eluted with toluene and toluene / diethyl acetate 40: 1. In addition to little starting product, 39 mg (68%)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne des bisadducts de fullerènes C70 de la formule (I) pouvant être obtenus par cyclopropanation successive de C70 avec deux différents composés α-halo-CH-acides, les deux additions intervenant à différents hémisphères. Les bisadducts de fullerènes C70 s'utilisent entre autres comme produits de départ pour préparer de nouveaux dérivés contenant des fullerènes et peuvent servir à produire des composants optoélectroniques.
PCT/EP1996/002395 1995-06-14 1996-06-03 Bisadducts asymetriques de fullerenes c70, procede de preparation et d'utilisation WO1997000235A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19521626A DE19521626A1 (de) 1995-06-14 1995-06-14 Unsymmetrische Bisaddukte von Fulleren C¶7¶¶0¶, Verfahren zu ihrer Herstellung und deren Verwendung
DE19521626.1 1995-06-14

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Publication Number Publication Date
WO1997000235A1 true WO1997000235A1 (fr) 1997-01-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011504168A (ja) * 2007-09-21 2011-02-03 ソレンネ ベーヴェー フラーレン多付加体組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009062456A1 (fr) 2007-11-13 2009-05-22 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Composant à semi-conducteurs photoélectrique à base de dérivé de fullerène

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025424A1 (fr) * 1993-04-24 1994-11-10 Hoechst Aktiengesellschaft Derives fullerenes, leur procede de fabrication et leur utilisation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025424A1 (fr) * 1993-04-24 1994-11-10 Hoechst Aktiengesellschaft Derives fullerenes, leur procede de fabrication et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BINGEL C ET AL: "Biscyclopropanation of C70", LIEBIGS ANN. (LANAEM,09473440);95; (8); PP.1551-3, HOECHST AG, ZENTRALFORSCHUNG;FRANKFURT/MAIN; D-65926; GERMANY (DE), XP002015141 *
BINGEL C: "Cyclopropanation of fullerenes", CHEM. BER. (CHBEAM,00092940);93; VOL.126 (8); PP.1957-9, HOECHST AG;HAUPTLAB.; FRANKFURT/MAIN; D-65926; GERMANY (DE), XP000572393 *
HERRMANN A ET AL: "Multiple cyclopropanations of C70. Synthesis and characterization of bis-, tris-, and tetrakis-adducts and chiroptical properties of bis-adducts with chiral addends, including a recommendation for the configurational description of fullerene derivatives with a chiral addition pattern", HELV. CHIM. ACTA (HCACAV,0018019X);95; VOL.78 (7); PP.1673-704, ETH-ZENTRUM;LABORATORIUM ORGANISCHE CHEMIE; ZURICH; CH-8092; SWITZ. (CH), XP002015142 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011504168A (ja) * 2007-09-21 2011-02-03 ソレンネ ベーヴェー フラーレン多付加体組成物

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DE19521626A1 (de) 1996-12-19

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