JP5494491B2 - N-type semiconductors composed of fullerene compounds - Google Patents

Description

  The present invention relates to an n-type semiconductor comprising a fullerene compound, and more specifically to an n-type semiconductor comprising a fullerene compound having a monosaccharide or sugar alcohol residue.

Fullerene having a soccer ball-like structure composed of 60 carbon atoms (hereinafter referred to as “C60”) is a compound that exhibits particularly excellent properties among n-type semiconductor materials, and uses a vapor deposition method in an ultrahigh vacuum. It is known that a thin film capable of exhibiting electron mobility similar to that of amorphous silicon can be obtained by forming a film (see Non-Patent Document 1).
However, since the thin film made of C60 needs to be formed by a vapor deposition method, it is difficult to cope with an increase in area, and even if it can be accommodated, there is a high possibility that a large production cost will be required.

Therefore, development of a material capable of forming a film by using a coating method that can easily cope with an increase in area without increasing the manufacturing cost is demanded.
So far, [6,6] -phenyl C61-butyric acid methyl ester (hereinafter referred to as “PCBM”), which is a C60 derivative introduced with a substituent, and C60 introduced with a fluorinated alkyl group have been developed. It has been reported that an organic FET can be produced by spin coating using this material (see Patent Document 1 and Non-Patent Document 2).
In addition, C60-fused N-methylpyrrolidine-meta-C12 phenyl (C60MC12), which is a C60 derivative having a long-chain alkyl group introduced therein, has been developed. By using this material, the crystallinity of the resulting thin film is improved. As a result, it has been reported that the electron mobility (0.067 cm ² / Vs) is higher than that of PCBM (see Patent Document 2 and Non-Patent Document 3).

  As described above, in recent years, an n-type semiconductor thin film using a soluble fullerene compound has been developed and its characteristics are improving. However, when viewed as a thin film, there is a problem in that the aggregation is partially caused and the uniformity is low. There is.

JP 2007-251086 A JP 2006-60169 A

Applied Physics Letters, Vol.82, No.25, p4581-p4583, (2003) Advanced Materials, Vol.15, No.24, p2084-p2088, (2003) Applied Physics Letters, Vol.87, p153506-1-p153506-3, (2005)

  This invention is made | formed in view of such a situation, and it aims at providing the n-type semiconductor material soluble in the organic solvent which can give a uniform thin film.

  As a result of intensive studies to achieve the above object, the present inventors have found that a fullerene compound having a monosaccharide residue or a sugar alcohol residue has good solubility in an organic solvent, and this compound. In addition to finding out that the uniformity of the thin film obtained from the varnish contained therein is good, the inventors have found that it can be driven as an n-type semiconductor and completed the present invention.

〔式中、Ｒ¹〜Ｒ⁵は、それぞれ独立して、水素原子またはＯＲ⁷（Ｒ⁷は単糖残基または糖アルコール残基を表す。）基を示し、Ｒ⁶は、炭素数１〜５のアルキル基を示す。ただし、Ｒ¹〜Ｒ⁵のうちの少なくとも１つは、前記ＯＲ⁷基である。〕
２． 前記単糖残基が、テトロース残基、ペントース残基またはヘキソース残基である１のｎ型半導体、
３． 前記単糖残基または糖アルコール残基が、アロシル基、アラビノシル基、エリトロシル基、フルクトシル基、ガラクトシル基、グルコシル基、グロシル基、イノシトール残基、リキソシル基、マンノシル基、リボシル基、シアル酸残基、ソルボシル基、タガロシル基、タロシル基またはキシロシル基である１のｎ型半導体、
４． 前記単糖残基または糖アルコール残基が有する水酸基のうち少なくとも１つが、保護基で保護されている１〜３のいずれかのｎ型半導体、
５． 前記保護基が、アルキル基、ベンジル基、ｐ−メトキシベンジル基、ｔ−ブチル基、メトキシメチル基、２−テトラヒドロピラニル基、エトキシエチル基、アセチル基、ピバロイル基、ベンゾイル基、トリメチルシリル基、トリエチルシリル基、ｔ−ブチルジメチルシリル基、トリイソプロピルシリル基、またはｔ−ブチルジフェニルシリル基である４のｎ型半導体、
６． １〜５のいずれかのｎ型半導体と、有機溶媒とを含み、前記ｎ型半導体が有機溶媒に溶解しているワニス、
７． ６のワニスから得られるｎ型有機半導体薄膜、
８． １〜５のいずれかのｎ型半導体を含むｎ型有機半導体薄膜、
９． ７または８のｎ型有機半導体薄膜を備える有機半導体素子、
１０． ７または８のｎ型有機半導体薄膜を備える電界効果型トランジスタ、
１１． ７または８のｎ型有機半導体薄膜を備える有機薄膜太陽電池、
１２． 下記式（２）で表されるフラーレン化合物

〔式中、Ｒ¹〜Ｒ⁵は、それぞれ独立して、水素原子またはＯＲ⁷（Ｒ⁷は単糖残基または糖アルコール残基を表す。）基を示し、Ｒ⁶は、炭素数１〜５のアルキル基を示す。ただし、Ｒ¹〜Ｒ⁵のうちの少なくとも２つは、前記ＯＲ⁷基である。〕
を提供する。That is, the present invention
1. An n-type semiconductor comprising a fullerene compound represented by the following formula (1):

[Wherein, R ^{1 to} R ⁵ each independently represents a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or a sugar alcohol residue) group, and R ⁶ represents a carbon number of 1 to 5 represents an alkyl group. However, at least one of R ^{1 to} R ⁵ is the OR ⁷ group. ]
2. 1 n-type semiconductor wherein the monosaccharide residue is a tetrose residue, a pentose residue or a hexose residue;
3. The monosaccharide residue or sugar alcohol residue is an allosyl group, arabinosyl group, erythrosyl group, fructosyl group, galactosyl group, glucosyl group, grosyl group, inositol residue, lysosyl group, mannosyl group, ribosyl group, sialic acid residue 1 n-type semiconductor which is a sorbosyl group, a tagarosyl group, a tarosyl group or a xylosyl group,
4). Any one of the n-type semiconductors 1 to 3, wherein at least one of the hydroxyl groups of the monosaccharide residue or sugar alcohol residue is protected with a protecting group;
5. The protective group is an alkyl group, benzyl group, p-methoxybenzyl group, t-butyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl group, triethyl. 4 n-type semiconductors which are a silyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, or a t-butyldiphenylsilyl group,
6). A varnish containing any one of the n-type semiconductors 1 to 5 and an organic solvent, wherein the n-type semiconductor is dissolved in the organic solvent;
7). N-type organic semiconductor thin film obtained from 6 varnishes,
8). An n-type organic semiconductor thin film comprising any one of n-type semiconductors of 1 to 5,
9. An organic semiconductor element comprising 7 or 8 n-type organic semiconductor thin film;
10. A field effect transistor comprising 7 or 8 n-type organic semiconductor thin film;
11. An organic thin film solar cell comprising 7 or 8 n-type organic semiconductor thin films,
12 Fullerene compound represented by the following formula (2)

[Wherein, R ^{1 to} R ⁵ each independently represents a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or a sugar alcohol residue) group, and R ⁶ represents a carbon number of 1 to 5 represents an alkyl group. However, at least two of R ^{1 to} R ⁵ are the OR ⁷ group. ]
I will provide a.

Since the n-type semiconductor of the present invention has good solubility in an organic solvent, a thin film can be formed by a solution process such as a coating method.
Therefore, the area of the semiconductor element can be easily increased and the manufacturing cost can be reduced.
Moreover, since the thin film obtained by using the n-type semiconductor of the present invention is excellent in uniformity without aggregation, the characteristics of the element provided with this thin film are improved.

It is a figure which shows the confocal laser micrograph of the film-forming surface of the PCBM thin film produced in the comparative example 2. FIG. 6 is a diagram illustrating a two-dimensional film formation surface of a PCBM thin film manufactured in Comparative Example 2. FIG. 6 is a view showing a three-dimensional film formation surface of a PCBM thin film produced in Comparative Example 2. FIG. It is a figure which shows the confocal laser micrograph of the film-forming surface of the thin film produced in Example 12. FIG. 10 is a view showing a two-dimensional film formation surface of a thin film produced in Example 12. FIG. 10 is a view showing a three-dimensional film formation surface of a thin film produced in Example 12. FIG. It is a figure which shows the two-dimensional film-forming surface of the thin film produced in Example 13. It is a figure which shows the three-dimensional film-forming surface of the thin film produced in Example 13. FIG. It is a figure which shows the confocal laser micrograph of the film-forming surface of the thin film produced in Example 14. FIG. It is a figure which shows the two-dimensional film-forming surface of the thin film produced in Example 14. It is a figure which shows the three-dimensional film-forming surface of the thin film produced in Example 14. FIG. It is a figure which shows the two-dimensional film-forming surface of the thin film produced in Example 15. FIG. It is a figure which shows the three-dimensional film-forming surface of the thin film produced in Example 15. It is a figure which shows the two-dimensional film-forming surface of the thin film produced in Example 16. FIG. 11 is a view showing a three-dimensional film formation surface of a thin film produced in Example 16. 6 is a view showing a two-dimensional film formation surface of a thin film produced in Example 17. FIG. 6 is a view showing a three-dimensional film formation surface of a thin film produced in Example 17. FIG. It is a figure which shows the two-dimensional film-forming surface of the thin film produced in Example 18. FIG. FIG. 10 is a view showing a three-dimensional film formation surface of a thin film produced in Example 18. 14 is a graph showing transistor characteristics of the element manufactured in Example 19. FIG. 22 is a graph showing transistor characteristics of the element manufactured in Example 20. FIG.

Hereinafter, the present invention will be described in more detail.
As represented by the following formula (1), the n-type semiconductor according to the present invention is a C60 compound having a phenyl-substituted pyrrolidine skeleton, wherein a monosaccharide residue or a sugar alcohol residue is an ortho, meta, or para group of a phenyl group. It consists of a compound to which at least one is added via a position.

In the formula (1), R ^{1 to} R ⁵ each independently represent a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or a sugar alcohol residue), and R ^{1 to} R ⁵ At least one of them is an OR ⁷ group.
Although it does not specifically limit as a monosaccharide residue, In this invention, a tetrose residue, a pentose residue, and a hexose residue are suitable, and a hexose residue is especially preferable.

Examples of the tetroses residue include an erythrosyl group which is an erythrose residue.
Examples of the pentose residue include an arabinosyl group which is an arabinose residue, a lyxosyl group which is a lyxose residue, a ribosyl group which is a ribose residue, and a xylosyl group which is a xylose residue.
Hexose residues include allose residues that are allose residues, fructose residues that are fructosyl groups, galactose residues that are galactosyl groups, glucose residues that are glucosyl groups, growth residues that are grosyl groups, and mannose residues. Examples thereof include a mannosyl group, a tagarosyl group which is a tagarose residue, a tarosyl group which is a talose residue, and a sialic acid residue.
Examples of sugar alcohol residues include inositol residues.
Among these, in the present invention, a hexose residue is preferable, and a galactosyl group and a glucosyl group are particularly preferable.

R ⁶ is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t -Butyl group, n-pentyl group, etc. are mentioned, and a methyl group is particularly preferable.

In consideration of further improving the solubility of the n-type semiconductor of the present invention in an organic solvent, it is preferable that at least one hydroxyl group of the monosaccharide residue or the sugar alcohol residue is protected with a protective group, More preferably, all hydroxyl groups are protected with protecting groups.
In this case, the protecting group is not particularly limited, and may be appropriately selected from protecting groups generally used for protecting the sugar hydroxyl group.
Specific examples thereof include alkyl group, benzyl group, p-methoxybenzyl group, t-butyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl group, A triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, a t-butyldiphenylsilyl group and the like can be mentioned, and an acetyl group is particularly preferable.

  The C60 compound represented by the above formula (1) is a monosaccharide published in “Synthesis and Electrochemical Properties of Water-Soluble Fullerene Derivatives Having Sugar Units” (The 81st Spring Annual Meeting of the Chemical Society of Japan, March 2002). It can be synthesized according to a method for synthesizing a C60 compound having a residue. One example is as shown in the following scheme.

The varnish of the present invention contains the above-described C60 compound and an organic solvent, and the C60 compound is dissolved in the organic solvent.
Here, the organic solvent is not particularly limited as long as it has the ability to dissolve the C60 compound. For example, benzene, toluene, xylene, chlorobenzene, diethyl ether, tetrahydrofuran, dioxane, acetone, ethyl acetate, Examples thereof include carbon sulfide, dichloroethane, chloroform, and dichloromethane.
The content of the C60 compound in the varnish is not particularly limited as long as it is an amount that can be dissolved in an organic solvent, but is preferably 0.01 to 20% by mass in consideration of operability such as applicability. 0.5-3 mass% is more preferable.

An n-type organic semiconductor thin film can be formed on a base material by apply | coating the varnish demonstrated above on a base material, and evaporating a solvent.
The method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, and a spray method.
The method for evaporating the solvent is not particularly limited. For example, the solvent may be evaporated in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using a hot plate or an oven.
Although a calcination temperature will not be specifically limited if a solvent can be evaporated, It is preferable to carry out at 80-100 degreeC.

  Although the film thickness of a semiconductor thin film is not specifically limited, 50-100 nm is suitable. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate during coating.

By using the varnish of the present invention, there is an advantage that a thin film can be produced by a simple method as compared with a method that is not a solution process such as a vapor deposition method and can easily cope with an increase in area.
In addition, as a formation method of the thin film containing the n-type semiconductor of this invention, it is not restricted to the solution process using the said coating method, Other conventionally well-known methods, such as a vapor deposition method, can also be used.

The n-type organic semiconductor thin film described above can be suitably used as a semiconductor layer constituting a semiconductor element such as a field effect transistor, a light emitting diode, a photoelectric conversion element, or an organic thin film solar cell.
Since the semiconductor element of the present invention is characterized by using the above-mentioned fullerene compound having a monosaccharide residue or a sugar alcohol residue as an n-type semiconductor, the constituent members of other elements are appropriately selected from conventionally known members. Can be used.

A field effect transistor will be described as an example.
A field effect transistor generally includes a substrate, a gate electrode and a gate insulating film, a source electrode and a drain electrode, and an n-type organic semiconductor layer. As the n-type organic semiconductor layer, The n-type organic semiconductor thin film described above is used.
The arrangement of the gate electrode, gate insulating film, source electrode, drain electrode and n-type organic semiconductor layer is such that the gate electrode and gate insulating film are stacked on the substrate, and the n-type organic semiconductor thin film is stacked on the substrate. There are various forms such as a form in which the source electrode and the drain electrode are stacked on the substrate, and any form can be used in the present invention.

Examples of the substrate include a silicon substrate, a glass substrate, and a plastic substrate such as polyethylene terephthalate.
Examples of the material constituting the gate electrode include p-doped silicon, n-doped silicon, indium / tin oxide (ITO), conductive polymers such as doped polythiophene and polyaniline, and metals such as gold, silver, platinum, and chromium. Etc.
Examples of the material constituting the gate insulating film include inorganic compounds such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, and tantalum oxide, and organic compounds such as polyvinyl alcohol, polyvinyl phenol, polymethyl methacrylate, and cyanoethyl pullulan. .
Examples of the material constituting the source electrode and the drain electrode include gold, silver, platinum, chromium, aluminum, indium, alkali metal (Li, Na, K, Rb, Cs), and alkaline earth metal (Mg, Ca, Sr). , Ba) and the like.

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the analyzer used in the Example is as follows.
(1) Melting point: Trace melting point measuring device (manufactured by Yanagimoto Seisakusho Co., Ltd., MP-S3)
(2) NMR: Superconducting nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., JNM-EX270 and JNM-ECS 400)
(3) IR: Fourier transform infrared spectrophotometer (JASCO FT / IR-7000, manufactured by JASCO Corporation)
(4) MS: Mass spectrometer (manufactured by JEOL Ltd., JMS-AX500, and BRUKER, autoflex II MALDI TOF / TOF MS)
(5) Optical rotation: Polarimeter (manufactured by JASCO Corporation, DIP-1000 type)
(6) UV-VIS spectrum: UV-visible spectrophotometer (manufactured by Hitachi, Ltd., U-2000 type Hitachi double beam spectrophotometer)
(7) HPLC: High performance liquid chromatograph (Hitachi Ltd., L-6000 Hitachi high performance liquid chromatograph)

Synthesis Example 1 Synthesis of 2-formylphenyltetra-O-acetyl-β-D-glucopyranoside (2)

Under a nitrogen atmosphere, tetra-O-acetyl-α-D-glucopyranosyl bromide (1) (822 mg, 2.0 mmol) was added to a quinoline solution (2.0 ml) of o-hydroxybenzaldehyde (124 mg, 1.0 mmol). , And silver oxide (463 mg, 2.0 mmol) were added and stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a brown viscous oil (780 mg).
The residue was subjected to column chromatography (BW-300, manufactured by Fuji Silysia Chemical Ltd., hereinafter the same), and colorless viscous oil (660 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from ethanol to obtain colorless needle crystals (2) (400 mg, 88%). The analysis results of the obtained product are as follows.

Anal. Calcd for C₂₁H₂₄O₁₁ : C, 55.75 ; H, 5.35%.
Found : C, 55.84 ; H, 5.37%.Colorless needles (Ethanol), mp 138-139 ° C. (Lit. mp 125-124 ° C)
IR (KBr) 2966 (CH), 1763, 1688 (C = O), 1603, 1485 (C = C), 1234, 1071, 1042 (OC = O), 764 cm ^-1 (C H ).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.06 (3H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.08 (3H, s, CH ₃ ), 3.87-3.98 (1H, m, 5 -H), 4.19 (1H, dd, J = 2.5, 12.2 Hz, 6-H), 4.31 (1H, dd, J = 5.5, 12.2 Hz, 6-H), 5.14-5.26 (2H, m, 2- , 3-H), 5.29-5.44 (2H, m, 1-, 4-H), 7.13 (1H, d, J = 8.4 Hz, Ar-H), 7.21 (1H, dd, J = 7.6, 8.4 Hz , Ar-H), 7.57 (1H, ddd, J = 1.7, 7.6, 8.4 Hz, Ar-H), 7.87 (1H, dd, J = 1.7, 7.6 Hz, Ar-H), 10.35 (1H, s, (CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.59 (CH ₃ × 3), 20.66 (CH ₃ ), 61.78 (CH ₂ ), 68.16, 70.91, 72.22, 72.42 (2, 3, 4, 5-C), 99.03 (1-C), 115.96, 123.63, 126.22, 128.34, 135.74, 158.76 (Ar-C), 169.22, 169.38, 170.19, 170.51 (CH ₃ CO), 189.14 (Ar-CO).
FAB-MS (m-NBA) m / z 452 (M ⁺ ), 451 ([MH] ⁺ ).

Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.84; H, 5.37%.

Synthesis Example 2 Synthesis of 3-formylphenyltetra-O-acetyl-β-D-glucopyranoside (3)

Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (1) was added to a quinoline solution (2.0 ml) of m-hydroxybenzaldehyde (123 mg, 1.0 mmol). ) (822 mg, 2.0 mmol) and silver oxide (463 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (764 mg).
The residue was subjected to column chromatography, and a colorless viscous oil (493 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from ethanol to obtain colorless needle crystals (3) (436 mg, 96%). The analysis results of the obtained product are as follows.

Anal. Calcd for C₂₁H₂₄O₁₁ : C, 55.75 ; H, 5.35%.
Found : C, 55.78 ; H, 5.36%.Colorless needles (Ethanol), mp 105-106 ℃. (Lit. mp 108-109 ℃)
IR (KBr) 3070, 2944 (CH), 1760, 1736, 1700 (C = O), 1595, 1485 (C = C), 1236, 1220, 1089, 1058, 1038 (OC = O), 803, 770 cm ^-1 (CH).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.05 (3H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.10 (3H, s, CH ₃ ), 3.98 (1H, ddd, J = 2.7 , 5.7, 9.9 Hz, 5-H), 4.20 (1H, dd, J = 2.7, 12.4 Hz, 6-H), 4.27 (1H, dd, J = 5.9, 12.2 Hz, 6-H), 5.12-5.38 (4H, m, 1, 2, 3, 4-H), 7.26 (1H, ddd, J = 1.4, 3.0, 8.1 Hz, 5'-H), 7.49 (1H, t, J = 8.1 Hz, 4 ' -H), 7.51 (1H, t, J = 1.4 Hz, 2'-H), 7.69 (1H, td, J = 1.4, 7.6 Hz, 6'-H), 9.98 (1H, s, CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.59 (CH ₃ × 2), 20.65 (CH ₃ × 2), 61.98 (CH ₂ ), 68.19, 71.05, 72.29, 72.61 (2, 3, 4, 5-C ), 98.60 (1-C), 115.96 (3'-C), 123.63 (5'-C), 126.22 (4'-C), 128.34 (2'-C), 135.74 (6'-C), 158.76 (1'-C), 169.29, 169.43, 170.19, 170.67 (CH ₃ CO), 191.46 (CHO).

Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.78; H, 5.36%.

Synthesis Example 3 Synthesis of 4-formylphenyltetra-O-acetyl-β-D-glucopyranoside (4)

Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (1) was added to a quinoline solution (2.0 ml) of p-hydroxybenzaldehyde (123 mg, 1.0 mmol). ) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (702 mg).
The residue was subjected to column chromatography, and a colorless viscous oil (417 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from ethanol to obtain colorless needle crystals (4) (375 mg, 83%). The analysis results of the obtained product are as follows.

Colorless needles (Ethanol), mp 147-148 ℃. (Lit. mp 149-150 ℃)
IR (KBr) 1754, 1694 (C = O), 1236, 1056 cm ^-1 (OC = O).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.05 (3H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.08 (3H, s, CH ₃ ), 3.94 (1H, ddd, J = 2.5 , 5.5, 10.1 Hz, 5-H), 4.18 (1H, dd, J = 2.5, 12.2 Hz, 6-H), 4.30 (1H, dd, J = 5.5, 12.2 Hz, 6-H), 5.14-5.38 (4H, m, 1, 2, 3, 4-H), 7.11, 7.86 (each 2H, d, J = 8.9 Hz, Ar-H), 9.93 (1H, s, CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.61 (CH ₃ × 3), 20.68 (CH ₃ ), 61.87 (6-C), 68.12, 71.01, 72.33, 72.54 (2, 3, 4, 5-C) , 98.04 (1-C), 116.78 (2'-C), 131.46 (4'-C), 131.82 (3'-C), 161.24 (1'-C), 169.23, 169.40, 170.20, 170.49 (CH ₃ CO), 190.71 (CHO).
FAB-MS (m-NBA) m / z 452 (M ⁺ ), 451 ([MH] ⁺ ).
Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.66; H, 5.37%

Synthesis Example 4 Synthesis of 2-formylphenyltetra-O-acetyl-β-D-galactopyranoside (6)

Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide (5) was added to a quinoline solution (2.0 ml) of o-hydroxybenzaldehyde (124 mg, 1.0 mmol). ) (822 mg, 2.0 mmol) and silver oxide (463 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a white viscous oil (747 mg).
The residue was subjected to column chromatography, and a colorless viscous oil (652 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from hexane-diethyl ether (7: 2) to obtain colorless needle crystals (6) (454 mg, 98%). The analysis results of the obtained product are as follows.

Anal. Calcd for C₂₁H₂₄O₁₁ : C, 55.75 ; H, 5.35%.
Found : C, 55.94 ; H, 5.44%.Colorless needles [Diethyl ether-n-Hexane (7/2)], mp 113-114 ° C.
IR (KBr) 2982 (CH), 1748, 1698 (C = O), 1603, 1487 (C = C), 1234, 1093, 1044 (COC), 768 cm ^-1 (CH).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.03 (3H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.21 (3H, s, CH ₃ ), 4.07-4.33 (3H, m, 5 -, 6-H), 5.16 (1H, dd, J = 3.4, 10.5 Hz, 3-H), 5.17 (1H, d, J = 8.0 Hz, 1-H), 5.50 (1H, d, J = 3.4 Hz, 4-H), 5.60 (1H, dd, J = 8.0, 10.5 Hz, 2-H), 7.14 (1H, d, J = 8.4 Hz, 6'-H), 7.19 (1H, t, J = 7.6 Hz, 4'-H), 7.57 (1H, ddd, J = 1.7, 7.6, 8.4 Hz, 5'-H), 7.87 (1H, dd, J = 1.7, 7.6 Hz, 3'-H), 10.37 (1H, s, CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.58 (CH ₃ ), 20.66 (CH ₃ × 3), 61.28 (CH ₂ ), 66.74, 68.34, 70.58, 71.27 (2, 3, 4, 5-C), 99.44 (1-C), 115.72 (6'-C), 123.50 (4'-C), 126.09 (2'-C), 128.28 (3'-C), 135.72 (5'-C), 158.81 (1 '-C), 169.34, 170.10, 170.20, 170.33 (CH ₃ CO), 189.29 (CHO).
FAB-MS (m-NBA) m / z 452 (M ⁺ ), 451 ([MH] ⁺ ).

Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.94; H, 5.44%.

Synthesis Example 5 Synthesis of 3-formylphenyltetra-O-acetyl-β-D-galactopyranoside (7)

Under a nitrogen stream, m-hydroxybenzaldehyde (122 mg, 1.0 mmol) in a quinoline solution (2.0 ml) was added 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide (5 ) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (751 mg).
The residue was subjected to column chromatography, and a colorless viscous oil (445 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from hexane-diethyl ether (7: 2) to obtain colorless prism crystals (7) (381 mg, 85%). The analysis results of the obtained product are as follows.

Anal. Calcd for C₂₁H₂₄O₁₁ : C, 55.75 ; H, 5.35%.
Found : C, 55.83 ; H, 5.36%.Colorless prisms [Diethyl ether-n-Hexane (7/2)], mp 96-97 ° C.
IR (KBr) 2986 (CH), 1752, 1707 (C = O), 1597, 1487 (C = C), 1228, 1083, 1065 (COC), 801, 687 cm ^-1 (CH).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.03 (3H, s, CH ₃ ), 2.08 (3H, s, CH ₃ ), 2.10 (3H, s, CH ₃ ), 2.20 (3H, s, CH ₃ ) , 4.14 (1H, ddd, J = 0.8, 5.1, 7.0 Hz, 5-H), 4.20 (1H, d, J = 5.1 Hz, 6-H), 4.21 (1H, d, J = 7.0 Hz, 6- H), 5.14 (1H, dd, J = 3.4, 10.5 Hz, 3-H), 5.15 (1H, d, J = 8.0 Hz, 1-H), 5.49 (1H, dd, J = 3.4, 0.8 Hz, 4-H), 5.53 (1H, dd, J = 8.0, 10.5 Hz, 2-H), 7.28 (1H, ddd, J = 1.3, 3.0, 7.6 Hz, 6'-H), 7.49 (1H, t, J = 7.6 Hz, 5'-H), 7.53 (1H, dd, J = 1.3, 3.0 Hz, 2'-H), 7.59 (1H, dt, J = 7.6, 1.3 Hz, 4'-H), 9.99 (1H, s, CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.59 (CH ₃ ), 20.63 (CH ₃ ), 20.66 (CH ₃ ), 20.75 (CH ₃ ), 61.63 (CH ₂ ), 66.97, 68.50, 70.74, 71.43 (2 , 3, 4, 5-C), 99.17 (1-C), 115.18, 123.70, 125.95, 130.31 (2 ', 4', 5 ', 6'-C), 137.91 (3'-C), 157.32 ( 1'-C), 169.40, 170.10, 170.22, 170.56 (CH ₃ CO), 191.50 (CHO).

Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.83; H, 5.36%.

Synthesis Example 6 Synthesis of 4-formylphenyltetra-O-acetyl-β-D-galactopyranoside (8)

  Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide (5) was added to a quinoline solution (2.0 ml) of p-hydroxybenzaldehyde (123 mg, 1.0 mmol). ) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (725 mg). The residue was subjected to column chromatography, and a colorless viscous oil (436 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from hexane-diethyl ether (7: 2) to obtain colorless needle crystals (8) (392 mg, 87%). The analysis results of the obtained product are as follows.

Anal. Calcd for C₂₁H₂₄O₁₁ : C, 55.75 ; H, 5.35%.
Found : C, 55.82 ; H, 5.36%.Colorless needles [Diethyl ether-n-Hexane (7/2)], mp 118-119 ° C.
IR (KBr) 2832 (CH), 1742, 1702 (C = O), 1605, 1510 (C = C), 1228, 1083, 1050 (COC), 843 cm ^-1 (CH).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.03 (3H, s, CH ₃ ), 2.08 (6H, s, CH ₃ × 2), 2.20 (3H, s, CH ₃ ), 4.10-4.30 (3H, m , 5, 6-H), 5.15 (1H, dd, J = 3.8, 10.5 Hz, 3-H), 5.19 (1H, d, J = 8.0 Hz, 1-H), 5.49 (1H, d, J = 3.8 Hz, 4-H), 5.53 (1H, dd, J = 8.0, 10.5 Hz, 2-H), 7.12 (2H, d, J = 8.4 Hz, 2 ', 6'-H), 7.86 (2H, d, J = 8.4 Hz, 3 ', 5'-H), 9.93 (1H, s, CHO).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.59 (CH ₃ ), 20.66 (CH ₃ × 2), 20.72 (CH ₃ ), 61.37 (CH ₂ ), 66.76, 68.39, 70.67, 71.34 (2, 3, 4 , 5-C), 99.58 (1-C), 116.75 (2 ', 6'-C), 131.84 (3', 4 ', 5'-C), 161.29 (1'-C), 169.32, 170.10, 170.19, 170.35 (CH ₃ CO), 190.74 (CHO).

Anal.Calcd for C ₂₁ H ₂₄ O ₁₁ : C, 55.75; H, 5.35%.
Found: C, 55.82; H, 5.36%.

Synthesis Example 7 Synthesis of 2,4-bis (2,3,4,6-tetra-O-acetyl-β-D-glucosyloxy) benzaldehyde (9)

  Under a nitrogen stream, tetra-O-acetyl-α-D-glucopyranosyl bromide (1) (1233 mg, 3) was added to a quinoline solution (3.0 ml) of 2,4-dihydroxybenzaldehyde (138 mg, 1.0 mmol). 0 mmol) and silver oxide (495 mg, 3.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 ml), and insoluble matters were filtered off. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (1085 mg) as a residue. The residue was subjected to column chromatography, and yellow viscous oil (801 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was extracted with diethyl ether (30 ml), and yellow viscous oil (105 mg) was filtered off as an insoluble material. Next, the extract was concentrated to obtain a white viscous oil (733 mg, 92%). This was recrystallized from hexane-ethanol (3: 1) to obtain colorless needle crystals (9) (680 mg, 85%, mp 179-180 ° C.). The analysis results of the obtained product are as follows.

Colorless needles, [n-Hexane-Ethanol (3: 1)], mp 179-180 ° C.
IR (KBr) 2966 (CH), 1760, 1688 (C = O), 1607, 1497 (C = C), 1226, 1040 (OC = O), 820 cm ^-1 (CH).
¹ H NMR (270 MHz CDCl ₃ ) δ 2.05 (9H, s, CH ₃ ), 2.07 (12H, s, CH ₃ ), 2.12 (3H, s, CH ₃ ), 3.85-4.02 (2H, m, 6- H), 4.17 (2H, ddd, J = 2.5, 9.7, 12.4 Hz, 5-H), 4.29 (2H, dd, J = 5.3, 12.4 Hz, 6-H), 5.06-5.43 (8H, m, 1 , 2, 3, 4-H), 6.67 (1H, d, J = 2.1 Hz, 3'-H), 6.74 (1H, dd, J = 2.1, 8.9 Hz, 5'-H), 7.85 (1H, d, J = 8.9 Hz, 6'-H), 10.21 (1H, s, CHO).

Synthesis Example 8 Synthesis of 3,5-bis (2,3,4,6-tetra-O-acetyl-β-D-glucosyloxy) benzaldehyde (10)

  Under a nitrogen stream, tetra-O-acetyl-α-D-glucopyranosyl bromide (1) (613 mg, 1.5 mmol) was added to a quinoline solution (2 ml) of 3,5-dihydroxybenzaldehyde (69 mg, 0.5 mmol). , And silver oxide (347 mg, 1.5 mmol) were added and stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with chloroform (50 ml), and insoluble matters were filtered off. Next, the extract was washed 5 times with 1% hydrochloric acid (20 ml) and then washed 5 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate, and a yellow solid (682 mg) was obtained as a residue. The residue was subjected to column chromatography, and a white solid (301 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2). This was recrystallized from ethanol to obtain colorless needle crystals (10) (241 mg, 60%, mp 113-114 ° C.). The analysis results of the obtained product are as follows.

Colorless needles, (Ethanol), mp 113-114 ° C.
IR (KBr) 2966 (CH), 1756, 1702 (C = O), 1609, 1460 (C = C), 1234, 1215, 1080, 1069, 1042 (OC = O), 907 cm ^-1 (CH).
¹ H NMR (270 MHz CDCl ₃ ) δ 2.04 (6H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.10 (6H, s, CH ₃ ), 3.94 (2H, ddd, J = 2.7, 5.7, 11.4 Hz, 5-H), 4.18 (2H, dd, J = 2.7, 12.2 Hz, 6-H), 4.25 (2H, dd, J = 5.7, 12.2 Hz , 6-H), 5.09-5.38 (8H, m, 1, 2, 3, 4-H), 6.86 (1H, t, J = 2.3 Hz, 4'-H), 7.21 (2H, d, J = 2.3 Hz, 2 ', 6'-H), 9.90 (1H, s, CHO).

Synthesis Example 9 Synthesis of 2,4,6-tris (2,3,4,6-tetra-O-acetyl-β-D-glucosyloxy) benzaldehyde (11)

  Under a nitrogen stream, tetra-O-acetyl-α-D-glucopyranosyl bromide (1) (924 mg, 2) was added to a quinoline solution (3 ml) of 2,4,6-trihydroxybenzaldehyde (77 mg, 0.5 mmol). .25 mmol) and silver oxide (519 mg, 2.25 mmol) were added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was extracted with benzene (50 ml), and insoluble matters were filtered off. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow oil (723 mg) as a residue. The residue was subjected to column chromatography, and white viscous oil (407 mg) was obtained from the fraction eluted with hexane-ethyl acetate (2: 3). This was recrystallized from ethanol to obtain a white powder (11) (367 mg, 64%, mp 225-226 ° C.). The analysis results of the obtained product are as follows.

White powder, (Ethanol), mp 225-226 ° C.
IR (KBr) 2948 (CH), 1760, 1698 (C = O), 1607 (C = C), 1230, 1061, 1044 (OC = O), 907 cm ^-1 (CH).
¹ H NMR (270 MHz CDCl ₃ ) δ 2.04 (9H, s, CH ₃ ), 2.05 (3H, s, CH ₃ ), 2.06 (15H, s, CH ₃ ), 2.09 (3H, s, CH ₃ ), 2.13 (6H, s, CH ₃ ), 3.85-4.36 (9H, m, 5, 6-H), 5.10-5.48 (12H, m, 1, 2, 3, 4-H), 6.49 (2H, s, Ar-H), 10.14 (1H, s, CHO).

[1] Production of C60 derivative [Example 1] Synthesis of C60 (13) having 2- (tetra-O-acetyl-β-D-glucopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, C60 (288 mg, 0.4 mmol) in a dry p-xylene solution (200 ml) was added to o-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 1. D-glucopyranoside (2) (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (537 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (105 mg, 36%) from the carbon disulfide eluate, a black-brown solid [267 mg, 56% (87%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was dissolved by heating with benzene (4 ml), and then ethanol (20 ml) was added under cooling and reprecipitated to obtain a black-brown solid (13) [228 mg, 48% (74%)]. The analysis results of the obtained product are as follows.

Dark brown solid, mp> 300 ° C.
Relative ratio of diastereomers determined by ¹ H NMR: 2/3
IR (KBr) 2952, 2784 (CH), 1760 (C = O), 1226, 1040 (OC = O), 756 (CH), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCl ₃ ) δ 1.96 (1.2H, s, CH ₃ ), 2.02, 2.03 (each 1.2H, s, CH ₃ ), 2.05 (3.6H, s, CH ₃ ), 2.07 (3H , s, CH ₃ ), 2.29 (1.8H, s, CH ₃ ), 2.74 (1.2H, s, N-CH ₃ ), 2.75 (1.8H, s, N-CH ₃ ), 3.75-3.88 (1H, m, 5'-H), 4.02-4.35 (3H, m, one of 5-H, 6'-H), 4.97 (0.6H, d, J = 8.9 Hz, 5-H), 5.04 (0.4H, d, J = 10.1 Hz, 5-H), 5.14-5.47 (4.6H, m, 1 ', 2', 3 ', 4'-H, 2-H), 5.63 (0.4H, s, 2-H ), 7.06-7.14 (1H, m, Ar-H), 7.17-7.34 (2H, m, Ar-H), 7.98-8.08 (1H, m, Ar-H).
FAB-MS (m-NBA) m / z 1200 ([M + H] ⁺ ), 720 (C ₆₀ ).
UV-VIS (CHCl ₃ ) λmax nm (log ε) 431 (3.53).
HPLC (ODS, CHCl ₃ , flow rate 1 ml / min) retention time 2.56 min.

[Example 2] Synthesis of C60 (15) having 3- (tetra-O-acetyl-β-D-glucopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, a m-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 2 was added to a dry p-xylene solution (200 ml) of C60 (288 mg, 0.4 mmol). D-glucopyranoside (3) (181 mg, 0.4 mmol) and sarcosine (37 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (502 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. C60 (98 mg, 34%) was recovered from the carbon disulfide eluate, and a black-brown solid [229 mg, 48% (72%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitation to obtain a black-brown solid (15) [223 mg, 46% (71%)]. The analysis results of the obtained product are as follows.

Brown solid, mp> 300 ° C.
Relative ratio of diastereomers determind by ¹ H NMR: 8/7
IR (KBr) 2950, 2782 (CH), 1760 (C = O), 1228, 1050 (OC = O), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCl ₃ : CS ₂ = 1: 2) δ 1.96 (3H, s, CH ₃ ), 1.97 (4.6H, s, CH ₃ ), 1.99 (1.4H, s, CH ₃ ), 2.01 (1.4H, s, CH ₃ ), 2.03 (1.6H, s, CH ₃ ), 2.78 (1.6H, s, N-CH ₃ ), 2.79 (1.4H, s, N-CH ₃ ), 4.04 ( 1H, dd, J = 2.7, 9.5 Hz, 6'-H), 4.23 (1H, d, J = 9.7 Hz, 5-H), 4.22-4.33 (1H, m, 6'-H), 4.87 (1H , s, 2-H), 4.94 (0.54H, d, J = 9.2 Hz, 5-H), 4.95 (0.46H, d, J = 9.2 Hz, 5-H), 4.96-5.24 (4H, m, 1 ', 2', 3 ', 4'-H), 6.83-6.93 (1H, m, Ar-H), 7.24-7.34 (1H, m, Ar-H), 7.35-7.59 (2H, m, Ar -H).
UV-VIS (CHCl ₃ ) λmax nm (log ε) 431 (3.59).
HPLC (ODS, CHCl ₃ , flow rate 1ml / min) retention time 2.61 min.

Example 3 Synthesis of C60 (17) having 4- (tetra-O-acetyl-β-D-glucopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, p-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 3 was added to a dry p-xylene solution (200 ml) of C60 (288 mg, 0.4 mmol). D-glucopyranoside (4) (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (533 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (135 mg, 47%) from the carbon disulfide eluate, a dark brown solid [216 mg, 45% (85%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitated to obtain a black-brown solid (17) [158 mg, 33% (76%)]. The analysis results of the obtained product are as follows.

Brown solid, mp> 300 ° C.
IR (KBr) 2950 (CH), 1758 (C = O), 1226, 1038 (OC = O), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.03, 2.04, 2.05, 2.07 (each 3H, s, CH ₃ ), 2.78 (3H, s, N-CH ₃ ), 3.89 (1H, ddd, J = 2.1, 5.5, 10.1 Hz, 5'-H), 4.16 (1H, dd, J = 2.1, 12.3 Hz, 6'-H), 4.25, 4.98 (each 1H, d, J = 9.7 Hz, 5-H), 4.26 -4.35 (1H, m, 6'-H), 4.90 (1H, s, 2-H), 5.09-5.34 (4H, m, 1 ', 2', 3 ', 4'-H), 7.05, 7.74 (each 2H, d, J = 8.9 Hz, Ar-H).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.61 (CH ₃ × 2), 20.72, 20.77 (CH ₃ ), 40.00 (N-CH ₃ ), 61.94 (6'-C), 68.25 (CH), 68.28, 68.98 (3, 4-C), 69.99 (5-C), 71.16, 72.04, 72.69 (CH), 83.00 (2-C), 98.85 (1'-C), 117.03 (2``-C), 130.60 (3``-C), 131.86, 131.95, 135.70, 135.87, 136.46, 136.91, 139.60, 139.89, 139.93, 140.20, 141.54, 141.70, 141.83, 141.94, 141.99, 142.05, 142.10 (2C), 142.14, 142.17, 142.26 (2C), 142.59 (2C), 142.71, 143.02, 143.18, 144.38, 144.42, 144.60, 144.72, 145.17, 145.24 (2C), 145.30, 145.35 (2C), 145.44, 145.50, 145.53 (2C), 145.98, 146.13, 146.16 (2C), 146.20 (2C), 146.32 (2C), 146.45, 146.65, 147.33 (2C), 153.22, 153.37, 154.00, 156.22, 156.75, 156.82 (C ₆₀ , 1``-, 4 ''- C), 169.31, 169.40, 170.24, 170.58 (C = O).
FAB-MS (m-NBA) m / z 1200 ([M + H] ⁺ ), 720 (C ₆₀ ).
UV-VIS (CHCl ₃ ) λmax nm (log ε) 431 (3.68).
HPLC (ODS, CHCl ₃ , flow rate 1ml / min) retention time 2.62 min.
Anal.Calcd for C ₈₃ H ₂₉ O ₁₀ N: C, 83.07; H, 2.44; N, 1.17%.
Found: C, 82.26; H, 2.90; N, 1.25%.

Example 4 Synthesis of C60 (19) having 2- (tetra-O-acetyl-β-D-galactopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, C60 (288 mg, 0.4 mmol) in dry p-xylene solution (200 ml) was added to o-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 4. D-galactopyranoside (6) (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (574 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (88 mg, 31%) from the carbon disulfide eluate, a black-brown solid [274 mg, 57% (82%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was dissolved by heating with benzene (4 ml), ethanol (20 ml) was added under cooling, and reprecipitation was performed to obtain a black-brown solid (19) [213 mg, 44% (64%)]. The analysis results of the obtained product are as follows.

Brown solid, mp> 300 ° C.
Relative ratio of diastereomers determind by ¹ H NMR: 3/2
IR (KBr) 2946, 2782 (CH), 1752 (C = O), 1216, 1073, 1042 (COC), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCl ₃ ) δ 1.94-2.15 (9H, m, CH ₃ ), 2.27 (1.7H, s, CH ₃ ), 2.29 (1.3H, s, CH ₃ ), 2.73 (1.3H, s, N-CH ₃ ), 2.76 (1.7H, s, N-CH ₃ ), 3.87-4.08 (2H, m, 5'-, 6'-H), 4.22 (1H, d, J = 6.8 Hz, 6'-H), 4.28 (0.6H, d, J = 9.3 Hz, 5-H), 4.29 (0.4H, d, J = 9.3 Hz, 5-H), 4.96 (0.4H, d, J = 9.3 Hz, 5-H), 4.99 (0.6H, d, J = 9.3 Hz, 5-H), 5.05-5.27 (2H, m, 1'-, 3'-H), 5.28-5.51 (2H, m, 2'-, 4'-H), 5.41 (0.6H, s, 2-H), 5.65 (0.4H, s, 2-H), 6.97-7.36 (3H, m, 4 "-, 5"-, 6 "-H), 8.02 (0.6H, dd, J = 1.7, 7.6 Hz, 3" -H), 8.06 (0.4H, dd, J = 1.7, 7.6 Hz, 3 "-H).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.61 (CH ₃ × 4), 20.81 (CH ₃ × 2), 20.92, 21.29 (CH ₃ ), 39.86 (N-CH ₃ ), 40.36 (N-CH ₃ ) , 61.02, 61.10 (6'-C), 66.67, 66.83, 68.62, 68.79, 70.64, 70.78 (2C), 71.16 (2 ', 3', 4 ', 5'-C), 69.16, 69.38 (3 or 4 -C), 69.90, 70.01 (5-C), 75.35, 75.40 (2-C), 77.23 (3 or 4-C), 97.61, 100.81 (1'-C), 113.73 (Ar-C), 118.00 ( Ar-C), 123.30 (Ar-C), 124.53 (Ar-C), 126.41 (1 "or 2" -C), 128.34 (2C) (1 "or 2" -C), 128.93 (Ar-C) , 129.16 (Ar-C), 129.25 (1 "or 2" -C), 130.11 (Ar-C), 130.73 (Ar-C), 135.18, 135.25, 136.12, 136.46 (2C), 136.49 (2C), 139.37 , 139.46, 139.75, 140.05, 140.09 (2C), 141.58, 141.63, 141.70 (2C), 141.88, 141.96, 142.06 (2C), 142.12 (2C), 142.21 (2C), 142.24 (2C), 142.46 (2C), 142.50 (2C), 142.59 (2C), 142.68, 142.87, 142.94, 143.07, 144.31 (2C), 144.47, 144.53 (3C), 145.05, 145.14 (2C), 145.19 (2C), 145.26 (2C), 145.33, 145.44 , 145.50 (2C), 145.55, 145.71 (2C), 145.87, 145.91 (2C), 146.00, 146.07 (2C), 146.16 (2C), 146.23 (2C), 146.38, 146.57, 146.61, 146. 74, 147.26 (2C), 147.46, 153.85 (2C), 154.45 (2C), 154.59 (2C), 155.33, 156.60, 156.69 (C ₆₀ -C), 168.82, 169.11, 170.06, 170.15, 170.22, 170.28, 170.35 ( C = O).
UV-VIS (CHCl ₃ ) λmax nm (log ε) 257 (5.09), 333 (4.44), 431 (3.59).
HPLC (ODS, CHCl ₃ , flow rate 1ml / min) retention time 2.59 min.

[Example 5] Synthesis of C60 (21) having 3- (tetra-O-acetyl-β-D-galactopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, m-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 5 was added to a dry p-xylene solution (200 ml) of C60 (289 mg, 0.4 mmol). D-galactopyranoside (7) (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (574 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. C60 (125 mg, 43%) was recovered from the carbon disulfide eluate, and a black-brown solid [222 mg, 46% (81%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was heated and dissolved with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitated to obtain a black-brown solid (21) [202 mg, 42% (74%)]. The analysis results of the obtained product are as follows.

Brown solid, mp> 300 ° C.
Relative ratio of diastereomers determind by ¹ H NMR: 1/1
IR (KBr) 1754 (C = O), 1218, 1075, 1046 (COC), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCl ₃ ) δ 2.01 (3H, s, CH ₃ ), 2.03 (1.5H, s, CH ₃ ), 2.05 (1.5H, s, CH ₃ ), 2.06 (1.5H, s, CH ₃ ), 2.07 (1.5H, s, CH ₃ ), 2.17 (1.5H, s, CH ₃ ), 2.18 (1.5H, s, CH ₃ ), 2.80 (1.5H, s, N-CH ₃ ), 2.81 (1.5H, s, N-CH ₃ ), 3.97-4.07 (1H, m, 5'-H), 4.10-4.23 (2H, m, 6'-H), 4.26 (1H, d, J = 9.3 Hz, 5-H), 4.91 (1H, s, 2-H), 4.97 (0.5H, d, J = 9.3 Hz, 5-H), 4.98 (0.5H, d, J = 9.3 Hz, 5-H ), 5.00 (1H, d, J = 8.0 Hz, 1'-H), 5.06 (0.5H, dd, J = 3.4, 5.5 Hz, 3'-H), 5.10 (0.5H, dd, J = 3.4, 5.5 Hz, 3'-H), 5.38-5.55 (2H, m, 2 ', 4'-H), 6.92-7.04 (1H, m, Ar-H), 7.30-7.40 (2 H, m, Ar- H), 7.40-7.81 (1H, m, Ar-H).
¹³ C NMR (67.8 MHz, CDCl ₃ ) δ 20.58 (CH ₃ × 2), 20.66 (CH ₃ × 2), 20.70 (CH ₃ × 2), 20.72, 20.86 (CH ₃ ), 39.98 (N-CH ₃ × 2), 61.31 (6'-C × 2), 66.70 (2C), 68.59, 68.62, 70.73 (2C), 71.00, 70.03 (2 ', 3', 4 ', 5'-C), 69.00 (3 or 4-C), 69.90 (5-C), 77.23 (3 or 4-C), 83.13 (2-C), 100.07 (1'-C × 2), 116.60, 118.33, 124.47, 128.32 (2C), 129.31 (2C), 129.77 (Ar-C), 135.67, 135.90, 135.94, 136.37, 136.66, 136.73, 139.06, 139.10, 139.40, 139.75, 139.84, 140.20, 141.51, 141.56, 141.69, 141.74 (2C), 141.94, 142.03 ( 2C), 142.12, 142.15, 142.21 (2C), 142.59 (2C), 142.69, 143.00, 143.18, 144.33, 144.40, 144.53, 144.58, 144.71, 145.16, 145.23, 145.26, 145.33 (2C), 145.41, 145.46, 145.50 ( 2C), 145.53, 145.66, 145.69, 145.95 (2C), 146.11, 146.16, 146.20, 146.29, 146.39, 146.63, 147.28, 147.31, 153.10, 153.19, 153.91, 156.12 (2C), 157.36 (C ₆₀ , 1``, 2``-C), 169.40, 169.43, 170.10, 170.20 (C = O).
HPLC (ODS, CHCl ₃ , flow rate 1ml / min) retention time 2.58 min.

Example 6 Synthesis of C60 (23) having 4- (tetra-O-acetyl-β-D-galactopyranosyloxy) phenyl-substituted pyrrolidine

Under a nitrogen stream, p-formylphenyl 2,3,4,6-tetra-O-acetyl-β- obtained in Synthesis Example 6 was added to a dry p-xylene solution (200 ml) of C60 (288 mg, 0.4 mmol). D-galactopyranoside (8) (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (513 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (109 mg, 38%) from the carbon disulfide eluate, a black-brown solid [427 mg, 51% (83%)] was obtained from the eluate of benzene-ethyl acetate (5: 1). Further, the black-brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitation to obtain a black-brown solid (23) [202 mg, 42% (68%)].

Brown solid, mp> 300 ° C.
IR (KBr) 1754 (C = O), 1228, 1077 (COC), 772 (CH), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz, CDCL ₃ ) δ 2.01 (3H, s, CH ₃ ), 2.05 (3H, s, CH ₃ ), 2.06 (3H, s, CH ₃ ), 2.17 (3H, s, CH ₃ ) , 2.78 (3H, s, N-CH ₃ ), 4.03-4.31 (3H, m, 5'-, 6'-H), 4.25 (1H, d, J = 9.5 Hz, 5-H), 4.90 (1H , s, 2-H), 4.98 (1H, d, J = 9.5 Hz, 5-H), 5.05-5.17 (2H, m, 1'-, 3'-H), 5.42-5.54 (2H, m, 2'-, 4'-H), 7.06 (2H, d, J = 8.9 Hz, Ar-H), 7.74 (2H, d, J = 7.2 Hz, Ar-H).
HPLC (ODS, CHCl ₃ , flow rate 1.00ml / min) retention time 2.58min.

[Example 7] Synthesis of C60 (25) having 2,4-bis (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -substituted pyrrolidine

  Under a nitrogen stream, the precursor (9) (319 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) obtained in Synthesis Example 7 were added to a dry p-xylene solution (200 ml) of C60 (288 mg, 0.4 mmol). ) And heated to reflux for 8 hours while removing water using a Dean-Stark trap. A black-brown solid (704 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. C60 (95 mg, 33%) was recovered from the carbon disulfide eluate, and a black-brown solid [326 mg, 53% (79%)] was obtained from the benzene-ethyl acetate (5: 2) eluate. The black-brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitation to obtain a brown solid (25) [292 mg, 47% (70%), mp 192-194 ° C.]. It was. The analysis results of the obtained product are as follows.

Relative ration of diastereomers determind by ¹ H NMR: 1/1
Brown solid, mp 192-194 ° C.
IR (KBr) 2948, 2940, 2784 (CH), 1758 (C = O), 1222, 1040 (OC = O), 905 (CH), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz CDCl ₃ ) δ 1.94 (1.5H, s, CH ₃ ), 2.02 (1.5H, s, CH ₃ ), 2.03 (1.5H, s, CH ₃ ), 2.03 (3H, s, CH ₃ ), 2.04 (3H, s, CH ₃ ), 2.05 (1.5H, s, CH ₃ ), 2.06 (4.5H, s, CH ₃ ), 2.07 (1.5H, s, CH ₃ ), 2.08 (3H, s, CH ₃ ), 2.10 (1.5H, s, CH ₃ ), 2.25 (1.5H, s, CH ₃ ), 2.70 (3H, s, N-CH ₃ ), 3.79-3.99 (2H, m, 6 ' -H), 4.08 (1H, ddd, J = 2.7, 9.8, 12.5 Hz, 5'-H), 4.16 (1H, dd, J = 9.8, 12.5 Hz, 5'-H), 4.20-4.41 (3H, m, 5, 6'-H), 4.96 (0.5H, d, J = 9.5 Hz, 5-H), 4.99 (0.5H, d, J = 9.5 Hz, 5-H), 4.91-5.49 (8.5H , m, 2, 1 ', 2', 3 ', 4'-H), 5.53 (0.5H, s, 2-H), 6.72 (0.5H, d, J = 2.3 Hz, 3``-H) , 6.75 (0.5H, d, J = 2.3 Hz, 3``-H), 6.81 (0.5H, dd, J = 2.3, 8.6 Hz, 5``-H), 6.87 (0.5H, dd, J = 2.3, 8.6 Hz, 5``-H), 7.92 (0.5H, d, J = 8.6 Hz, 6 ''-H), 7.96 (0.5H, d, J = 8.6 Hz, 6``-H).
FAB-MS (m-NBA) m / z 1545 ([M] ⁺ ) 720 (C ₆₀ ).
HPLC (ODS, CHCl ₃ , flow rate 1.00 ml / min) retention time 2.42 min.

[Example 8] Synthesis of C60 (27) having 3,5-bis (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -substituted pyrrolidine

  Under a nitrogen stream, C60 (288 mg, 0.4 mmol) in a dry p-xylene solution (200 ml) was mixed with the precursor (10) obtained in Synthesis Example 8 (319 mg, 0.4 mmol) and sarcosine (35 mg, 0.4 mmol). ) And heated to reflux for 8 hours while removing water using a Dean-Stark trap. A black-brown solid (731 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (99 mg, 34%) from the carbon disulfide eluate, a black-brown solid [327 mg, 53% (80%)] was obtained from the eluate of benzene-ethyl acetate (5: 2). The black brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitation to obtain a brown solid (27) [278 mg, 45% (68%), mp 255-257 ° C.]. It was. The analysis results of the obtained product are as follows.

Relative ration of diastereomers determind by ¹ H NMR: 1/1
Brown solid, mp 255-257 ° C.
IR (KBr) 2950, 2784 (CH), 1760 (C = O), 1220, 1040 (OC = O), 907 (CH), 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz CDCl ₃ ) δ 2.03 (6H, s, CH ₃ ), 2.03 (9H, s, CH ₃ ), 2.06 (4.5H, s, CH ₃ ), 2.08 (1.5H, s, CH ₃ ), 2.10 (3H, s, CH ₃ ), 2.80 (1.5H, s, N-CH ₃ ), 2.80 (1.5H, s, N-CH ₃ ), 3.78-4.91 (2H, m, 5'-H ), 4.12 (2H, dd, J = 2.3, 9.6 Hz, 6'-H), 4.26 (2H, dd, J = 2.3, 9.6 Hz, 6'-H), 4.26-4.41 (1H, m, 5- H), 4.85 (0.5H, s, 2-H), 4.86 (0.5H, s, 2-H), 4.96 (0.5H, d, J = 9.6 Hz, 5-H), 4.97 (0.5H, d , J = 9.6 Hz, 5-H), 5.01-5.47 (8H, m, 1 ', 2', 3 ', 4'-H), 6.58 (0.5H, t, J = 2.3 Hz, 4``- H), 6.64 (0.5H, t, J = 2.3 Hz, 4``-H), 7.26 (2H, s, 2 '', 6 ''-H).
FAB-MS (m-NBA) m / z 1546 ([M + H] ⁺ ) 720 (C ₆₀ ).
HPLC (ODS, CHCl ₃ , flow rate 1.00 ml / min) retention time 2.41 min.

[Example 9] Synthesis of C60 (29) having 2,4,6-tris (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -substituted pyrrolidine

  Under a nitrogen stream, the precursor (11) (344 mg, 0.3 mmol) and sarcosine (27 mg, 0.3 mmol) obtained in Synthesis Example 9 were added to a dry p-xylene solution (200 ml) of C60 (216 mg, 0.3 mmol). ) And heated to reflux for 8 hours while removing water using a Dean-Stark trap. A black-brown solid (621 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to column chromatography. After recovering C60 (60 mg, 28%) from the carbon disulfide eluate, a black-brown solid [346 mg, 61% (85%)] was obtained from the eluate of benzene-ethyl acetate (1: 1). The black-brown solid was dissolved by heating with benzene (4 ml), and ethanol (20 ml) was added under cooling and reprecipitated to obtain a brown solid (29) [235 mg, 41% (57%), mp174-176 ° C.]. It was. The analysis results of the obtained product are as follows.

Relative ration of diastereomers determind by ¹ H NMR: 8/7
Brown solid, mp 174-176 ℃.
IR (KBr) 2950, 2780 (CH), 1758 (C = O), 1609, (C = C), 1220, 1040 (OC = O), 907 (CH) 526 cm ^-1 (C ₆₀ ).
¹ H NMR (270 MHz CDCl ₃ ) δ 1.95 (1.4H, s, CH ₃ ), 1.96 (1.6H, s, CH ₃ ), 2.01 (1.6H, s, CH ₃ ), 2.02 (3.2H, s, _{CH 3), 2.03 (4.6H,} s, CH 3), 2.04 (3H, s, CH 3), 2.05 (3.2H, s, CH 3), 2.07 (4.4H, s, CH 3), 2.08 (3H , s, CH ₃ ), 2.08 (2.8H, s, CH ₃ ), 2.10 (4.4H, s, CH ₃ ), 2.19 (1.4H, s, CH ₃ ), 2.25 (1.4H, s, CH ₃ ) , 2.59 (1.6H, s, N-CH ₃ ), 2.73 (1.4H, s, N-CH ₃ ), 3.81-4.47 (10H, m, 5, 5 ', 6'-H), 4.79-5.73 ( 14H, m, 2, 5, 1 ', 2', 3 ', 4'-H), 6.34 (0.5H, d, J = 2.1 Hz, Ar-H), 6.37 (0.5H, d, J = 2.1 Hz, Ar-H), 6.40 (0.5H, d, J = 2.1 Hz, Ar-H), 6.50 (0.5H, d, J = 2.1 Hz, Ar-H).
FAB-MS (m-NBA) m / z 1892 ([M + H] ⁺ ) 720 (C ₆₀ ).
HPLC (ODS, CHCl ₃ , flow rate 1.00 ml / min) retention time 2.37 min.

[2] Solubility test of C60 derivative [Comparative Example 1]
10 mg of PCBM was measured, dichloroethane (hereinafter referred to as DCE) was added thereto, and the concentration (mass%) when dissolved was calculated. In PCBM, even when 0.99 g (1% by mass solution) of DCE was added, it could not be completely dissolved.

[Example 10]
A solubility test was performed in the same manner as in Comparative Example 1 except that the C60 compound (13) obtained in Example 1 was used. As a result, it was completely dissolved when 0.2033 g of DCE was added. The concentration at this time was calculated to be 4.69% by mass.

[Example 11]
A solubility test was performed in the same manner as in Comparative Example 1 except that the C60 compound (19) obtained in Example 4 was used. As a result, when 0.4083 g of DCE was added, all dissolved. The concentration at this time was calculated to be 2.39% by mass.
The results of Comparative Example 1 and Examples 10 and 11 are summarized in Table 1 below. As shown in Table 1, it can be seen that the C60 compound having a monosaccharide residue has very good solubility in an organic solvent as compared with PCBM.

[3] Evaluation of film formation surface of C60 derivative [Comparative Example 2]
DCE was added to PCBM to prepare a 0.01 g / ml varnish. After passing this varnish through a 0.2 μm filter, a PCBM film was formed on the ITO substrate by a spin coating method (1000 rpm, 20 sec.), And then baked at 100 ° C. for 1 hour to produce a thin film.
About the obtained thin film, the film-forming surface was observed using a confocal laser microscope (The laser tech company make, real-time scanning laser microscope, 1LM21D), and a scanning probe microscope (SII Nano Technology company make, Nano Navi L-trace II). Were used to evaluate the surface roughness and the shape of the film. FIG. 1 shows a confocal laser micrograph of the PCBM deposition surface, FIG. 2 shows the result of the PCBM two-dimensional deposition surface, and FIG. 3 shows the result of the PCBM three-dimensional deposition surface.
As shown in FIG. 1, it was confirmed that aggregates were formed in the PCBM thin film. Moreover, it was 216.2 nm when the surface roughness at this time was measured by AFM. As shown in FIGS. 2 and 3, it was confirmed that the unevenness of the aggregate was considerably large on the film surface.

[Example 12]
DCE was added to the C60 compound (13) obtained in Example 1 to prepare a 0.01 g / ml varnish. Using this varnish, a thin film was produced under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness 40.3 nm). FIG. 4 shows a confocal laser micrograph of the film formation surface, FIG. 5 shows the result of the two-dimensional film formation surface, and FIG. 6 shows the result of the three-dimensional film formation surface.
As shown in FIG. 4, no agglomerates as observed in Comparative Example 1 were observed in the micrograph. Moreover, it was 3.66 nm when the average surface roughness at this time was measured by AFM. As shown in FIGS. 5 and 6, unevenness was observed on the film surface, but it can be seen that it is considerably smaller than that of Comparative Example 1. This unevenness is considered to be an unevenness formed by moisture in the air being dried on the film surface during firing. From these results, it became clear that a film better than PCBM can be obtained by using C60 compound (13).

[Example 13]
DCE was added to the C60 compound (13) obtained in Example 1 to prepare a 0.01 g / ml varnish. The varnish was passed through a 0.2 μm filter, and then formed on an ITO substrate by spin coating (1000 rpm, 20 sec.) In a glove box (in a nitrogen atmosphere). Then, it baked at 100 degreeC in the vacuum for 1 hour, and produced the thin film (film thickness 39.0 nm). About the obtained thin film, surface roughness and the shape of the film were evaluated. The result of the two-dimensional film formation surface is shown in FIG. 7, and the result of the three-dimensional film formation surface is shown in FIG. As shown in FIGS. 7 and 8, it was clarified that by performing baking in a vacuum, the unevenness disappears because it is not affected by moisture, and a thin film having a better film formation surface can be obtained. . Moreover, it was 0.63 nm when the average surface roughness at this time was measured by AFM.

[Example 14]
DCE was added to the C60 compound (19) obtained in Example 4 to prepare a varnish of 0.01 g / ml. Using this varnish, a thin film was produced under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness 43.0 nm). FIG. 9 shows a confocal laser micrograph of the film formation surface, FIG. 10 shows the result of the two-dimensional film formation surface, and FIG. 11 shows the result of the three-dimensional film formation surface.
9-11, it turns out that the thin film of the surface property similar to Example 12 is obtained. Moreover, it was 7.84 nm when the average surface roughness at this time was measured by AFM.

[Example 15]
DCE was added to the C60 compound (19) obtained in Example 4 to prepare a varnish of 0.01 g / ml. The varnish was passed through a 0.2 μm filter, and then formed on an ITO substrate by spin coating (1000 rpm, 20 sec.) In a glove box (in a nitrogen atmosphere). Then, it baked at 100 degreeC for 1 hour in the vacuum, and produced the thin film (film thickness 42.9 nm). About the obtained thin film, surface roughness and the shape of the film were evaluated. The result of the two-dimensional film formation surface is shown in FIG. 12, and the result of the three-dimensional film formation surface is shown in FIG. As shown in FIGS. 12 and 13, it was clarified that by performing baking in a vacuum, the unevenness disappears because of not being affected by moisture, and a thin film having a better film formation surface can be obtained. . Moreover, it was 1.28 nm when the average surface roughness at this time was measured by AFM.

[Example 16]
DCE was added to the C60 compound (25) obtained in Example 7 to prepare a 1% by mass varnish. Using this varnish, a thin film was produced under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness 68.6 nm). FIG. 14 shows the result of the two-dimensional film formation surface, and FIG. 15 shows the result of the three-dimensional film formation surface.
As shown in FIGS. 14 and 15, it can be seen that a thin film having the same surface property as that of Example 12 was obtained. Moreover, it was 2.75 nm when the average surface roughness at this time was measured by AFM.

[Example 17]
DCE was added to the C60 compound (27) obtained in Example 8 to prepare a 1% by mass varnish. Using this varnish, a thin film was produced under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness 72.1 nm). The result of the two-dimensional film formation surface is shown in FIG. 16, and the result of the three-dimensional film formation surface is shown in FIG.
As shown in FIGS. 16 and 17, it can be seen that a thin film having the same surface property as that of Example 12 was obtained. Moreover, it was 25.3 nm when the average surface roughness at this time was measured by AFM.

[Example 18]
DCE was added to the C60 compound (29) obtained in Example 9 to prepare a 1% by mass varnish. Using this varnish, a thin film was produced under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness 72.1 nm). FIG. 18 shows the result of the two-dimensional film formation surface, and FIG. 19 shows the result of the three-dimensional film formation surface.
As shown in FIGS. 18 and 19, it can be seen that a thin film having the same surface property as that of Example 12 was obtained. Moreover, it was 5.53 nm when the average surface roughness at this time was measured by AFM.

  Table 2 shows the average surface roughness of the thin films obtained in Comparative Example 2 and Examples 12-18. As shown in Table 2, it is clear that by using C60 compounds (13), (19), (25), (27), (29), a thin film having a better film-forming surface than PCBM can be obtained. It became. It can also be seen that by baking in vacuum, unevenness due to moisture can be prevented, and the film can be formed more smoothly.

[4] Measurement of mobility [Example 19]
As the substrate, a silicon substrate with a thermal oxide film having a thickness of 300 nm was used. A comb-shaped gold electrode having a channel length L = 25 μm and a channel width W = 76 mm was used as the gate electrode. The SiO ₂ surface was subjected to hexamethyldisilazane (HMDS) treatment.
The C60 compound (19) obtained in Example 4 was dissolved in dichloromethane, and 0.02 g / ml varnish was prepared in the atmosphere. This varnish was dropped on the substrate through a filter of Φ = 0.2 μm in a glove box, and spin coated at 1500 rpm for 20 seconds. The n-type organic semiconductor layer was formed by drying for 1 hour on a hot plate at 100 ° C. as it was.
The measurement chamber was brought into a glove box, the FET was charged so as not to be exposed to the atmosphere, and immediately vacuumed to evaluate the transistor characteristics. The evaluation results are shown in FIG.
In general, the drain current _ID in the saturated state can be expressed by the following formula. That is, the mobility μ of the organic semiconductor can be obtained from the slope of the graph when the square root of the absolute value of the drain current I _D is plotted on the vertical axis and the gate voltage V _G is plotted on the horizontal axis.
I _D = WCμ (V _G −V _T ) ² / 2L
In the above equation, W is the channel width of the transistor, L is the channel length of the transistor, C is the capacitance of the gate insulating film, V _T is the threshold voltage of the transistor, and μ is the mobility. When the mobility μ of the C60 compound (19) was calculated based on this formula, it was 5.00 × 10 ⁻⁴ cm ² / Vs. The threshold voltage and the on / off ratio were 13.6 V and 10 ⁵ to 10 ⁶ , respectively. Thus, it was revealed that the C60 compound (19) having a smooth film surface is driven as an n-type semiconductor.

[Example 20]
As the substrate, a silicon substrate with a thermal oxide film having a thickness of 300 nm was used. A comb-shaped gold electrode having a channel length L = 25 μm and a channel width W = 76 mm was used as the gate electrode. The SiO ₂ surface was used untreated.
The C60 compound (13) obtained in Example 1 was dissolved in dichloromethane, and 0.02 g / ml varnish was prepared in the air. This varnish was dropped on the substrate through a filter of Φ = 0.2 μm in a glove box, and spin coated at 1500 rpm for 20 seconds. The n-type organic semiconductor layer was formed by drying for 1 hour on a hot plate at 100 ° C. as it was.
The measurement chamber was brought into a glove box, the FET was charged so as not to be exposed to the atmosphere, and immediately vacuumed to evaluate the transistor characteristics. The evaluation results are shown in FIG. When the electron mobility of the C60 compound (13) was calculated based on the above formula, 6.73 × 10 ⁻⁴ cm ² / Vs, the threshold voltage, and the on / off ratio were 38.4 V, 10 ⁵ ˜, respectively. 10 ⁶ . Thus, it became clear that the C60 compound (13) having a smooth film surface is driven as an n-type semiconductor.

Claims (12)

An n-type semiconductor comprising a fullerene compound represented by the following formula (1).

[Wherein, R ^{1 to} R ⁵ each independently represents a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or a sugar alcohol residue) group, and R ⁶ represents a carbon number of 1 to 5 represents an alkyl group. However, at least one of R ^{1 to} R ⁵ is the OR ⁷ group. ]   The n-type semiconductor according to claim 1, wherein the monosaccharide residue is a tetrose residue, a pentose residue or a hexose residue.   The monosaccharide residue or sugar alcohol residue is an allosyl group, arabinosyl group, erythrosyl group, fructosyl group, galactosyl group, glucosyl group, grosyl group, inositol residue, lysosyl group, mannosyl group, ribosyl group, sialic acid residue The n-type semiconductor according to claim 1, which is a sorbosyl group, a tagarosyl group, a tarosyl group or a xylosyl group.   The n-type semiconductor according to any one of claims 1 to 3, wherein at least one of hydroxyl groups of the monosaccharide residue or sugar alcohol residue is protected with a protecting group.   The protective group is an alkyl group, benzyl group, p-methoxybenzyl group, t-butyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl group, triethyl. The n-type semiconductor according to claim 4, which is a silyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, or a t-butyldiphenylsilyl group.   A varnish comprising the n-type semiconductor according to any one of claims 1 to 5 and an organic solvent, wherein the n-type semiconductor is dissolved in the organic solvent.   An n-type organic semiconductor thin film obtained from the varnish according to claim 6.   The n-type organic-semiconductor thin film containing the n-type semiconductor of any one of Claims 1-5.   An organic semiconductor element provided with the n-type organic semiconductor thin film of Claim 7 or 8.   A field effect transistor comprising the n-type organic semiconductor thin film according to claim 7 or 8.   An organic thin film solar cell comprising the n-type organic semiconductor thin film according to claim 7 or 8. A fullerene compound represented by the following formula (2).

[Wherein, R ^{1 to} R ⁵ each independently represents a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or a sugar alcohol residue) group, and R ⁶ represents a carbon number of 1 to 5 represents an alkyl group. However, at least two of R ^{1 to} R ⁵ are the OR ⁷ group. ]

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