JP2003212880A - Method for producing fullerene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To selectively synthesize a double adduct derivative in which two organic groups are added to a fullerene skeleton and to isolate and purify the derivative in a high yield. <P>SOLUTION: This double adduct derivative of fullerene is produced by reacting fullerene with an organometallic compound as a Grignard reagent in the presence of an oxidizing agent such as oxygen, etc. The production of C<SB>60</SB>äCH<SB>2</SB>Si(CH<SB>3</SB>)<SB>3</SB>}<SB>2</SB>, a trimethylsilylmethyl group double adduct using a trimethylsilylmethyl Grignard reagent is cited as a concrete example. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fullerene derivative. More specifically, it relates to a method for producing a double addition derivative of fullerene by addition reaction of an organic group to fullerene.

[0002]

2. Description of the Related Art Since the mass production method of C ₆₀ was established in 1990, studies on fullerenes have been vigorously conducted. As a result, many fullerene derivatives have been synthesized and their various functions have been clarified. Along with that, electronic conductive materials using fullerene derivatives, semiconductors,
Various applications of physiologically active substances are being developed (for example, as a review, Hyundai Kagaku April 1992, p. 12, Hyundai Kagaku Jun. 2000, p. 46, Acc. Chem. Res., 199).
8, 98, 2527 etc.).

As a typical fullerene derivative, there is a compound in which an organic group such as a phenyl group or an alkyl group is added to a fullerene skeleton (hereinafter sometimes referred to as an addition derivative or an adduct). If a specific number of organic groups of a specific type can be added to a fullerene, a fullerene derivative having desired physical properties can be produced, which is extremely useful. From such a viewpoint, studies have been conducted for selectively synthesizing a fullerene compound to which a specific number of organic groups are added, and isolating and purifying the fullerene compound in a high yield.

The present inventors have developed a fullerene compound (hereinafter referred to as a 10-polyaddition derivative, or 10
It has been reported by synthesizing various fullerene compounds (sometimes referred to as polyaddition products) and fullerene compounds having five organic groups bonded thereto (hereinafter sometimes referred to as 5-polyaddition derivatives or 5-polyaddition products) (Japanese Patent Application Laid-Open No. H10 (1998) -109242). No. 167994, Japanese Patent Laid-Open No. 11-25
5509, Japanese Patent Application No. 2001-43180, J. Am.
Chem. Soc. 1996, 118, 12850, Org. Lett. 2000, 2,
1919, Chem. Lett. 2000, 1098). In addition, a fullerene compound to which three organic groups are added (hereinafter, a triple addition derivative,
Or sometimes referred to as a triple addition product),
The metal complex was also reported separately (Japanese Patent Laid-Open No. 11-25.
5508, J. Am. Chem. Soc. 1998, 120, 8285,
Org. Lett. 2000, 2, 1919.).

On the other hand, as a synthesis example of a fullerene compound (hereinafter sometimes referred to as a double addition derivative or a double addition product) in which two organic groups are bonded, two alkyl groups are C.
_A method for synthesizing a C ₆₀ derivative added to ₆₀ has been reported (J. Org. Chem. 1994, 59, 1246). According to the above document, C ₆₀ and Me ₂ SiYCH ₂ MgCl (Y = Me, H, Ph, CH), which is one of Grignard reagents, is used.
═CH ₂ , OiPr), and when water and the like are added to quench after the reaction, when THF is used as a reaction solvent, a C ₆₀ hydroalkylated product C ₆₀ (CH ₂ SiMe ₂ Y)
While (H) is obtained, it has been reported that when toluene is used, a C ₆₀ double adduct C ₆₀ (CH ₂ SiMe ₂ Y) ₂ is obtained (wherein each of the above chemical formulas, Me Represents a methyl group and Ph represents a phenyl group. The same applies in the following description). However, the mechanism of formation of this double adduct is unknown, and it is described in the literature that it is also unknown.

[0006]

However, according to the method described in the above literature, the yield of the produced C ₆₀ double adduct is low, and the method for efficiently and selectively obtaining the double adduct is as follows. Not enough. According to the description in the above document, Y =
In the case of Me, Ph, CH = CH ₂ , although the double adduct is the main product in all cases, this is analyzed by HPLC (hi
The isolated yields when isolated by gh-performance liquid chromatography: 5%, 6% and 5%, respectively, are not satisfactory.

From the above background, it is possible to selectively synthesize a double adduct in which two organic groups are added to a fullerene skeleton and to isolate and purify the fullerene derivative at a high yield. A manufacturing method has been desired.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a fullerene derivative which can selectively synthesize a double addition derivative in which two organic groups are added to a fullerene skeleton and which can be isolated and purified in a high yield. Providing a manufacturing method.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted diligent studies to improve the isolation yield in the synthesis reaction of the double adduct, and as a result, generally, Grigna
The addition reaction of the rd reagent is carried out in an inert atmosphere in order to suppress the production of impurities due to oxidation, but it is not carried out in an inert atmosphere but in the presence of an oxidizing agent such as oxygen. It was found that the double adduct can be obtained in a high yield by carrying out the reaction in step 1, and completed the present invention.

That is, the gist of the present invention relates to a method for producing a fullerene derivative, which comprises producing a double addition derivative of fullerene by reacting a fullerene with an organometallic compound in the presence of an oxidizing agent. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The method for producing a fullerene derivative according to the present invention is characterized by a step of producing a double addition derivative of fullerene by reacting a fullerene with an organometallic compound in the presence of an oxidizing agent.

Here, fullerene refers to a carbon cluster formed by arranging carbon atoms in a spherical or rugby ball shape. Specific examples include C ₆₀ (so-called buckminster fullerene), C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C.
_Examples include ₈₄ , C ₉₀ , C ₉₄ , C ₉₆ and higher carbon clusters, but C ₆₀ or C ₇₀ is preferable as the fullerene as a reaction raw material in the production method of the present invention. The method for producing fullerene is not particularly limited, and fullerene produced by a known method can be used as a raw material for a fullerene derivative. It may be a purified single product,
It may be a mixture of two or more fullerenes.

An organometallic compound (hereinafter sometimes referred to as an organometallic reagent) is an organic group added to fullerene (in this specification, "organic group" is defined as a general term for groups containing carbon). And a metal element, which has a bond between the carbon in the organic group and the metal element.

The organic group of the organometallic compound (that is, the organic group added to the fullerene) is not particularly limited in its kind, and various kinds can be selected and used, but usually, it has 1 to 20 carbon atoms. Organic groups in the range of are used. Specifically, linear or branched chain alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group; cyclic alkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; vinyl group, propenyl group, hexenyl group A linear or branched chain alkenyl group such as a group; a cyclopentenyl group,
A cycloalkenyl group such as a cyclohexenyl group; a heterocyclic group such as a 2-thienyl group, a 2-pyridyl group and a furfuryl group; an aryl group such as a phenyl group and a naphthyl group; an aralkyl group such as a benzyl group and a phenethyl group; an acetyl group, Propionyl group, butyryl group, valeryl group, isovaleryl group, cyclohexylcarbonyl group, benzoyl group and other linear or branched chain or cyclic acyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, etc. A chain or branched chain alkoxy group; a propenyloxy group,
A straight or branched chain alkenyloxy group such as butenyloxy group, pentenyloxy group; methylthio group, ethylthio group, n-propylthio group, n-butylthio group, s
linear or branched chain alkylthio group such as ec-butylthio group, tert-butylthio group; cyano group; isocyanato group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; hydroxy group; hydroxyamino group; hydroxy Imino group; formyl group; sulfonic acid group; carboxyl group; amino group; acylamino group; carbamate group; carboxylic ester group;
Examples thereof include a carbamoyl group; a sulfamoyl group; a sulfonic acid ester group; a sulfonamide group; and a silyl group. Note that some of the above-mentioned various organic groups may be further substituted with the above-mentioned various organic groups.

Among these organic groups, an organic group having a methylene group at the bonding portion with the metal element, that is, the following formula (i)
The organic group represented by is preferable because the reactivity of the organometallic compound becomes high. -CH ₂ -R ₁ ··· formula (i) In the above formula (i), R ₁ is 1 a hydrogen atom or a carbon atoms
Represents 19 organic groups.

Particularly, -R _{1 in the} above formula (i) is represented by the following formula (i
Organic groups represented by i) are preferred. —Si (R ₂ ) (R ₃ ) (R ₄ ) ... Formula (ii) In the above formula (ii), R ₂ , R ₃ and R ₄ may each independently have a substituent. Represents a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, and an amino group. The substituent is not particularly limited, and examples thereof include an alkoxy group, a halogen group and an amino group. Note that R ₂ , R ₃ and R ₄ may be the same or different.

On the other hand, as a specific example of the metal element in the organometallic compound, the typical element belongs to any one of Group 1A, Group 2A and Group 3B of the periodic table (group 18 long-period element periodic table). The elements include almost all transition elements (elements belonging to any of Group 3A to Group 8A, Group 1B and Group 2B of the periodic table). Among these metal elements, an element belonging to Group 1A or 2A of the periodic table or copper is preferable, and lithium or magnesium is particularly preferable.

Specific examples of preferred organometallic compounds in the present invention include organolithium reagents, organomagnesium reagents, organocopper reagents, organozinc reagents and the like. Examples of the organic lithium reagent include methyllithium, ethyllithium, propyllithium, butyllithium and its isomers, phenyllithium, naphthyllithium and its isomers, and the like.

Examples of organomagnesium reagents include dialkyl magnesium and Grignard reagents. Any of them can be used, but the Grignard reagent is more preferable from the viewpoint of easy availability and the like. Examples of dialkyl magnesium include dimethyl magnesium, diphenyl magnesium, and methyl ethyl magnesium. On the other hand, the Grignard reagent includes CH ₃ MgCl, CH ₃
MgBr, CH ₃ MgI, C ₂ H ₅ MgCl, C ₂ H ₅ Mg
Br, C ₂ H ₅ MgI, C ₃ H ₇ MgCl, C ₃ H ₇ MgB
r, CH ₂ = CHCH ₂ MgCl, CH ₂ = CHCH ₂ Mg
Br, C ₅ H ₁₁ MgCl, C ₅ H ₁₁ MgBr, C ₆ H ₁₃ M
Examples thereof include gBr, C ₆ H ₁₃ MgBr, C ₆ H ₁₃ MgBr, and the compounds shown below.

[0020]

[Chemical 1]

The organocopper reagent and the organozinc reagent are usually an organometallic compound containing a metal element belonging to any of Group 1A, Group 2A and Group 3B of the Periodic Table, and a copper compound or a zinc compound. What is prepared from is used.

Among these organometallic compounds, the Grignard reagent is most preferable, and in particular, the Grignard reagent having a methylene group at the bonding portion of the organic group with the metal element, that is, the Grignard reagent represented by the following formula (I) is It is preferable because it has high reactivity. XMg—CH ₂ —R ₁ ... Formula (I) In the above formula (I), R ₁ is a hydrogen atom or a carbon number of 1 to 1.
19 represents an organic group, and X represents a halogen atom.

Particularly, -R _{1 in the} above formula (I) is represented by the following formula (I
The Grignard reagent represented by I) is preferred. —Si (R ₂ ) (R ₃ ) (R ₄ ) ... Formula (II) In the above formula (II), R ₂ , R ₃ and R ₄ may each independently have a substituent. Represents a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, and an amino group. The substituent is not particularly limited, and examples thereof include an alkoxy group, a halogen group and an amino group. Note that R ₂ , R ₃ and R ₄ may be the same or different.

Specific preferred examples of the above Grignard reagents include C ₂ H ₅ MgBr, C ₃ H ₇ MgCl, CH ₂ =
Examples include CHCH ₂ MgCl, C ₆ H ₁₃ MgBr, and the compounds shown below.

[Chemical 2]

Of these, the following compounds and the like are particularly preferable.

[Chemical 3]

The ratio of the fullerene to the organometallic compound used is usually 2 to 20 equivalents, preferably 2 to 15 equivalents of the fullerene to the fullerene from the viewpoint of efficiently causing the reaction between the fullerene and the organometallic compound. Equivalent amount, particularly preferably 2 to 10 equivalent amount.

When the fullerene and the organometallic compound are reacted, it is preferable to dissolve or disperse the fullerene and the organometallic compound in a solvent to carry out the reaction. The solvent is not particularly limited as long as it can dissolve or disperse the fullerene and the organometallic compound uniformly, but various organic solvents are usually used. However,
When a solvent having a relatively high polarity such as THF is used, a hydroalkylated product tends to be preferentially produced instead of a double adduct, and therefore a hydrocarbon solvent having a relatively low polarity or a halogenated hydrocarbon solvent is used. It is preferable. Above all,
Since aliphatic hydrocarbons have a poor ability to dissolve fullerenes, the reaction rate tends to be extremely slow. Therefore, it is particularly preferable to use an aromatic hydrocarbon solvent or a halogenated aromatic hydrocarbon solvent having a high solubility of fullerenes. . Specific examples thereof include benzene, toluene, xylenes, ethylbenzene, chlorobenzene, orthodichlorobenzene and derivatives thereof, and among them, chlorobenzene and orthodichlorobenzene having high solubility of fullerene are preferable.

The ratio of the solvent to the fullerene and the organometallic compound is not particularly limited as long as the fullerene and the organometallic compound can be sufficiently dissolved or dispersed in the solvent. However, from the viewpoint of efficiently causing the reaction, the weight ratio of fullerene to the solvent is usually 0.0001 to 1
0% by weight, preferably 0.001 to 5% by weight, particularly preferably 0.1 to 1% by weight, and the weight ratio of the organometallic compound to the solvent is usually 0.0001 to 10% by weight, preferably 0. The amount is preferably 0.001 to 3% by weight, particularly preferably 0.01 to 2% by weight.

The production method of the present invention is characterized in that the fullerene and the organometallic compound are reacted in the presence of an oxidizing agent. The oxidizing agent is not particularly limited, and various known oxidizing agents can be arbitrarily selected and used. Specifically, molecular oxygen (O _2), ozone (O _3), nitric oxide (NO), nitrogen dioxide (NO _2), hydrogen peroxide, permanganic acid, chromic acid, chloric acid, pyridine -N- Oxide, N-methylmorpholine-N-oxide and the like. However, if the oxidizing power is too strong, the production ratio of the product in which the fullerene skeleton is oxidized becomes high,
Not preferable. For this reason, molecular oxygen (O ₂ ) is preferable among the above-mentioned various oxidizing agents.

When a gas such as molecular oxygen is used as the oxidant, it may be used in a state of being mixed with another gas in order to adjust its oxidizing power. Examples of the gas mixed with the molecular oxygen include inert gases such as nitrogen, helium, and argon, but since they are inexpensive and easily available,
Preference is given to using nitrogen. The oxygen / nitrogen mixed gas ratio may be appropriately selected in consideration of the types of fullerenes and organic metal compounds used and the oxidizing power of oxygen, but usually dry air (oxygen / nitrogen ≈ 1/4) or dry A mixed gas of air and nitrogen (oxygen / nitrogen <1/4) is used.
That is, the oxygen concentration in the oxygen / nitrogen mixed gas is usually 1 to
It is about 20%. If the oxygen concentration is too low, the selectivity of the hydroalkylated product tends to be high because the rate of the double addition reaction is slow, while conversely, if the oxygen concentration is too high, the oxidation of the fullerene skeleton tends to be remarkable. However, in any case, the selective production rate of the double adduct decreases, which is not preferable.

The amount of the oxidizing agent used is based on the fullerene.
It is usually 0.5 to 10 ⁶ equivalents, preferably 1 to 10 ⁵ equivalents, and particularly preferably 1 to 10 ⁴ equivalents. When the amount of the oxidizing agent used is too small, the selective formation reaction of the double adduct is not sufficiently promoted, and when it is too large, side reactions such as oxidation of the fullerene skeleton tend to occur preferentially.

In addition, various catalysts for accelerating the reaction and various additives according to various purposes may be used. The types of catalysts and additives are not particularly limited and may be appropriately selected depending on the type of fullerene derivative (type of addition group) to be produced.

The reaction system of the fullerene and the organometallic compound is optional and may be a closed system, an open system or a gas distribution system. The reaction system is not particularly limited, and can be appropriately selected in consideration of the types and amounts of fullerenes and organometallic compounds used. However, due to the nature of the reaction
Usually, it is preferable to carry out as a batch reaction using a single-stage reaction tank.

The order and method of adding the fullerene and the organometallic compound to the reaction vessel are arbitrary, but usually, a solution or dispersion in which one of the fullerene and the organometallic compound (preferably fullerene) is dissolved or dispersed in a solvent. It is preferable to prepare the liquid in a reaction tank and add the other of the fullerene and the organometallic compound (preferably the organometallic compound) as a solution or a slurry while stirring the liquid.

As the method of supplying the oxidizing agent, various methods can be selected and used according to the type and state of the oxidizing agent. When the oxidizing agent is a liquid, it may be added directly to the reaction solution. When the oxidizing agent is a gas such as molecular oxygen, the upper surface of the reaction solution may be filled or the reaction solution may be foamed. Further, when the reaction system is a gas flow system, it is preferable to carry out the reaction while circulating an oxidizing agent as a gas on the upper surface of the reaction liquid.

The reaction temperature is usually in the range of -78 to 100 ° C, preferably 0 to 50 ° C. If the reaction temperature is too low, the reaction rate is insufficient, and if it is too high, side reactions tend to occur preferentially. The reaction pressure is not particularly limited, and may be near normal pressure or high pressure, but near normal pressure is preferable. The reaction time depends on the type of fullerene and organometallic compound used,
An appropriate range may be appropriately selected depending on the type of solvent, the type of oxidizing agent, the reaction system, and the like.

In the present invention, the fullerene double adduct is selectively produced by reacting the fullerene with the organometallic compound under the above conditions. The double adduct produced by the reaction does not need to be purified if the selective production rate is high. However, since it is usually obtained as a crude product mixed with raw materials fullerene, trace amounts of by-products such as hydroalkylated products and oxides, when a highly pure double adduct is required, the crude product is obtained. It is necessary to isolate and purify the double adduct from Examples of the method for isolating and purifying the double adduct include a method by chromatography such as HPLC and a method by solvent extraction using an organic solvent and the like.

In particular, in the present invention, the hydroalkyl derivative and oxide of fullerene, which are the main by-products of the reaction, and the fullerene of the starting material, are more organic than those of the target double adduct of fullerene (comparative Since it has low solubility in a general organic solvent having a low polarity, isolation / purification by solvent extraction becomes possible. Isolation / purification by solvent extraction is simpler and less expensive than purification by chromatography. Therefore, in the present invention, the fullerene double adduct is isolated / purified by solvent extraction using an organic solvent or the like. Is preferred.

The solvent extraction may be carried out at room temperature or with a warm solvent by a method such as Soxhlet extraction. The type of organic solvent used for solvent extraction is not particularly limited, and may be appropriately selected and used depending on the types of fullerene and organometallic compound and the types of addition groups. Usually, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene and dichlorobenzene; alcohols such as ethanol and isopropanol are used. . Among these, aliphatic hydrocarbons such as hexane and heptane and aromatic hydrocarbons such as benzene and toluene are preferable. These organic solvents may be used alone or as a mixed solvent of two or more kinds.

According to the method for producing a fullerene derivative of the present invention described above, a fullerene double addition derivative can be selectively synthesized by reacting a fullerene with an organometallic compound in the presence of an oxidizing agent. It becomes possible to isolate and purify this in a high yield. Therefore, it becomes easy to produce a fullerene derivative having desired physical properties suitable for various uses such as an electron conductive material, a semiconductor, and a physiologically active substance. In addition, 2 of fullerene with high purity produced
The polyaddition derivative is also useful as a material for synthesizing various substances such as a fullerene triple addition derivative.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded, and may be freely implemented with appropriate changes. It is possible.

Example: In an atmosphere of dry air, 500 mg of C60 was dissolved in 150 mL of orthodichlorobenzene, and room temperature (25 ° C.)
- at atmospheric pressure, and it reacted by adding 8 equivalents of trimethylsilylmethyl Grignard reagent (CH _{3) 3} SiCH ₂ MgCl in diethyl ether solution (concentration: about 1.0 M). After 2 hours, 0.5 mL of saturated aqueous ammonium chloride solution was added to quench the excess Grignard reagent. Under reduced pressure 7
The solvent was distilled off at 0 ° C., and the residue was dissolved in 100 mL of toluene. By passing through a silica gel short path using toluene as a developing solvent, magnesium salts and the like produced as by-products are removed. Toluene was distilled off to obtain 611 mg of a black solid (crude product).

Regarding the crude product obtained by the reaction, H
PLC (Column: BuckyPre manufactured by Nacalai Tesque, Inc.
p, mobile layer: toluene / 2-propanol = 7/3, flow rate: 1 mL / min, detection: 350 nm UV), analysis showed that trimethylsilylmethyl group double adduct C ₆₀ {CH ₂ Si (CH ₃ ) ₃ } ₂ peaks were observed. The purity of the double adduct based on the peak area ratio is about 7
It was 0%. No peak of C ₆₀ , which is the reaction raw material, was observed. The peak of the by-product of the reaction is C ₆₀
{CH ₂ Si (CH ₃ ) ₃ } ₃ H (peak area ratio 3%), C
Each peak of ₆₀ {CH ₂ Si (CH ₃ ) ₃ } H (peak area ratio 6%) was observed, and other unknown peaks were observed. These unknown peaks are
C ₆₀ {CH ₂ Si (CH ₃ ) ₃ } H (O) or C ₆₀ {CH ₂
It was presumed to be a peak of an oxidant such as Si (CH ₃ ) ₃ } (OH).

The crude product described above can be extracted with hot hexane.
Almost pure C by₆₀{CH ₂Si (CH₃)₃}₂
was gotten. The isolated yield was 335 mg (54% yield).
It was. In addition, HPLC (column: B manufactured by Nacalai Tesque, Inc.)
uckyPrep, Mobile bed: Toluene / 2-Propane
By preparatively purifying the corresponding peak at
Is almost pure C₆₀{CH₂Si (CH₃)₃}₂Is obtained
It was The structure of the product is J. Org. Chem. 1994, 59,
1246 (Supplementary Material) NMR, IR,
It was identified by comparison with the UV data.

Comparative example Similar to the example except that it was under an atmosphere of pure nitrogen.
An experiment was conducted under the conditions to obtain a crude product from the reaction. Profit
HP for the obtained composition organisms under the same conditions as in the example.
When analyzed by LC, C₆₀{CH₂Si
(CH₃)₃} H peak has an area ratio of 10%, C of the raw material₆₀of
Peaks are observed at an area ratio of 90%, and C₆₀{CH
₂Si (CH₃) ₃}₂No peak was observed.

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, a fullerene double-addition derivative can be selectively synthesized by reacting a fullerene with an organometallic compound in the presence of an oxidizing agent, and at the same time, it can be obtained in high yield. It can be separated and purified.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Matsuo             Central Bank Hongo Ma 5-28-3 Hongo, Bunkyo-ku, Tokyo             Nsion 601 F-term (reference) 4H049 VN01 VP02 VQ02 VQ06 VR24                       VS05 VS96

Claims (8)

[Claims] 1. Production of a fullerene derivative, characterized in that a fullerene derivative is produced by reacting a fullerene with an organometallic compound in the presence of an oxidizing agent to produce a double addition derivative in which two organic groups are added to the fullerene. Method. 2. The method for producing a fullerene derivative according to claim 1, wherein the oxidizing agent is molecular oxygen. 3. The method for producing a fullerene derivative according to claim 2, wherein the molecular oxygen is supplied as dry air. 4. The organometallic compound has 1 to 20 carbon atoms.
The method for producing a fullerene derivative according to any one of claims 1 to 3, wherein the fullerene derivative has the organic group of. 5. The method for producing a fullerene derivative according to claim 1, wherein the organometallic compound is a Grignard reagent. 6. The Grignard reagent has the following formula (I) XMg—CH ₂ —R ₁ ... Formula (I) (wherein R ₁ is a hydrogen atom or a carbon number of 1 to 19). And X represents a halogen atom), the process for producing a fullerene derivative according to claim 5. 7. In the above formula (I), —R ₁ is the following formula (II) —Si (R ₂ ) (R ₃ ) (R ₄ ) ... Formula (II) (wherein the above formula (II ), R ₂ , R ₃ and R ₄ each independently have 1 to 10 carbon atoms which may have a substituent.
Of the above, which may be the same or different from each other), and a method for producing the fullerene derivative according to claim 6. 8. The double addition derivative of fullerene is recovered by extracting with an organic solvent from a crude product produced by a reaction between the fullerene and the organometallic compound. A method for producing the fullerene derivative according to any one of items 1 to 7.