JP6893443B2 - Fullerene derivatives and lubricants - Google Patents

Description

The present invention relates to fullerene derivatives and lubricants.

Perfluoropolyether compounds are excellent in heat resistance, chemical resistance, and oxidation resistance, and because they have a large viscosity index, there is little change in fluidity (viscosity) in a wide temperature range from low temperature to high temperature, and good lubricity. Demonstrate. In addition to being nonflammable, perfluoropolyether compounds have almost no effect on polymer materials such as rubber and plastic, and have low vapor pressure, low evaporation loss, low surface tension, and high electrical insulation. It also has properties such as properties, and is known to exhibit high performance over an extremely wide range as a lubricant. Therefore, the perfluoropolyether compound is widely used in vacuum pump oil as a lubricating oil, a lubricant such as a magnetic disk / tape, a heat medium, a non-adhesive agent, and other applications.

_{On the other hand, C 60} , which is a kind of fullerene, is known to be useful as a lubricant.

In Non-Patent Document 1, the friction coefficient of the silicon substrate formed with the deposited film of C ₆₀ is confirmed to be reduced. Further, Non-Patent Document 1 also proposes a fullerene derivative in which a perfluoropolyether group is introduced into fullerene, but a specific compound and a method for synthesizing the fullerene are not described.

Further, C ₆₀ is known to exhibit excellent properties as an additive to conventional lubricating oils.

In Non-Patent Document 2, are measured as those painted ordinary lubricating oil to the surface of the copper foil, the frictional resistance but painted those of C ₆₀ was added 5% to the oil. Friction resistance is measured by rubbing a steel roller with a load. As a result, _{it has been confirmed that when C 60} is added, the wear resistance is improved as compared with the case where C 60 is not added.

Patent Document 1 describes a lubricant composed of a mixture of fullerene, a carboxyl derivative of fullerene, or a fullerene derivative to which an ester group is bonded, and a perfluoropolyether compound.

Patent Documents 2 to 6 describe a lubricant composed of a fullerene derivative having a perfluoropolyether group in a ring structure condensed with fullerene. The molecular structure of these fullerene derivatives is that each ring structure is condensed over two adjacent carbon atoms on the fullerene skeleton.

On the other hand, Patent Document 7 and Non-Patent Document 3 describe a modification reaction of fullerene, which is characterized by reacting an organic copper reagent prepared from a Grignard reagent and a copper compound with fullerene.

Further, Patent Document 8 describes a compound synthesized by the methods described in Patent Document 7 and Non-Patent Document 3, and a part of the compound is soluble in a general organic solvent such as hexane. Is described.

Further, in Non-Patent Document 4 and Non-Patent Document 5, derivatives having a total of 5 perfluoroalkyl groups on the fullerene skeleton, which were synthesized by the methods described in Patent Document 7 and Non-Patent Document 3, were used. The formation of vesicles is described.

However, the use of the above compounds as lubricants is not described.

Japanese Unexamined Patent Publication No. 2006-131874 Japanese Patent No. 5600202 Japanese Patent No. 5600222 International Publication No. 2015/125940 International Publication No. 2017/006812 Japanese Unexamined Patent Publication No. 2017-14192 Japanese Patent No. 4699233 Japanese Patent No. 4109458

Appl. Phys. Lett. 62, 3253 (1993) Russian Journal of Applied Chemistry 75, 1330 (2002) Chem. Rev. 108, 3016 (2008) Angew. Chem. Int. Ed. 49, 1665 (2010) J. Am. Chem. Soc. 133, 6364 (2011)

In general, even if a compound having a fullerene skeleton is used as a lubricant, the compound having a fullerene skeleton easily aggregates, so that good dispersibility cannot be obtained and sufficient wear resistance cannot be imparted to the object. There is a problem.

In Patent Document 1, a mixture of a fullerene or a fullerene derivative and a perfluoropolyether compound is used as a lubricant because the affinity between the fullerene or the fullerene derivative and the perfluoropolyether compound is not sufficient and it easily aggregates. However, there is a problem that sufficient wear resistance cannot be imparted to the object.

Patent Documents 2 to 6 propose fullerene derivatives having a fullerene skeleton and a perfluoropolyether group in order to solve the above problems. In the fullerene derivatives described in Patent Documents 2 to 6, the ring structure introduced on the fullerene skeleton to impart a perfluoropolyether group is condensed over two carbon atoms on the fullerene skeleton. It is characterized by being.

On the other hand, when a lubricant layer is formed on the surface of the carbon protective film of a magnetic recording medium such as a hard disk, some lubricant that is not adsorbed on the surface of the carbon protective film is removed each time the head flies. As a result, the lubricant gradually becomes thinner, and there is a risk of eventually leading to a crash. In order to prevent such a phenomenon, the amount of the lubricant adsorbed on the surface of the carbon protective film needs to be higher than a predetermined ratio, that is, the bonded ratio of the lubricant layer needs to be high.

The bonded ratio of the lubricant layer is the ratio of the lubricant remaining after immersing the hard disk forming the lubricant layer in a solvent to wash away the lubricant not adsorbed on the surface of the carbon protective film.

The fullerene derivatives described in Patent Documents 2 to 6 need to increase the number of perfluoropolyether groups in order to improve lubricity. For this purpose, it is conceivable to increase the number of ring structures, but since the ring structures are condensed over two carbon atoms on the fullerene skeleton, they are adsorbed as the number of ring structures increases. The surface area of the π-conjugated system that contributes to is reduced. In addition, when a plurality of ring structures are imparted on the fullerene skeleton, the ring structures are likely to be formed at positions separated from each other due to thermodynamic factors, which also reduces the surface area of the π-conjugated system on the fullerene skeleton. It becomes.

From the above, even if a compound having a fullerene skeleton is used as a lubricant, the surface area of the π-conjugated system on the fullerene skeleton that contributes to adsorption is insufficient, so that a lubricant layer having a high bonded ratio can be formed. There is a problem that it is difficult.

One aspect of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fullerene derivative capable of forming a lubricant layer having a high bonded ratio.

That is, the present invention includes the following configurations.
[1] General formula

（式中、ＦＬＮはフラーレン骨格であり、Ａは、一般式
Ａ_１−ＣＨ_２−Ｏ−・・・（Ａ）
（式中、Ａ_１は、１価のパーフルオロポリエーテル基である。）
で表される基、または、一般式
Ａｒ−ＣＯＯ−ＣＨ_２−Ａ_２−ＣＨ_２−ＯＣＯ−・・・（Ｂ）
（式中、Ａｒはアリール基またはアラルキル基であり、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される基であり、Ｒは水素原子またはメチル基であり、ｋは５〜１０の整数であり、ｍは０〜２の整数であり、ｎは１〜５の整数である。）
で表される化合物であるフラーレン誘導体。
［２］前記フラーレン骨格がＣ_６０である［１］に記載のフラーレン誘導体。
［３］前記Ａ_１及びＡ_２のパーフルオロポリエーテル基の炭素数が５〜１００である［１］または［２］に記載のフラーレン誘導体。
［４］前記Ａ_１及びＡ_２のパーフルオロポリエーテル基が、一般式
−（ＣＦ_２）_ｘＯ−・・・（Ｃ）
（式中、ｘは１〜５の整数である。）
で表される基を含む［１］〜［３］のいずれか一項に記載のフラーレン誘導体。
［５］前記Ａ_１及びＡ_２のパーフルオロポリエーテル基は、前記ｘが１または２である前記一般式（Ｃ）で表される基を１〜５０個含む［４］に記載のフラーレン誘導体。
［６］前記Ａ_１及びＡ_２のパーフルオロポリエーテル基の平均式量が２５０〜６０００の範囲内である［１］〜［５］のいずれか一項に記載のフラーレン誘導体。
［７］前記Ａ_１及びＡ_２のパーフルオロポリエーテル基が直鎖である［１］〜［６］のいずれか一項に記載のフラーレン誘導体。
［８］前記ｋが５または１０である［１］〜［７］のいずれか一項に記載のフラーレン誘導体。
［９］化学式

(In the formula, FLN is a fullerene skeleton, and A is the general formula A _1- CH _2- O-... (A).
(In the formula, A ₁ is a monovalent perfluoropolyether group.)
A group represented by or, the general formula _{Ar-COO-CH 2 -A 2} -CH 2 -OCO- ··· (B)
(In the formula, Ar is an aryl group or an aralkyl group, and A ₂ is a divalent perfluoropolyether group.)
Is a group represented by, R is a hydrogen atom or a methyl group, k is an integer of 5 to 10, m is an integer of 0 to 2, and n is an integer of 1 to 5. )
A fullerene derivative which is a compound represented by.
Fullerene derivative according to [2] the fullerene skeleton is a _{C 60} [1].
[3] The fullerene derivative according to [1] or [2], _{wherein the perfluoropolyether groups of A 1} and A _{2 have 5 to 100 carbon atoms.}
[4] _{The perfluoropolyether groups of A 1} and A ₂ have the general formula − (CF ₂ ) _x O − ··· (C).
(In the formula, x is an integer from 1 to 5.)
The fullerene derivative according to any one of [1] to [3], which contains a group represented by.
[5] _{The fullerene derivative according to [4], wherein the perfluoropolyether groups A 1} and A ₂ contain 1 to 50 groups represented by the general formula (C) in which x is 1 or 2. ..
[6] The fullerene derivative according to any one of [1] to [5], _{wherein the average formula amount of the perfluoropolyether groups of A 1} and A _{2 is in the range of 250 to 6000.}
[7] The fullerene derivative according to any one of [1] to [6], _{wherein the perfluoropolyether groups of A 1} and A _{2 are linear.}
[8] The fullerene derivative according to any one of [1] to [7], wherein k is 5 or 10.
[9] Chemical formula

（式中、Ａ_１は、１価のパーフルオロポリエーテル基である。）
で表される化合物、化学式

(In the formula, A ₁ is a monovalent perfluoropolyether group.)
Compound represented by, chemical formula

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ _ｆ ^２ 中の（ＣＦ _２ Ｏ）と（ＣＦ _２ ＣＦ _２ Ｏ）との順序は任意である。）
で表される化合物、化学式

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary .)
Compound represented by, chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物、化学式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物、または、化学式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, or chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物である［１］〜［８］のいずれか一項に記載のフラーレン誘導体。
［１０］［１］〜［９］のいずれか一項に記載のフラーレン誘導体を含有する潤滑剤。
［１１］フラーレン骨格を有しないパーフルオロポリエーテル化合物をさらに含有する［１０］に記載の潤滑剤。
［１２］一般式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
The fullerene derivative according to any one of [1] to [8], which is a compound represented by.
[10] A lubricant containing the fullerene derivative according to any one of [1] to [9].
[11] The lubricant according to [10], which further contains a perfluoropolyether compound having no fullerene skeleton.
[12] General formula

（式中、ＦＬＮはフラーレン骨格であり、Ａ_２は、２価のパーフルオロポリエーテル基であり、Ｒは水素原子またはメチル基であり、ｋは５〜１０の整数であり、ｍは０〜２の整数であり、ｎは１〜５の整数である。）
で表される化合物であるフラーレン誘導体。
［１３］化学式

(In the formula, FLN is a fullerene skeleton, A ₂ is a divalent perfluoropolyether group, R is a hydrogen atom or a methyl group, k is an integer of 5 to 10, and m is 0 to 0. It is an integer of 2 and n is an integer of 1-5.)
A fullerene derivative which is a compound represented by.
[13] Chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物、化学式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物、化学式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物、または、化学式

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, or chemical formula

（式中、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される化合物である［１２］に記載のフラーレン誘導体。

(In the formula, A ₂ is a divalent perfluoropolyether group.)
The fullerene derivative according to [12], which is a compound represented by.

One aspect of the present invention can provide a fullerene derivative capable of forming a lubricant layer having a high bonded ratio.

The configuration of the embodiment of the present invention will be described below. The present invention can be carried out with appropriate modifications without changing the gist thereof.

(Fullerene derivative)
The fullerene derivative of this embodiment has a general formula.

（式中、ＦＬＮはフラーレン骨格であり、Ａは、一般式
Ａ_１−ＣＨ_２−Ｏ−・・・（Ａ）
（式中、Ａ_１は、１価のパーフルオロポリエーテル基である。）
で表される基、または、一般式
Ａｒ−ＣＯＯ−ＣＨ_２−Ａ_２−ＣＨ_２−ＯＣＯ−・・・（Ｂ）
（式中、Ａｒはアリール基またはアラルキル基であり、Ａ_２は、２価のパーフルオロポリエーテル基である。）
で表される基であり、Ｒは水素原子またはメチル基であり、ｋは５〜１０の整数であり、ｍは０〜２の整数であり、ｎは１〜５の整数である。）
で表されるフラーレン誘導体、並びに、これらフラーレン誘導体の合成に際し、中間体となりうるパーフルオロポリエーテル基を有するフラーレン誘導体である。

(In the formula, FLN is a fullerene skeleton, and A is the general formula A _1- CH _2- O-... (A).
(In the formula, A ₁ is a monovalent perfluoropolyether group.)
A group represented by or, the general formula _{Ar-COO-CH 2 -A 2} -CH 2 -OCO- ··· (B)
(In the formula, Ar is an aryl group or an aralkyl group, and A ₂ is a divalent perfluoropolyether group.)
Is a group represented by, R is a hydrogen atom or a methyl group, k is an integer of 5 to 10, m is an integer of 0 to 2, and n is an integer of 1 to 5. )
It is a fullerene derivative represented by, and a fullerene derivative having a perfluoropolyether group which can be an intermediate in the synthesis of these fullerene derivatives.

However, when the synthesis of a fullerene derivative is not referred to below, the former fullerene derivative is simply referred to as a "fullerene derivative".

The perfluoropolyether group is a group in which a plurality of fluorocarbon groups are bonded by an ether bond.

The fullerene derivative of the present embodiment has k benzene-derived groups on the fullerene skeleton, and k benzene-derived groups are represented by n groups represented by the general formula (A), or n groups, respectively. Since it is substituted with a group represented by the general formula (B), a lubricant layer having a high bonded ratio can be formed.

The k benzene-derived groups on the fullerene skeleton may be the same or at least partially different.

The perfluoropolyether groups of A ₁ and A ₂ have the general formula − (CF ₂ ) _x O − ··· (C).
(In the formula, x is an integer from 1 to 5.)
It is preferable to include a group represented by.

Further, _{the perfluoropolyether groups of A 1} and A ₂ more preferably contain 1 to 50 groups represented by the general formula (C) in which x is 1 or 2. This is because the organic fluorine compound containing such a structure is industrially produced, easily available, and industrially usable.

In the fullerene derivative of the present embodiment, _{the perfluoropolyether group of A 1} and A ₂ has a group represented by the general formula (C), so that the perfluoropolyether group is represented by the general formula (C). The solubility of the fullerene derivative having no group in a fluorine-based solvent is increased, and as a result, the fullerene derivative can be more uniformly applied to the surface to be coated.

The groups represented by the general formula (C) contained in the perfluoropolyether groups of _{A 1} and A _{2 may be the same, or at least a part thereof may be different.}

Further, the group represented by the general formula (C) may have a fullerene skeleton bonded in any direction via an aromatic ring or the like.

The perfluoropolyether groups of A ₁ and A ₂ preferably have 5 to 100 carbon atoms, and more preferably 5 to 40 carbon atoms. When the perfluoropolyether group has 5 to 100 carbon atoms, it has good solubility in a fluorine-based solvent, is easy to apply, and has sufficient solubility in a general organic solvent, so that it has a structure by an organic reaction. Easy to convert.

The average formula amount (Mn) of the perfluoropolyether groups of A ₁ and A ₂ is preferably in the range of 250 to 6000, and more preferably in the range of 280 to 3000. When _{the average formula amount (Mn) of the perfluoropolyether groups of A 1} and A ₂ is 250 to 6000, the solubility in a fluorine-based solvent is good, the coating is easy, and the perfluoropolyether group is easily applied to a general organic solvent. Since it has sufficient solubility, it is easy to change the structure by an organic reaction.

The perfluoropolyether groups of A ₁ and A ₂ may be linear or branched, but are preferably linear.

The fullerene derivative of the present embodiment has improved lubricity and solubility in a fluorine-based solvent because the perfluoropolyether groups of _{A 1} and A _{2 are linear.}

The perfluoropolyether group may have a substituent, if necessary.

When A is a group represented by the general formula (A), the structure _{of the non-bonded terminal of A 1} , that is, the terminal structure that is not a portion bonded to the fullerene skeleton via a group derived from benzene or the like, is For example, a perfluoroalkyl group such as a trifluoromethyl group or a perfluorobutyl group can be mentioned.

When A is a group represented by the general formula (B), examples of Ar include an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group and a phenylpropyl group.

Examples of the fullerene skeleton in the fullerene derivative of the present embodiment include a C ₆₀ skeleton, a C ₇₀ skeleton, a C ₇₆ skeleton, a C ₇₈ skeleton, and a higher-order fullerene skeleton. Among them, the _C60 skeleton is preferable.

C ₆₀ skeleton can be industrially easily obtained a high purity than other fullerene skeleton. Therefore, the fullerene derivative of the present embodiment can have high purity, and can improve lubricity and smoothness.

The fullerene derivative of the present embodiment preferably has k of 5 or 10. Such compounds are easy to synthesize with a relatively small number of steps.

When m is 2, the fullerene derivative of the present embodiment may have two hydrogen atoms or methyl groups on the fullerene skeleton, or may have one hydrogen atom and one methyl group. Good.

(Method of synthesizing fullerene derivative)
The fullerene derivative of the present embodiment can be synthesized, for example, according to the following two types of synthesis methods.

[When A is a group represented by the general formula (A)]
The fullerene derivative of the present embodiment is, for example, an organic copper prepared from phenyl iodide having a group represented by the general formula (A), an isopropylmagnesium chloride-lithium chloride complex, and a copper (I) -dimethyl sulfide complex. It can be synthesized from reagents and fullerene.

The above reaction can be carried out in a solvent.

The reaction solvent for preparing the organocopper reagent is not particularly limited as long as it is a solvent capable of stabilizing the organometallic species, and may be described as, for example, diethyl ether or tetrahydrofuran (hereinafter, "THF"). ) And the like.

The reaction solvent for the addition reaction using the organic copper reagent and fullerene as a starting material is not particularly limited as long as it is a solvent capable of dissolving fullerene and stabilizing the organic copper reagent. For example, THF. And o-dichlorobenzene (hereinafter, may be referred to as “ODCB”) mixed solvent and the like can be mentioned.

The reaction is preferably carried out in an inert gas atmosphere with stirring. By carrying out the above reaction in an atmosphere of an inert gas, the formation of by-products can be suppressed.

The preparation of the organic copper reagent is preferably carried out at −20 ° C. or lower because the organic copper reagent is thermally unstable.

Further, when the reaction rate is not sufficient, the addition reaction of the organic copper reagent to the fullerene is preferably carried out while heating.

After adding a Bronsted acid such as saturated aqueous ammonium chloride solution or a methylating agent such as iodomethane to the reaction mixture, the reaction mixture is filtered through Celite while flowing a fluorine-containing solvent such as AK225 (manufactured by Asahi Glass Co., Ltd.), and the reaction solvent and the reaction solvent are added by a rotary evaporator. A crude product can be obtained by distilling off the elution solvent.

[When A is a group represented by the general formula (B)]
The fullerene derivative of the present embodiment is prepared from, for example, an aryl iodide having an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an isopropylmagnesium chloride-lithium chloride complex, and a copper (I) -dimethylsulfide complex. A fullerene derivative synthesized from an organic copper reagent and fullerene can be synthesized as a precursor.

Specifically, the fullerene derivative of the present embodiment has a general formula.

（式中、ＦＬＮ、Ｒ、ｋ、ｍ、ｎは、一般式（１）と同一であり、Ｒ^１はメチル基、エチル基などの炭化水素基である。）
で表される化合物から合成することができる。

(In the formula, FLN, R, k, m, n are the same as those in the general formula (1), and R ¹ is a hydrocarbon group such as a methyl group or an ethyl group.)
It can be synthesized from the compound represented by.

The reaction for synthesizing the compound represented by the general formula (2) can be carried out in a solvent.

The reaction solvent for preparing the organocopper reagent is not particularly limited as long as it is a solvent capable of stabilizing the organometallic species, and examples thereof include ether solvents such as diethyl ether and THF.

The reaction solvent for adding the organic copper reagent to the fullerene is not particularly limited as long as it is a solvent capable of dissolving the fullerene and stabilizing the organic copper reagent, but for example, a mixture of THF and ODCB is used. A solvent and the like can be mentioned.

The reaction is preferably carried out in an inert gas atmosphere with stirring. By carrying out the above reaction in an atmosphere of an inert gas, the formation of by-products can be suppressed.

The preparation of the organic copper reagent is preferably carried out at −20 ° C. or lower because the organic copper reagent is thermally unstable.

Further, when the reaction rate is not sufficient, the addition reaction of the organic copper reagent is preferably carried out while heating.

Bronsted acid such as saturated aqueous ammonium chloride solution or methylating agent such as iodomethane is added to the reaction mixture, and then filtered through Celite while flowing an organic solvent known to dissolve a fullerene derivative such as toluene, and rotary. A crude product can be obtained by distilling off the reaction solvent and the elution solvent with an evaporator.

^{Next, the chemical formula R 1} OCO- of the compound represented by the general formula (2)
In the presence of an acid catalyst, the group represented by the general formula HOCH _2- A _2- CH ₂ OH ... (3)
(In the formula, A ₂ is the same as the general formula (1).)
By transesterifying with the compound represented by

（式中、ＦＬＮ、Ａ_２、Ｒ、ｋ、ｍ、ｎは、一般式（１）と同一である。）
で表される化合物（中間体）を得ることができる。

(In the formula, FLN, A ₂ , R, k, m, n are the same as the general formula (1).)
A compound (intermediate) represented by is obtained.

In the above reaction, generally known inorganic acids and organic acids can be used as the acid catalyst, for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid (hereinafter, "TfOH"). ".) And so on.

As the compound represented by the general formula (3), an industrially produced compound can be used, and examples thereof include the Fomblin (registered trademark) series (manufactured by Solvay Specialty Polymers).

The above reaction can be carried out in a solvent.

The solvent is not particularly limited as long as it is a solvent capable of dissolving the compound represented by the general formula (2) and the compound represented by the general formula (3), and is, for example, toluene, xylene, and ODCB. An aromatic solvent capable of dissolving a fullerene derivative such as, hexafluorobenzene, AK-225 (manufactured by Asahi Glass Co., Ltd.), hexafluorotetrachlorobutane (hereinafter, may be referred to as "HFTCB") and the like. A mixed solvent with a fluorine-based solvent can be mentioned.

The above reaction is preferably carried out in an atmosphere of an inert gas with heating and stirring. By carrying out the above reaction in an atmosphere of an inert gas, the formation of by-products can be suppressed.

Further, it is preferable that the above reaction is carried out by attaching a Soxhlet extractor equipped with a glass fiber cylindrical filter paper containing molecular sieves, heating the extract to a temperature exceeding the boiling point of the solvent to be used, and refluxing the solvent. By removing the alcohol having a small molecular weight such as methanol produced as a by-product by such a method, the transesterification reaction can be efficiently promoted.

The reaction mixture is cooled to room temperature, and after appropriate neutralization by adding aqueous ammonia or the like, the reaction solvent is distilled off by a rotary evaporator, and the obtained mixture is dissolved in a fluorine-based solvent such as AK-225 (manufactured by Asahi Glass Co., Ltd.). A crude product can be obtained by removing impurities such as unreacted fullerene or a fullerene derivative by filtering and distilling off the solvent again.

Finally, the compound represented by the general formula (1 ') to the (intermediate), by carrying out known reactions, the general formula _{HO-CH 2 -A 2 -CH 2} -OOC-
The unbonded end of the group represented by, that is, the hydroxyl group, is represented by the general formula ArOCO-.
(In the formula, Ar is the same as the general formula (1).)
A crude product can be obtained by converting to a group represented by.

The crude products obtained by the above two synthetic methods can be used as a lubricant, but if higher purity is required, the crude products can be further added to silica gel column chromatography or carbon dioxide. After purification by a supercritical fluid extraction method or the like, it can be used as a lubricant.

The carbon dioxide supercritical fluid extraction method is a supercritical fluid extraction method in which a crude product is placed in a pressure vessel and liquefied carbon dioxide flows into the pressure vessel while maintaining the pressure and temperature in the pressure vessel. It is a method of purifying a state by extracting the target compound into supercritical carbon dioxide.

The temperature inside the pressure vessel is preferably 31 ° C. or higher and 80 ° C. or lower. If the temperature inside the pressure vessel is less than 31 ° C., carbon dioxide does not reach the supercritical state, and if it exceeds 80 ° C., the extraction power of supercritical carbon dioxide becomes weak.

The pressure in the pressure vessel is preferably 7.38 MPa or more and 30 MPa or less. If the pressure in the pressure vessel is less than 7.38 MPa, carbon dioxide will not be in a supercritical state, and if it exceeds 30 MPa, the pressure resistance of the device will be required, and as a result, the price of the device will increase. The manufacturing cost is high.

(lubricant)
The lubricant of the present embodiment contains the fullerene derivative of the present embodiment. As the lubricant of the present embodiment, the fullerene derivative of the present embodiment may be used alone, or in addition to the fullerene derivative of the present embodiment, other lubricants may be used as long as the effect of the lubricant of the present embodiment is not impaired. It may further contain an agent, an additive generally used as a lubricant, and the like.

The other lubricant is not particularly limited, and examples thereof include perfluoropolyether compounds having no fullerene skeleton.

Examples of the perfluoropolyether compound having no fullerene skeleton include Fombulin (registered trademark) series (manufactured by Solvay Specialty Polymers).

Since the fullerene derivative of the present embodiment has a perfluoropolyether group, it has a high affinity with a perfluoropolyether compound having no fullerene skeleton. Therefore, even when the lubricant of the present embodiment contains the fullerene derivative of the present embodiment and the perfluoropolyether compound having no fullerene skeleton, the fullerene derivative of the present embodiment is uniform in the lubricant of the present embodiment. Can be dispersed or dissolved in.

When the lubricant of the present embodiment contains the fullerene derivative of the present embodiment and a perfluoropolyether compound having no fullerene skeleton, the content of the fullerene derivative in the lubricant is 0.1% by mass or more and 100. It is preferably less than%, more preferably 1% by mass or more and less than 100%, and particularly preferably 10% by mass or more and less than 100%. This makes it possible to exhibit better adsorptivity on the surface to which the lubricant is applied.

The lubricant of the present embodiment can be used by being applied to the surface of a magnetic recording medium such as a hard disk, for example.

The method of applying the lubricant is not particularly limited, but for example, a spin coating method, a dip method, or the like can be used.

When applying a lubricant to the surface of a magnetic recording medium using the dip method, for example, after immersing the magnetic recording medium in a lubricant solution contained in a dipping tank of a dip coating device, the magnetic recording medium is removed from the dipping tank. Pull up at the specified speed.

The concentration of the fullerene derivative in the lubricant solution is preferably 0.0001% by mass or more.

Hereinafter, the present invention will be specifically described based on examples. The present invention is not limited to the examples.

( ^{1 1} H-NMR)
After dissolving the sample (about 10 mg to ₃₀ mg) in a mixed solvent of CDCl 3 / hexafluorobenzene (about 0.5 mL), the sample was placed in an NMR sample tube having a diameter of 5 mm, and ¹ H-NMR analysis was performed under the following conditions. ..

Device: Fourier transform nuclear magnetic resonance device JNM-EX270 (manufactured by JEOL Ltd.)
Measurement temperature: Room temperature At this time, tetramethylsilane was added as a reference substance to _{the CDCl 3 / hexafluorobenzene mixed solvent.}

(MS)
A sample (about 1 mg) was dissolved in toluene (about 0.5 mL), filtered through a membrane filter, and mass spectrometry was performed under the following conditions.

Equipment: Quadrupole LC / MS system Agilent 6120 (manufactured by Agilent Technologies)
Ionization conditions: APCI-
(Example 1)
The fullerene derivative of this embodiment was produced according to the following synthetic example.

(Synthesis Example 1)
Synthesis of compound 1 (C1): [Reaction formula (3)]
Fluorinated triethylene glycol monomethyl ether (manufactured by Exfluor, 10 g, 25 mmol, formula amount of perfluoropolyether group 367) and pyridine (2.4 g, 30 mmol) were added to dichloromethane (100 mL), and trifluoromethane was added to the obtained solution. A solution of sulfonic acid anhydride (8.8 g, 31 mmol) in dichloromethane (30 mL) was added dropwise. The obtained mixture was stirred at room temperature for 20 hours, and then the reaction mixture was washed once with pure water (100 mL) and saturated aqueous sodium carbonate solution (100 mL). The obtained organic layer was filtered and then concentrated by a rotary evaporator to obtain Compound 1 (C1) (13 g, 24 mmol, yield 95%) as a pale yellow oily substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the pale yellow oily substance was Compound 1 represented by the following chemical formula (C1).

^{1 1} H-NMR δ [ppm]: 4.72 (t, 2H).

（合成例２）
化合物２（Ｃ２）の合成：［反応式（４）］
合成例１で得た化合物１（２．４ｇ、４．５ｍｍｏｌ）と４−ヨードフェノール（０．９０ｇ、４．１ｍｍｏｌ）とをＮ，Ｎ−ジメチルホルムアミド（２０ｍＬ）に加え、得られた溶液に炭酸セシウム（２．１ｇ、６．５ｍｍｏｌ）を加えた。得られた混合物を室温で１８時間攪拌した後、反応混合物をロータリーエバポレーターで濃縮した。得られた混合物を純水（３０ｍＬ）と酢酸エチル（３０ｍＬ）を用いて分液し、さらに水層を酢酸エチル（２０ｍＬ）で二度抽出した。得られた有機層を水洗し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、褐色油状の粗生成物（２．６ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン−酢酸エチル（２４：１））で粗生成物を精製することで、無色油状物質として、化合物２（Ｃ２）（２．３ｇ、３．８ｍｍｏｌ、収率９４％）を得た。

(Synthesis Example 2)
Synthesis of compound 2 (C2): [Reaction formula (4)]
Compound 1 (2.4 g, 4.5 mmol) and 4-iodophenol (0.90 g, 4.1 mmol) obtained in Synthesis Example 1 were added to N, N-dimethylformamide (20 mL) to the obtained solution. Cesium carbonate (2.1 g, 6.5 mmol) was added. The resulting mixture was stirred at room temperature for 18 hours and then the reaction mixture was concentrated on a rotary evaporator. The obtained mixture was separated using pure water (30 mL) and ethyl acetate (30 mL), and the aqueous layer was further extracted twice with ethyl acetate (20 mL). The obtained organic layer was washed with water and dried over magnesium sulfate. After filtration, the mixture was concentrated on a rotary evaporator to obtain a crude brown oil product (2.6 g). By purifying the crude product by silica gel column chromatography (developing solvent: hexane-ethyl acetate (24: 1)), compound 2 (C2) (2.3 g, 3.8 mmol, yield 94) was prepared as a colorless oily substance. %) Was obtained.

^{From the analysis results of 1} H-NMR, it was confirmed that the colorless oily substance was compound 2 represented by the following chemical formula (C2).

^{1 1} H-NMR δ [ppm]: 4.32 (t, 2H), 6.71 (d, 2H), 7.61 (d, 2H).

（合成例３）
化合物３（Ｃ３）の合成：［反応式（５）］
合成例２で得た化合物２（０．３０ｇ、０．５０ｍｍｏｌ）とＴＨＦ（１０ｍＬ）の混合物を−２０℃まで冷却し、イソプロピルマグネシウムクロリド−塩化リチウム錯体のＴＨＦ溶液（約１４質量％、０．７ｍＬ、０．６ｍｍｏｌ）を滴下した。得られた混合物を−２０℃で３０分攪拌した後、臭化銅（Ｉ）−ジメチルスルフィド錯体（０．１３ｇ、０．６１ｍｍｏｌ）のＴＨＦ（５ｍＬ）懸濁液を加えた。得られた混合物を３５℃まで加熱した後、Ｃ_６０フラーレン（５１ｍｇ、７０μｍｏｌ）のＯＤＣＢ（１０ｍＬ）溶液を加えた。得られた混合物を６０℃で９０分攪拌した後、室温まで冷却し、ヨードメタン（１ｍＬ）を加えた。濾過した後、ロータリーエバポレーターで濃縮することで、橙色固体状の粗生成物（８８ｍｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン−酢酸エチル（１７：３））で粗生成物を精製することで、橙色固体状物質として、化合物３（Ｃ３）（１５ｍｇ、４．８μｍｏｌ、収率７％）を得た。

(Synthesis Example 3)
Synthesis of compound 3 (C3): [Reaction formula (5)]
The mixture of Compound 2 (0.30 g, 0.50 mmol) and THF (10 mL) obtained in Synthesis Example 2 was cooled to −20 ° C., and a THF solution of isopropylmagnesium chloride-lithium chloride complex (about 14% by mass, 0. 7 mL, 0.6 mmol) was added dropwise. The resulting mixture was stirred at −20 ° C. for 30 minutes and then a suspension of copper (I) bromide (I) -dimethyl sulfide complex (0.13 g, 0.61 mmol) in THF (5 mL) was added. The resulting mixture was heated to 35 ° _C., was added ODCB (10 mL) solution of _{C 60} fullerene (51mg, 70μmol). The resulting mixture was stirred at 60 ° C. for 90 minutes, cooled to room temperature and iodomethane (1 mL) was added. After filtration, the mixture was concentrated with a rotary evaporator to obtain a crude product (88 mg) in the form of an orange solid. By purifying the crude product by silica gel column chromatography (developing solvent: hexane-ethyl acetate (17: 3)), compound 3 (C3) (15 mg, 4.8 μmol, yield 7%) was obtained as an orange solid substance. ) Was obtained.

^{From the analysis results of 1} H-NMR, it was confirmed that the orange solid substance was compound 3 represented by the following chemical formula (C3).

^{1 1} H-NMR δ [ppm]: 1.70 (s, 3H), 4.16-4.26 (m, 6H), 4.34 (t, 4H), 6.90 (d, 2H), 7 .18-7.22 (m, 6H), 7.45 (d, 4H), 7.53 (d, 4H), 7.71 (d, 4H).

（合成例４）
化合物４（Ｃ４）の合成：［反応式（６）］
４−ヨード安息香酸メチル（１．６ｇ、６．０ｍｍｏｌ）とＴＨＦ（３０ｍＬ）の混合物を−２０℃まで冷却し、イソプロピルマグネシウムクロリド−塩化リチウム錯体のＴＨＦ溶液（約１４質量％、６．２ｍＬ、５．３ｍｍｏｌ）を滴下した。得られた混合物を−２０℃で１時間攪拌した後、臭化銅（Ｉ）−ジメチルスルフィド錯体（１．２ｇ、６．０ｍｍｏｌ）を加えた。得られた混合物を３５℃まで加熱した後、Ｃ_６０フラーレン（０．４８ｇ、０．６７ｍｍｏｌ）のＯＤＣＢ（３５ｍＬ）溶液を加えた。得られた混合物を６０℃で３時間攪拌した後、飽和塩化アンモニウム水溶液（１ｍＬ）を加えた。得られた混合物を濾過した後、ロータリーエバポレーターで濃縮することで、黒色固体状の粗生成物（０．８３ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン−酢酸エチル（９：１））で粗生成物を精製することで、赤褐色固体状物質として、化合物４（Ｃ４）（０．２５ｇ、０．１７ｍｍｏｌ、収率２６％）を得た。

(Synthesis Example 4)
Synthesis of compound 4 (C4): [Reaction formula (6)]
A mixture of methyl 4-iodobenzoate (1.6 g, 6.0 mmol) and THF (30 mL) was cooled to −20 ° C. and a solution of isopropylmagnesium chloride-lithium chloride complex in THF (approximately 14% by weight, 6.2 mL). 5.3 mmol) was added dropwise. The obtained mixture was stirred at −20 ° C. for 1 hour, and then copper (I) bromide-dimethyl sulfide complex (1.2 g, 6.0 mmol) was added. The resulting mixture was heated to 35 ° _C., was added ODCB (35 mL) solution of _{C 60} fullerene (0.48g, 0.67mmol). The obtained mixture was stirred at 60 ° C. for 3 hours, and then saturated aqueous ammonium chloride solution (1 mL) was added. The obtained mixture was filtered and then concentrated on a rotary evaporator to obtain a crude product (0.83 g) in the form of a black solid. By purifying the crude product by silica gel column chromatography (developing solvent: hexane-ethyl acetate (9: 1)), compound 4 (C4) (0.25 g, 0.17 mmol, yield) was obtained as a reddish brown solid substance. 26%) was obtained.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was compound 4 represented by the following chemical formula (C4).

^{1 1} H-NMR δ [ppm]: 3.90 (s, 3H), 3.93 (s, 6H), 3.97 (s, 6H), 5.34 (s, 1H), 7.44 (d) , 2H), 7.65 (d, 4H), 7.83-7.89 (m, 10H), 8.03 (d, 4H).

（合成例５）
化合物５（Ｃ５）の合成：［反応式（７）］
合成例４で得た化合物４（０．１４ｇ、０．１０ｍｍｏｌ）のＯＤＣＢ（６０ｍＬ）溶液に数平均分子量（Ｍ_ｎ）約２０００のフォンブリンＺｄｏｌ（ソルベイスペシャルティポリマーズ社製、パーフルオロポリエーテル基の平均式量（Ｍｎ）約２０００）（２．１ｇ、１．１ｍｍｏｌ）のＨＦＴＣＢ（６０ｍＬ）溶液を加えた。得られた混合物にトリフルオロメタンスルホン酸（１ｍＬ）を滴下した後、モレキュラーシーブス４Ａが入ったソックスレー抽出器とジムロート冷却管を取り付け、１９０℃に設定した湯浴で加熱し、２時間攪拌しながら還流した。反応混合物を室温まで冷却し、アンモニア水（１０ｍＬ）を加えて中和した後、ロータリーエバポレーターで濃縮した。得られた油状物質を適量のフッ素系溶媒ＡＫ−２２５（旭硝子社製）に溶解させた後、ロータリーエバポレーターで濃縮することで、黒色油状の粗生成物（２．３ｇ）を得た。

(Synthesis Example 5)
Synthesis of compound 5 (C5): [Reaction formula (7)]
A perfluoropolyether group of Fonbrin Zdol (manufactured by Solvay Specialty Polymers, Inc.) _{having a number average molecular weight (Mn} ) of about 2000 in an ODCB (60 mL) solution of compound 4 (0.14 g, 0.10 mmol) obtained in Synthesis Example 4. An average formula (Mn) of about 2000) (2.1 g, 1.1 mmol) of HFTCB (60 mL) solution was added. After dropping trifluoromethanesulfonic acid (1 mL) into the obtained mixture, a Soxhlet extractor containing Molecular Sieves 4A and a Dimroth condenser were attached, heated in a hot water bath set at 190 ° C., and refluxed with stirring for 2 hours. did. The reaction mixture was cooled to room temperature, neutralized by adding aqueous ammonia (10 mL), and concentrated on a rotary evaporator. The obtained oily substance was dissolved in an appropriate amount of a fluorine-based solvent AK-225 (manufactured by Asahi Glass Co., Ltd.) and then concentrated with a rotary evaporator to obtain a crude black oily product (2.3 g).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 14 MPa to remove impurities such as unreacted von Brin Zdol. Then, the pressure in the container was raised to 27 MPa, and compound 5 (C5) (0.77 g, yield 69%) was extracted as a reddish brown solid substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was the compound 5 represented by the following chemical formula (C5).

^{1 1} H-NMR δ [ppm]: 3.97 (br, 10H), 4.74 (br, 10H), 5.44 (brs, 1H), 7.61 (br, 2H), 7.83 (br) 4, H), 7.94 (br, 2H), 8.01 (br, 8H), 8.17 (br, 4H).

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
（合成例６）
化合物６（Ｃ６）の合成：［反応式（８）］
合成例５で得た化合物５（０．２０ｇ、１８μｍｏｌ）とトリエチルアミン（３５ｍｇ、０．３５ｍｍｏｌ）とをフッ素系溶媒ＡＫ−２２５（旭硝子社製）（１０ｍＬ）に加えた。得られた混合物を氷浴で冷却した後、塩化ベンゾイル（３２ｍｇ、０．２３ｍｍｏｌ）を加えた。得られた混合物を室温で１７時間攪拌した。反応混合物にアンモニア水（１ｍＬ）を加えた後、ロータリーエバポレーターで濃縮した。得られた赤褐色固体状物質を適量のテトラデカフルオロヘキサンに溶解させた後、ロータリーエバポレーターで濃縮することで、赤褐色固体状の粗生成物（１０１ｍｇ）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary.)
(Synthesis Example 6)
Synthesis of compound 6 (C6): [Reaction formula (8)]
Compound 5 (0.20 g, 18 μmol) obtained in Synthesis Example 5 and triethylamine (35 mg, 0.35 mmol) were added to a fluorine-based solvent AK-225 (manufactured by Asahi Glass Co., Ltd.) (10 mL). The resulting mixture was cooled in an ice bath and then benzoyl chloride (32 mg, 0.23 mmol) was added. The resulting mixture was stirred at room temperature for 17 hours. Ammonia water (1 mL) was added to the reaction mixture, and the mixture was concentrated on a rotary evaporator. The obtained reddish brown solid substance was dissolved in an appropriate amount of tetradecafluorohexane and then concentrated with a rotary evaporator to obtain a reddish brown solid crude product (101 mg).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 12 MPa to remove impurities. Then, the pressure in the container was raised to 27 MPa, and compound 6 (C6) (51 mg, yield 24%) was extracted as a reddish brown solid substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was the compound 6 represented by the following chemical formula (C6).

^{1 1} H-NMR δ [ppm]: 4.75 (br, 20H), 5.42 (brs, 1H), 7.24 (br, 10H), 7.41 (br, 15H), 7.62 (m) , 2H), 7.87 (br, 6H), 8.03 (br, 8H), 8.19 (br, 4H).

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
（合成例７）
化合物７（Ｃ７）の合成：［反応式（９）］
５−ヨードイソフタル酸ジメチル（２．９ｇ、８．９ｍｍｏｌ）とＴＨＦ（５０ｍＬ）の混合物を−２０℃まで冷却し、イソプロピルマグネシウムクロリド−塩化リチウム錯体のＴＨＦ溶液（約１４質量％、８．４ｍＬ、８．１ｍｍｏｌ）を滴下した。得られた混合物を−２０℃で１時間攪拌した後、臭化銅（Ｉ）−ジメチルスルフィド錯体（１．９ｇ、９．１ｍｍｏｌ）を加えた。得られた混合物を３０℃まで加熱した後、Ｃ_６０フラーレン（０．７２ｇ、１．０ｍｍｏｌ）のＯＤＣＢ（５０ｍＬ）溶液を加えた。得られた混合物を６０℃で４時間攪拌した後、飽和塩化アンモニウム水溶液（１ｍＬ）を加えた。得られた混合物を濾過した後、ロータリーエバポレーターにより溶液の体積を減少させた。得られた混合物にメタノールを加えることで、赤褐色固体状物質として、化合物７（Ｃ７）（１．５ｇ、０．９０ｍｍｏｌ、収率９０％）が析出した。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary.)
(Synthesis Example 7)
Synthesis of compound 7 (C7): [Reaction formula (9)]
A mixture of dimethyl 5-iodoisophthalate (2.9 g, 8.9 mmol) and THF (50 mL) was cooled to −20 ° C. and a solution of isopropylmagnesium chloride-lithium chloride complex in THF (approximately 14% by weight, 8.4 mL). 8.1 mmol) was added dropwise. The obtained mixture was stirred at −20 ° C. for 1 hour, and then copper (I) bromide-dimethyl sulfide complex (1.9 g, 9.1 mmol) was added. The resulting mixture was heated to 30 ° _C., was added ODCB (50 mL) solution of _{C 60} fullerene (0.72g, 1.0mmol). The obtained mixture was stirred at 60 ° C. for 4 hours, and then saturated aqueous ammonium chloride solution (1 mL) was added. After filtering the resulting mixture, the volume of the solution was reduced by a rotary evaporator. By adding methanol to the obtained mixture, compound 7 (C7) (1.5 g, 0.90 mmol, yield 90%) was precipitated as a reddish brown solid substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was compound 7 represented by the following chemical formula (C7).

^{1 1} H-NMR δ [ppm]: 3.69 (s, 6H), 3.75 (s, 12H), 3.84 (s, 12H), 5.37 (s, 1H), 8.23 (s) , 2H), 8.36 (s, 4H), 8.52 (s, 4H), 8.60 (s, 1H), 8.63 (s, 2H), 8.72 (s, 2H).

（合成例８）
化合物８（Ｃ８）の合成：［反応式（１０）］
合成例７で得た化合物７（０．１８ｇ、０．１１ｍｍｏｌ）のＯＤＣＢ（６０ｍＬ）溶液に数平均分子量（Ｍ_ｎ）約２０００のフォンブリンＺｄｏｌ（ソルベイスペシャルティポリマーズ社製、パーフルオロポリエーテル基の平均式量（Ｍｎ）約２０００）（４．１ｇ、２．１ｍｍｏｌ）のＨＦＴＣＢ（６０ｍＬ）溶液を加えた。得られた混合物にトリフルオロメタンスルホン酸（１ｍＬ）を滴下した後、モレキュラーシーブス４Ａが入ったソックスレー抽出器とジムロート冷却管を取り付け、１９０℃に設定した湯浴で加熱し、５時間攪拌しながら還流した。反応混合物を室温まで冷却し、アンモニア水（１０ｍＬ）を加えて中和した後、ロータリーエバポレーターで濃縮した。得られた油状物質を適量のフッ素系溶媒ＡＫ−２２５に溶解させた後、ロータリーエバポレーターで濃縮することで、黒色油状の粗生成物（４．２ｇ）を得た。

(Synthesis Example 8)
Synthesis of compound 8 (C8): [Reaction formula (10)]
A perfluoropolyether group of Fonbrin Zdol (manufactured by Solvay Specialty Polymers, Inc.) _{having a number average molecular weight (Mn} ) of about 2000 in an ODCB (60 mL) solution of compound 7 (0.18 g, 0.11 mmol) obtained in Synthesis Example 7. An HFTCB (60 mL) solution of an average formula (Mn) of about 2000) (4.1 g, 2.1 mmol) was added. After dropping trifluoromethanesulfonic acid (1 mL) into the obtained mixture, a Soxhlet extractor containing Molecular Sieves 4A and a Dimroth condenser were attached, heated in a hot water bath set at 190 ° C., and refluxed with stirring for 5 hours. did. The reaction mixture was cooled to room temperature, neutralized by adding aqueous ammonia (10 mL), and concentrated on a rotary evaporator. The obtained oily substance was dissolved in an appropriate amount of a fluorine-based solvent AK-225 and then concentrated with a rotary evaporator to obtain a crude black oily product (4.2 g).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 15 MPa to remove impurities such as unreacted von Brin Zdol. Then, the pressure in the container was raised to 27 MPa, and compound 8 (C8) (0.84 g, yield 37%) was extracted as a reddish brown solid substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was compound 8 represented by the following chemical formula (C8).

^{1 1} H-NMR δ [ppm]: 3.95 (br, 20H), 4.73 (br, 20H), 5.40 (brs, 1H), 8.22 (brs, 2H), 8.33 (brs) , 4H), 8.50 (brs, 4H), 8.61 (br, 3H), 8.73 (brs, 2H).

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
（合成例９）
化合物９（Ｃ９）の合成：［反応式（１１）］
合成例８で得た化合物８（０．４８ｇ、２２μｍｏｌ）とトリエチルアミン（８２ｍｇ、０．８１ｍｍｏｌ）とをフッ素系溶媒ＡＫ−２２５（１０ｍＬ）に加えた。得られた混合物を氷浴で冷却した後、１−ナフトイルクロリド（８１ｍｇ、０．４２ｍｍｏｌ）加えた。得られた混合物を室温で１７時間攪拌した。反応混合物にアンモニア水（１ｍＬ）を加えた後、ロータリーエバポレーターで濃縮した。得られた赤褐色固体状物質を適量のフッ素系溶媒ＡＫ−２２５に溶解させた後、ロータリーエバポレーターで濃縮することで、赤褐色固体状の粗生成物（４８５ｍｇ）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary.)
(Synthesis Example 9)
Synthesis of compound 9 (C9): [Reaction formula (11)]
Compound 8 (0.48 g, 22 μmol) obtained in Synthesis Example 8 and triethylamine (82 mg, 0.81 mmol) were added to the fluorine-based solvent AK-225 (10 mL). The resulting mixture was cooled in an ice bath and then 1-naphthoyl chloride (81 mg, 0.42 mmol) was added. The resulting mixture was stirred at room temperature for 17 hours. Ammonia water (1 mL) was added to the reaction mixture, and the mixture was concentrated on a rotary evaporator. The obtained reddish-brown solid substance was dissolved in an appropriate amount of the fluorine-based solvent AK-225 and then concentrated with a rotary evaporator to obtain a reddish-brown solid crude product (485 mg).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 16 MPa to remove impurities. Then, the pressure in the container was raised to 27 MPa, and compound 9 (C9) (405 mg, yield 83%) was extracted as a reddish brown solid substance.

^{From the analysis results of 1} H-NMR, it was confirmed that the reddish brown solid substance was compound 9 represented by the following chemical formula (C9).

^{1 1} H-NMR δ [ppm]: 4.77 (br, 40H), 5.53 (brs, 1H), 7.22 (br, 4H), 7.32-7.58 (m, 14H), 7 .75-8.30 (m, 17H), 8.48 (br, 9H), 8.58 (br, 3H), 8.73 (brs, 2H), 8.86 (br, 5H).

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
（合成例１０）
化合物１０（Ｃ１０）の合成：［反応式（１２）］
４−ヨード安息香酸メチル（０．２６ｇ、０．９８ｍｍｏｌ）とＴＨＦ（１ｍＬ）の混合物を−２０℃まで冷却し、イソプロピルマグネシウムクロリド−塩化リチウム錯体のＴＨＦ溶液（約１４質量％、１．０ｍＬ、０．９０ｍｍｏｌ）を滴下した。得られた混合物を−２０℃で１時間攪拌した後、臭化銅（Ｉ）−ジメチルスルフィド錯体（０．２１ｇ、１．０ｍｍｏｌ）とピリジン（０．７９ｇ、１０ｍｍｏｌ）を加えた。得られた混合物を３０℃まで加熱した後、合成例４で得られた化合物４（４８ｍｇ、３３μｍｏｌ）のＯＤＣＢ（１２ｍＬ）溶液を加えた。得られた混合物を４０℃で６時間攪拌した後、飽和塩化アンモニウム水溶液（１ｍＬ）を加えた。得られた混合物を濾過した後、ロータリーエバポレーターで濃縮することで、赤紫色固体状の粗生成物（０．２７ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン−酢酸エチル（２：１））で粗生成物を精製することで、赤褐色固体状物質として、化合物１０（Ｃ１０）（０．２５ｇ、０．１７ｍｍｏｌ、収率２６％）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary.)
(Synthesis Example 10)
Synthesis of compound 10 (C10): [Reaction formula (12)]
A mixture of methyl 4-iodobenzoate (0.26 g, 0.98 mmol) and THF (1 mL) was cooled to −20 ° C. and a solution of isopropylmagnesium chloride-lithium chloride complex in THF (approximately 14% by weight, 1.0 mL). 0.90 mmol) was added dropwise. The obtained mixture was stirred at −20 ° C. for 1 hour, and then copper (I) bromide-dimethyl sulfide complex (0.21 g, 1.0 mmol) and pyridine (0.79 g, 10 mmol) were added. The resulting mixture was heated to 30 ° C., and then a solution of compound 4 (48 mg, 33 μmol) obtained in Synthesis Example 4 in ODCB (12 mL) was added. The obtained mixture was stirred at 40 ° C. for 6 hours, and then saturated aqueous ammonium chloride solution (1 mL) was added. The obtained mixture was filtered and then concentrated on a rotary evaporator to obtain a reddish purple solid crude product (0.27 g). By purifying the crude product by silica gel column chromatography (developing solvent: hexane-ethyl acetate (2: 1)), compound 10 (C10) (0.25 g, 0.17 mmol, yield) was obtained as a reddish brown solid substance. 26%) was obtained.

Red-brown solid material, from analysis of MS, the compound 10 represented by the following chemical formula (C10) is a partial structure X ¹ was confirmed to be a two having fullerene derivative.

MS: 2072 ([MH] ^- )

（上記Ｘ^１の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（合成例１１）
化合物１１（Ｃ１１）の合成：［反応式（１３）］
合成例１０で得た化合物１０（２１ｍｇ、１０μｍｏｌ）のＯＤＣＢ（６０ｍＬ）溶液に数平均分子量（Ｍ_ｎ）約２０００のフォンブリンＺｄｏｌ（ソルベイスペシャルティポリマーズ社製、パーフルオロポリエーテル基の平均式量（Ｍｎ）約２０００）（０．４０ｇ、０．２０ｍｍｏｌ）のＨＦＴＣＢ（６０ｍＬ）溶液を加えた。得られた混合物にトリフルオロメタンスルホン酸（１ｍＬ）を滴下した後、モレキュラーシーブス４Ａが入ったソックスレー抽出器とジムロート冷却管を取り付け、１９０℃に設定した湯浴で加熱し、２時間攪拌しながら還流した。反応混合物を室温まで冷却し、アンモニア水（１０ｍＬ）を加えて中和した後、ロータリーエバポレーターで濃縮した。得られた油状物質を適量のフッ素系溶媒ＡＫ−２２５に溶解させた後、ロータリーエバポレーターで濃縮することで、褐色油状の粗生成物（０．５２ｇ）を得た。

(The structural formula of X ^1, 5-membered ring and 6 Inwa surrounding it in the center belongs to the fullerene skeleton.)
(Synthesis Example 11)
Synthesis of compound 11 (C11): [Reaction formula (13)]
Fomblin Zdol (manufactured by Solvay Specialty Polymers, Inc., perfluoropolyether group) _{having a number average molecular weight (Mn} ) of about 2000 in an ODCB (60 mL) solution of compound 10 (21 mg, 10 μmol) obtained in Synthesis Example 10 (average formula amount of perfluoropolyether group) A solution of about 2000) (Mn) (0.40 g, 0.20 mmol) in HFTCB (60 mL) was added. After dropping trifluoromethanesulfonic acid (1 mL) into the obtained mixture, a Soxhlet extractor containing Molecular Sieves 4A and a Dimroth condenser were attached, heated in a hot water bath set at 190 ° C., and refluxed with stirring for 2 hours. did. The reaction mixture was cooled to room temperature, neutralized by adding aqueous ammonia (10 mL), and concentrated on a rotary evaporator. The obtained oily substance was dissolved in an appropriate amount of a fluorine-based solvent AK-225 and then concentrated with a rotary evaporator to obtain a crude brown oily product (0.52 g).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 15 MPa to remove impurities such as unreacted von Brin Zdol. Then, the pressure in the container was raised to 27 MPa, and compound 11 (30 mg, yield 14%) represented by the following chemical formula (C11) was extracted as a brown solid substance.

^{From the 1} H-NMR analysis result of Synthesis Example 5, it was estimated that the ^{brown solid substance was a fullerene derivative having two of the following partial structures X2.}

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意であり、上記Ｘ^２の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（合成例１２）
化合物１２（Ｃ１２）の合成：［反応式（１４）］
合成例１２で得た化合物１２（３０ｍｇ、１．４μｍｏｌ）とトリエチルアミン（４４ｍｇ、０．４３ｍｍｏｌ）とをフッ素系溶媒ＡＫ−２２５（１０ｍＬ）に加えた。得られた混合物を氷浴で冷却した後、１−ナフトイルクロリド（３２ｍｇ、０．１７ｍｍｏｌ）加えた。得られた混合物を室温で１８時間攪拌した。反応混合物にアンモニア水（１ｍＬ）を加えた後、ロータリーエバポレーターで濃縮した。得られた赤褐色固体状物質を適量のテトラデカフルオロヘキサンに溶解させた後、ロータリーエバポレーターで濃縮することで、赤褐色固体状の粗生成物（５２ｍｇ）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. the order of the is arbitrary, in the above structural formula X ^2, 5-membered ring and 6 Inwa surrounding it in the center belongs to the fullerene skeleton.)
(Synthesis Example 12)
Synthesis of compound 12 (C12): [Reaction equation (14)]
Compound 12 (30 mg, 1.4 μmol) obtained in Synthesis Example 12 and triethylamine (44 mg, 0.43 mmol) were added to the fluorine-based solvent AK-225 (10 mL). The resulting mixture was cooled in an ice bath and then 1-naphthoyl chloride (32 mg, 0.17 mmol) was added. The resulting mixture was stirred at room temperature for 18 hours. Ammonia water (1 mL) was added to the reaction mixture, and the mixture was concentrated on a rotary evaporator. The obtained reddish brown solid substance was dissolved in an appropriate amount of tetradecafluorohexane and then concentrated with a rotary evaporator to obtain a reddish brown solid crude product (52 mg).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 16 MPa to remove impurities. Then, the pressure in the container was raised to 27 MPa, and compound 12 (C12) (12 mg, yield 38%) was extracted as a reddish brown solid substance.

Red-brown solid material, from the analysis As a result of ^{1 H-NMR} in Synthesis Example 9, was estimated to compound 12 represented by the following chemical formula (C12) is a fullerene derivative having two following partial structure X ^3.

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意であり、上記Ｘ^３の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（合成例１３）
化合物１３（Ｃ１３）の合成：［反応式（１５）］
４−ヨード安息香酸メチル（１．２ｇ、４．４ｍｍｏｌ）とＴＨＦ（５ｍＬ）の混合物を−２０℃まで冷却し、イソプロピルマグネシウムクロリド−塩化リチウム錯体のＴＨＦ溶液（約１４質量％、４．７ｍＬ、４．０ｍｍｏｌ）を滴下した。得られた混合物を−２０℃で１時間攪拌した後、臭化銅（Ｉ）−ジメチルスルフィド錯体（０．９１ｇ、４．４ｍｍｏｌ）とピリジン（３．２ｇ、４０ｍｍｏｌ）を加えた。得られた混合物を３０℃まで加熱した後、合成例７で得られた化合物７（０．３４ｇ、０．２０ｍｍｏｌ）のＯＤＣＢ（１０ｍＬ）溶液を加えた。得られた混合物を４０℃で２０時間攪拌した後、飽和塩化アンモニウム水溶液（１ｍＬ）を加えた。得られた混合物を濾過した後、ロータリーエバポレーターで濃縮することで、茶褐色固体状の粗生成物（２．７ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン−酢酸エチル（２：１））で粗生成物を精製することで、赤褐色固体状物質として、化合物１３（Ｃ１３）（０．２４ｇ、０．１０ｍｍｏｌ、収率５１％）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. the order of the is arbitrary, structural formulas of the above X ^3, 5-membered ring and 6 Inwa surrounding it in the center belongs to the fullerene skeleton.)
(Synthesis Example 13)
Synthesis of compound 13 (C13): [Reaction formula (15)]
A mixture of methyl 4-iodobenzoate (1.2 g, 4.4 mmol) and THF (5 mL) was cooled to −20 ° C. and a solution of isopropylmagnesium chloride-lithium chloride complex in THF (approximately 14% by weight, 4.7 mL). 4.0 mmol) was added dropwise. The obtained mixture was stirred at −20 ° C. for 1 hour, and then copper (I) bromide-dimethyl sulfide complex (0.91 g, 4.4 mmol) and pyridine (3.2 g, 40 mmol) were added. The resulting mixture was heated to 30 ° C., and then a solution of compound 7 (0.34 g, 0.20 mmol) obtained in Synthesis Example 7 in ODCB (10 mL) was added. The obtained mixture was stirred at 40 ° C. for 20 hours, and then a saturated aqueous solution of ammonium chloride (1 mL) was added. The obtained mixture was filtered and then concentrated on a rotary evaporator to obtain a brown solid crude product (2.7 g). By purifying the crude product by silica gel column chromatography (developing solvent: hexane-ethyl acetate (2: 1)), compound 13 (C13) (0.24 g, 0.10 mmol, yield) was obtained as a reddish brown solid substance. 51%) was obtained.

Red-brown solid material, from analysis of MS, the compound 13 represented by the following chemical formula (C13) was confirmed to be a fullerene derivative having a following partial structure X ¹ and the following partial structure Y ^1.

MS: 2362 ([MH] ^- )

（上記Ｘ^１及びＹ^１の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（合成例１４）
化合物１４（Ｃ１４）の合成：［反応式（１６）］
合成例１３で得た化合物１３（０．１１ｇ、４８μｍｏｌ）のＯＤＣＢ（６０ｍＬ）溶液に数平均分子量（Ｍ_ｎ）約２０００のフォンブリンＺｄｏｌ（ソルベイスペシャルティポリマーズ社製、パーフルオロポリエーテル基の平均式量（Ｍｎ）約２０００）（３．１ｇ、１．５ｍｍｏｌ）のＨＦＴＣＢ（６０ｍＬ）溶液を加えた。得られた混合物にトリフルオロメタンスルホン酸（１ｍＬ）を滴下した後、モレキュラーシーブス４Ａが入ったソックスレー抽出器とジムロート冷却管を取り付け、１９０℃に設定した湯浴で加熱し、５時間攪拌しながら還流した。反応混合物を室温まで冷却し、アンモニア水（１０ｍＬ）を加えて中和した後、ロータリーエバポレーターで濃縮した。得られた油状物質を適量のフッ素系溶媒ＡＫ−２２５に溶解させた後、ロータリーエバポレーターで濃縮することで、褐色油状の粗生成物（０．５２ｇ）を得た。

(In ^{the structural formulas of X 1} and Y ¹ , the central 5-membered ring and the 6-membered ring surrounding it belong to the fullerene skeleton.)
(Synthesis Example 14)
Synthesis of compound 14 (C14): [Reaction formula (16)]
Fomblin Zdol (manufactured by Solvay Specialty Polymers, perfluoropolyether group) _{having a number average molecular weight (Mn} ) of about 2000 in an ODCB (60 mL) solution of compound 13 (0.11 g, 48 μmol) obtained in Synthesis Example 13. A solution of HFTCB (60 mL) in an amount (Mn) of about 2000) (3.1 g, 1.5 mmol) was added. After dropping trifluoromethanesulfonic acid (1 mL) into the obtained mixture, a Soxhlet extractor containing Molecular Sieves 4A and a Dimroth condenser were attached, heated in a hot water bath set at 190 ° C., and refluxed with stirring for 5 hours. did. The reaction mixture was cooled to room temperature, neutralized by adding aqueous ammonia (10 mL), and concentrated on a rotary evaporator. The obtained oily substance was dissolved in an appropriate amount of a fluorine-based solvent AK-225 and then concentrated with a rotary evaporator to obtain a crude brown oily product (0.52 g).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 15 MPa to remove impurities such as unreacted von Brin Zdol. Then, the pressure in the container was raised to 27 MPa, and compound 14 (C14) (0.19 g, yield 13%) was extracted as a brown oily substance.

Brown oil, from the analysis As a result of ^{1 H-NMR} in Synthesis Example 5 was estimated to compound 14 represented by the following chemical formula (C14) is a fullerene derivative having a following partial structure X ² and following partial structure Y ^2.

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意であり、上記Ｘ^２及びＹ^２の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（合成例１５）
化合物１５（Ｃ１５）の合成：［反応式（１７）］
合成例１４で得た化合物１４（０．１９ｇ、６．０μｍｏｌ）とトリエチルアミン（６０ｍｇ、０．５９ｍｍｏｌ）とをフッ素系溶媒ＡＫ−２２５（１０ｍＬ）に加えた。得られた混合物を氷浴で冷却した後、１−ナフトイルクロリド（６４ｍｇ、０．３４ｍｍｏｌ）加えた。得られた混合物を室温で１８時間攪拌した。反応混合物にアンモニア水（１ｍＬ）を加えた後、ロータリーエバポレーターで濃縮した。得られた赤褐色固体状物質を適量のテトラデカフルオロヘキサンに溶解させた後、ロータリーエバポレーターで濃縮することで、赤褐色油状の粗生成物（０．２５ｇ）を得た。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. In ^{the structural formulas of X 2} and Y ² , the central 5-membered ring and the 6-membered ring surrounding it belong to the fullerene skeleton.)
(Synthesis Example 15)
Synthesis of compound 15 (C15): [Reaction formula (17)]
Compound 14 (0.19 g, 6.0 μmol) obtained in Synthesis Example 14 and triethylamine (60 mg, 0.59 mmol) were added to the fluorine-based solvent AK-225 (10 mL). The resulting mixture was cooled in an ice bath and then 1-naphthoyl chloride (64 mg, 0.34 mmol) was added. The resulting mixture was stirred at room temperature for 18 hours. Ammonia water (1 mL) was added to the reaction mixture, and the mixture was concentrated on a rotary evaporator. The obtained reddish brown solid substance was dissolved in an appropriate amount of tetradecafluorohexane and then concentrated with a rotary evaporator to obtain a reddish brown oily crude product (0.25 g).

Next, the crude product is placed in a thick stainless steel container (inner diameter 20 mm × depth 200 mm) having an inlet and an outlet, and the temperature inside the container is maintained at 60 ° C., and the supercritical phase chromatography pump PU Using −2086-CO2 (manufactured by Nippon Kogaku Co., Ltd.), supercritical carbon dioxide was sent to a container at a liquefied carbon dioxide equivalent flow rate of 2 mL / min. At this time, the pressure in the container was changed in the range of 9 to 16 MPa to remove impurities. Then, the pressure in the container was raised to 27 MPa, and compound 15 (C15) (0.17 mg, yield 84%) was extracted as a reddish brown oily substance.

Reddish brown oily substance, from the analysis As a result of ^{1 H-NMR} in Synthesis Example 9, was estimated to compound 15 represented by the following chemical formula (C15) is a fullerene derivative having a following partial structure X ³ and following partial structure Y ^3.

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意であり、上記Ｘ^３及びＹ^３の構造式中、中央の５員環とそれを囲む６員環はフラーレン骨格に属す。）
（実施例２）
Ａｒガス雰囲気中で、カーボンをターゲットとして用いた高周波マグネトロンスパッタにより、磁気ディスク用２．５インチガラスプランク上にＤＬＣ（Ｄｉａｍｏｎｄ−Ｌｉｋｅ Ｃａｒｂｏｎ）からなる保護膜を成膜し、模擬ディスクを作製した。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. the order of the is arbitrary, structural formulas of the X ³ and Y ^3, 5-membered ring and 6 Inwa surrounding it in the center belongs to the fullerene skeleton.)
(Example 2)
A protective film made of DLC (Diamond-Like Carbon) was formed on a 2.5-inch glass plank for a magnetic disk by high-frequency magnetron sputtering using carbon as a target in an Ar gas atmosphere to prepare a simulated disk.

Next, compound 3 (C3) was dissolved in tetradecafluorohexane to prepare a 0.001% by mass lubricant solution.

Next, using the dip method, a lubricant solution was applied to the surface of the protective film of the simulated disk by the method shown below. That is, after immersing the simulated disk in the lubricant solution contained in the dipping tank of the dip coating device for 30 seconds, the simulated disk is pulled up from the immersion tank to apply the lubricant solution to the surface of the protective film of the simulated disk. did. Then, the lubricant solution applied to the surface of the protective film of the simulated disc was dried to form a lubricant layer.

(Examples 3 to 6)
Protection of the simulated disk in the same manner as in Example 2 except that compound 6 (C6), compound 9 (C9), compound 12 (C12), and compound 15 (C15) were used instead of compound 3 (C3), respectively. A lubricant layer was formed on the surface of the film.

(Comparative Example 1)
Chemical formula instead of compound 3 (C3)

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約２０００であり、Ｒ_ｆ ^２中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
で表される化合物１６（Ｃ１６）を用いた以外は、実施例２と同様にして、模擬ディスクの保護膜の表面に潤滑剤層を形成しようとしたところ、化合物１６がテトラデカフルオロヘキサンに溶解しなかった。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary.)
When an attempt was made to form a lubricant layer on the surface of the protective film of the simulated disk in the same manner as in Example 2 except that the compound 16 (C16) represented by the above was used, the compound 16 was dissolved in tetradecafluorohexane. I didn't.

Compound 16 (C16) is a compound described in Patent Document 2 (Patent No. 5600202).

(Comparative Example 2)
Bertrel® XF (1,1,1,2,3,4,5,5,5-decafluoropentane) (manufactured by Mitsui DuPont Fluorochemicals) was used instead of tetradecafluorohexane. A lubricant layer was formed on the surface of the protective film of the simulated disk in the same manner as in Comparative Example 1 except for the above.

(Comparative Example 3)
Chemical formula instead of compound 3 (C3)

（式中、ｐ及びｑは平均重合度であり、パーフルオロポリエーテル基の平均式量（Ｍｎ）は約１３００であり、Ｒ_ｆ ^３中の（ＣＦ_２Ｏ）と（ＣＦ_２ＣＦ_２Ｏ）との順序は任意である。）
で表される化合物１７（Ｃ１７）を用いた以外は、実施例２と同様にして、模擬ディスクの保護膜の表面に潤滑剤層を形成した。

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 1300, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^3. The order with and is arbitrary.)
A lubricant layer was formed on the surface of the protective film of the simulated disc in the same manner as in Example 2 except that the compound 17 (C17) represented by the above was used.

Compound 17 (C17) is a compound described in Patent Document 5 (International Publication No. 2017/006812).

(Comparative Example 4)
Chemical formula instead of compound 3 (C3)

で表される化合物１８（Ｃ１８）を用いた以外は、実施例２と同様にして、模擬ディスクの保護膜の表面に潤滑剤層を形成した。

A lubricant layer was formed on the surface of the protective film of the simulated disc in the same manner as in Example 2 except that the compound 18 (C18) represented by the above was used.

Compound 18 (C18) is a compound described in Patent Document 6 (Japanese Unexamined Patent Publication No. 2017-14192).

Next, the average film thickness and bonded ratio of the lubricant layer were evaluated.

(Average film thickness of lubricant layer)
Using a Fourier transform infrared spectroscope Nicolet iS50 (manufactured by Thermo Fisher Scientific), the intensity of the absorption peak corresponding to the expansion and contraction vibration energy of the CF bond in the infrared absorption spectrum is measured by the high-sensitivity reflection method, and lubrication is performed. The average film thickness of the agent layer was determined. At this time, the film thickness of the lubricant layer was measured at four points each, and the average value was taken as the average film thickness.

(Bondid ratio of lubricant layer)
A simulated disk with a lubricant layer formed in Bertrel® XF (1,1,1,2,3,4,5,5,5-decafluoropentane) (manufactured by Mitsui DuPont Fluorochemical). Was immersed for 10 minutes, and then the simulated disk was pulled up to wash away the lubricant not adsorbed on the protective film of the simulated disk. Then, the surface of the simulated disc was dried.

The ratio of the average film thickness of the lubricant layers before and after the above treatment was defined as the bonded ratio.

Table 1 shows the evaluation results of the average film thickness and bonded ratio of the lubricant layer.

表１から、実施例２〜６で用いられた化合物３、６、９、１２、１５は、比較例２〜４で用いられた化合物１６〜１８に対し、ボンディドレシオが高い強固な潤滑剤層を形成できることがわかる。

From Table 1, compounds 3, 6, 9, 12, and 15 used in Examples 2 to 6 are strong lubricants having a higher bonded ratio than compounds 16 to 18 used in Comparative Examples 2 to 4. It can be seen that layers can be formed.

The fullerene derivative of the present embodiment is effective in forming a strong lubricant layer having a high bonded ratio.

Claims (13)

General formula

(In the formula, FLN is a fullerene skeleton, and A is the general formula A _1- CH _2- O-... (A).
(In the formula, A ₁ is a monovalent perfluoropolyether group.)
A group represented by or, the general formula _{Ar-COO-CH 2 -A 2} -CH 2 -OCO- ··· (B)
(In the formula, Ar is an aryl group or an aralkyl group, and A ₂ is a divalent perfluoropolyether group.)
Is a group represented by, R is a hydrogen atom or a methyl group, k is an integer of 5 to 10, m is an integer of 0 to 2, and n is an integer of 1 to 5. )
A fullerene derivative which is a compound represented by. Fullerene derivative according to claim 1 wherein the fullerene skeleton is a C _60. The fullerene derivative according to claim 1 or 2, wherein _{the perfluoropolyether groups of A 1} and A _{2 have 5 to 100 carbon atoms.} The perfluoropolyether groups of A ₁ and A ₂ have the general formula − (CF ₂ ) _x O − ··· (C).
(In the formula, x is an integer from 1 to 5.)
The fullerene derivative according to any one of claims 1 to 3, which contains a group represented by. The fullerene derivative according to claim 4, wherein the perfluoropolyether groups A ₁ and A ₂ contain 1 to 50 groups represented by the general formula (C) in which x is 1 or 2. The fullerene derivative according to any one of claims 1 to 5, wherein _{the average formula amount of the perfluoropolyether groups of A 1} and A _{2 is in the range of 250 to 6000.} The fullerene derivative according to any one of claims 1 to 6, wherein _{the perfluoropolyether groups of A 1} and A _{2 are linear.} The fullerene derivative according to any one of claims 1 to 7, wherein k is 5 or 10. Chemical formula

(In the formula, A ₁ is a monovalent perfluoropolyether group.)
Compound represented by, chemical formula

(In the formula, p and q are the average degree of polymerization, the average formula amount (Mn) of the perfluoropolyether group is about 2000, and (CF ₂ O) and (CF ₂ CF ₂ O) in _{R f} ^2. The order with and is arbitrary .)
Compound represented by, chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, or chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
The fullerene derivative according to any one of claims 1 to 8, which is a compound represented by. A lubricant containing the fullerene derivative according to any one of claims 1 to 9. The lubricant according to claim 10, further containing a perfluoropolyether compound having no fullerene skeleton. General formula

(In the formula, FLN is a fullerene skeleton, A ₂ is a divalent perfluoropolyether group, R is a hydrogen atom or a methyl group, k is an integer of 5 to 10, and m is 0 to 0. It is an integer of 2 and n is an integer of 1-5.)
A fullerene derivative which is a compound represented by. Chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
Compound represented by, or chemical formula

(In the formula, A ₂ is a divalent perfluoropolyether group.)
The fullerene derivative according to claim 12, which is a compound represented by.