TWI477489B - An n-type semiconductor composed of a fullerene compound - Google Patents

Description

An n-type semiconductor composed of a fullerene compound

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

It is known that fullerene (hereinafter referred to as "C60") having a soccer-like structure of 60 carbon atoms is a compound which exhibits particularly excellent characteristics among n-type semiconductor materials, in an ultra-high vacuum. When a film is formed by a vapor deposition method, a film which exhibits an electron mobility similar to that of the amorphous germanium can be obtained (see Non-Patent Document 1).

However, since the film composed of C60 is required to be formed by a vapor deposition method, it is difficult to cope with a large area, and even if it is required to have a large manufacturing cost, it is highly likely.

Therefore, development of a material that can form a film using a coating method that does not increase the manufacturing cost and increase the ratio of the production area is required.

So far, [6,6]-Phenyl C61-butyric acid methyl ester (hereinafter referred to as "PCBM") which has introduced a C60 derivative into which a substituent has been introduced, or C60 which introduces a fluorinated alkyl group, and has been reported It is understood that an organic FET can be produced by a spin coating method by using such a material (see Patent Document 1 and Non-Patent Document 2).

Further, C60-fused N-methylpyrrolidine-meta-C12 phenyl (C60MC12) which has been developed as a C60 derivative in which a long-chain alkyl group has been introduced has been reported, and it has been reported that the crystallinity of the obtained film is improved by using this material, and the result is improved. The electron mobility (0.067 cm ² /Vs) higher than the PCBM is displayed (refer to Patent Document 2 and Non-Patent Document 3).

As described above, an n-type semiconductor film using a soluble fullerene compound has been developed in recent years, and its characteristics are gradually improved. However, when it is seen as a film, there is a problem that partial aggregation is low and uniformity occurs.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2007-251086

[Patent Document 2] JP-A-2006-60169

[Non-patent literature]

[Non-Patent Document 1] Applied Physics Letters, Vol. 82, No. 25, p4581-p4583, (2003)

[Non-Patent Document 2] Advanced Materials, Vol. 15, No. 24, p2084-p2088, (2003)

[Non-Patent Document 3] Applied Physics Letters, Vol. 87, p153506-1-p153506-3, (2005)

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an n-type semiconductor material which can impart a uniform film and is soluble in an organic solvent.

The inventors of the present invention conducted repeated evaluations to achieve the above object, and found that the fullerene compound having a monosaccharide residue or a sugar alcohol residue has good solubility in an organic solvent, and a film obtained from a varnish containing the compound. The uniformity is good, and it has been found that it can be driven as an n-type semiconductor to complete the present invention.

That is, the present invention provides

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

【化1】

[wherein, 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) group, and R ⁶ represents an alkyl group having 1 to 5 carbon atoms. However, at least one of R ¹ to R ⁵ is the aforementioned OR ⁷ group].

2. An n-type semiconductor according to 1, wherein the aforementioned monosaccharide residue is a butyral residue, a pentose residue or a hexose residue;

3. The n-type semiconductor according to 1, wherein the monosaccharide residue or the sugar alcohol residue is an allosyl group, an arabinose group, a erythrosyl group, a fructosyl group, a galactosyl group, a glycosyl group, a gulose group, Inositol residue, lysyl, mannosyl, ribose, sialic acid residue, sorbitan, logerone, talose or xylosyl;

4. The n-type semiconductor according to any one of 1 to 3, wherein at least one of the hydroxyl groups of the aforementioned monosaccharide residue or sugar alcohol residue is protected by a protecting group;

5. An n-type semiconductor according to 4, wherein the aforementioned protecting group is an alkyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a methoxymethyl group, a 2-tetrahydropyranyl group, an ethoxy group. Ethyl, ethenyl, trimethylethenyl, benzindenyl, trimethyldecyl, triethyldecyl, t-butyldimethylalkyl, triisopropyldecyl, or t- Butyl diphenyl fluorenyl

A varnish characterized by containing the n-type semiconductor according to any one of 1 to 5 and an organic solvent, and the n-type semiconductor is dissolved in an organic solvent;

7. An n-type organic semiconductor film characterized by being obtained from a varnish of 6;

An n-type organic semiconductor thin film characterized by containing the n-type semiconductor according to any one of 1 to 5;

An organic semiconductor device characterized by comprising an n-type organic semiconductor thin film such as 7 or 8;

10. A field effect transistor characterized by having an n-type organic semiconductor film of 7 or 8;

An organic thin film solar cell characterized by having an n-type organic semiconductor thin film of 7 or 8;

12. A fullerene compound represented by the following formula (2),

[Chemical 2]

[wherein, 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) group, and R ⁶ represents an alkyl group having 1 to 5 carbon atoms. However, at least two of R ¹ to R ⁵ are the aforementioned OR ⁷ groups].

The n-type semiconductor of the present invention has a good solubility in an organic solvent, and can be formed into a thin film by a solution process such as a coating method.

Therefore, in addition to the large area of the semiconductor element, it is easy to reduce the manufacturing cost.

Further, since the film obtained by using the n-type semiconductor of the present invention has no aggregation and is excellent in uniformity, the characteristics of the element having the film are excellent.

Hereinafter, the present invention will be described in more detail.

In the n-type semiconductor of the present invention, as shown by the following formula (1), at least one monosaccharide residue or sugar alcohol residue is added to the ortho position of the phenyl group to the C60 compound having a phenyl-substituted pyrrolidine skeleton. And the compound of the alignment.

[化3]

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) group, and at least one of R ¹ to R ⁵ is an OR ⁷ group. .

The monosaccharide residue is not particularly limited. In the present invention, a butyral residue, a pentose residue, and a hexose residue are preferred, and a hexose residue is particularly preferred.

Examples of the butyric residue include an erythrosyl group of an erythrosyl residue.

Examples of the pentose residue include an arabinose group of an arabinose residue, a lysyl group of a threose residue, a ribose group of a ribose residue, and a xylosyl group of a xylose residue.

Examples of the hexose residue include an allose group of an arabose residue, a fructosyl group of a fructosyl residue, a galactosyl group of a galactose residue, a glucosyl group of a glucose residue, and an ancient sugar residue. A mannose group of a glucosyl group, a mannose residue, a logerone glycosyl group of a logerone sugar residue, a talose group of a talose residue, a sialic acid residue, and the like.

Examples of the sugar alcohol residue include inositol residues and the like.

Among these, in the present invention, a hexose residue is preferred, and a galactosyl group or a glucosyl group is particularly preferred.

Further, R ⁶ is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group. , n-pentyl, etc., especially methyl is preferred.

Further, in consideration of further improving the solubility of the n-type semiconductor of the present invention in an organic solvent, it is preferred that at least one of the hydroxyl groups of the monosaccharide residue or the sugar alcohol residue is protected by a protective group, and all of the hydroxyl groups are preferred. It is better to protect with a protective base.

In this case, the protecting group is not particularly limited as long as it is appropriately selected from the protective groups used for the protection of the general sugar hydroxyl group.

Specific examples thereof include an alkyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a methoxymethyl group, a 2-tetrahydropyranyl group, an ethoxyethyl group, an ethyl sulfonyl group, and a third group. a methyl ethyl fluorenyl group, a benzamidine group, a trimethyl decyl group, a triethyl decyl group, a t-butyl dimethyl decyl group, a triisopropyl decyl group, a t-butyl diphenyl fluorenyl group, or the like. In particular, it is preferred to use an acetamidine group.

The C60 compound represented by the above formula (1) can be disclosed according to "Synthesis and Electrochemical Characteristics of Water-Soluble Fullerene Derivatives Containing Sugar Units" (March 81 Annual Meeting of the Chemical Society of Japan, March 2002) A method for synthesizing a C60 compound having a monosaccharide residue is synthesized. If an example is given, it is as follows.

【化4】

【化5】

The varnish of the present invention contains the above-mentioned C60 compound and an organic solvent, and the C60 compound is dissolved in an organic solvent.

Here, the organic solvent is not particularly limited as long as it has a dissolving ability of the C60 compound, and examples thereof include benzene, toluene, hydrazine, chlorobenzene, diethyl ether, tetrahydrofuran, dioxane, acetone, ethyl acetate, and carbon disulfide. , dichloroethane, chloroform, dichloromethane, etc.

The content of the C60 compound in the varnish is not particularly limited as long as it is soluble in the organic solvent, and it is preferably 0.01 to 20% by mass, and 0.5 to 3% by mass, in consideration of workability such as coatability. good.

An n-type organic semiconductor thin film can be formed on a substrate by applying the above-described varnish to a substrate and evaporating the solvent.

The coating method of 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 inkjet method, and a spray coating method.

The evaporation method of the solvent is not particularly limited. For example, a hot plate or an oven may be used, and the solvent may be evaporated under an appropriate environment, that is, an inert gas such as air or nitrogen or a vacuum.

The firing temperature is not particularly limited as long as the solvent is used, and it is preferably carried out at 80 to 100 ° C.

The film thickness of the semiconductor thin film is not particularly limited, and is preferably 50 to 100 nm. The method of changing the film thickness includes a method of changing the solid content concentration in the varnish, changing the amount of the solution on the substrate during coating, and the like.

By using the varnish of the present invention, it is possible to produce a film in a simple manner as compared with the method of a solution process such as a non-evaporation method, and it is also advantageous in that it can easily correspond to a large area.

Further, the method for forming the film containing the n-type semiconductor of the present invention is not limited to the solution process using the above coating method, and other conventionally known methods such as a vapor deposition method may be used.

The above-described n-type organic semiconductor thin film can be suitably used as a semiconductor layer which constitutes a semiconductor element such as a field effect transistor, a light emitting diode, a photoelectric conversion element, or an organic thin film solar cell.

The semiconductor device of the present invention is characterized in that the above-described fullerene compound having a monosaccharide residue or a sugar alcohol residue is used as an n-type semiconductor, and the constituent members of the other elements are appropriately selected from those conventionally known. .

An example is given regarding a field effect transistor.

Field effect transistors generally include a substrate, a gate electrode, a gate insulator film, a source electrode, a drain electrode, and an n-type organic semiconductor layer. In the configuration, the n-type organic semiconductor thin film described above is used as the n-type organic semiconductor layer.

The gate electrode, the gate insulating film, the source, the drain, and the n-type organic semiconductor layer are disposed on the substrate in the form of a gate electrode and a gate insulating film, and the n-type organic semiconductor film is laminated on the substrate, and the substrate In the various forms of the form of the upper layer and the source of the drain, any of the forms can be used in the present invention.

Examples of the substrate include a ruthenium substrate, a glass substrate, and a plastic substrate such as polyethylene terephthalate.

Examples of the material constituting the gate include a conductive polymer such as p-doped germanium, n-doped germanium, indium ‧ tin oxide (ITO), doped polythiophene or polyaniline, gold, silver, and platinum. , metals such as chrome, etc.

Examples of the material constituting the gate insulating film include inorganic compounds such as cerium oxide, cerium nitride, aluminum oxide, aluminum nitride, and cerium oxide, polyvinyl alcohol, polyvinyl phenol, polymethacrylate, and cyanoethylpullulan. Organic compound.

Examples of the material constituting the source and the drain include gold, silver, platinum, chromium, aluminum, indium, alkali metals (Li, Na, K, Rb, and Cs), and alkaline earth metals (Mg, Ca, Sr, and Ba). )Wait.

[Examples]

Hereinafter, the present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the examples described below. Further, the analysis device used in the examples was as follows.

(1) Melting point: micro-melting point measuring device (manufactured by the company, Miyamoto Manufacturing Co., Ltd., MP-S3)

(2) NMR: superconducting nuclear magnetic resonance device (made by JEOL Co., Ltd., JNM-EX270 and JNM-ECS 400)

(3) IR: Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, JASCO FT/IR-7000)

(4) MS: mass spectrometer (manufactured by JEOL Ltd., JMS-AX500, and BRUKER, autoflex II MALDI TOF/TOF MS)

(5) Optical rotation: Optical rotation meter (manufactured by JASCO Corporation, DIP-1000 type)

(6) UV-VIS spectrophotometer: UV-visible spectrophotometer (manufactured by Hitachi, Ltd., U-2000-shaped Hitachi dual-beam spectrophotometer)

(7) HPLC: High-speed liquid chromatography device (manufactured by Hitachi, Ltd., L-6000 Hitachi High-Speed Liquid Chromatograph)

[Synthesis Example 1] Synthesis of 2-formylphenyltetra-O-ethylidene-β-D-glucopyranoside (2)

【化6】

4-O-Ethyl-α-D-bromoglucopyranose (1) (822 mg, 2.0) was added to a quinoline solution (2.0 ml) of o-hydroxybenzaldehyde (124 mg, 1.0 mmol) under nitrogen atmosphere. Methyl) and silver oxide (463 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration.

Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield brown oil (780 mg).

The residue was attached to a column chromatography analyzer (BW-300, manufactured by Fuji Silysia Chemical Co., Ltd., the same below), and separated by hexane-ethyl acetate (3:2) to obtain a colorless viscous oil (660 mg). ). This was recrystallized from ethanol to give colorless needle crystals (2) (400 mg, 88%). The analysis result of the obtained product was as follows. 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 (270MHz, 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=8.4Hz, 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] ⁺ ).

[Number 1]

-32.9 (c 1.03, CHCl ₃ ). 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-methylphenylphenyltetra-O-ethylidene-β-D-glucopyranoside (3)

【化7】

2,3,4,6-tetra-O-ethinyl-α-D-bromoglucopyranose was added to m-hydroxybenzaldehyde (123 mg, 1.0 mmol) in quinoline solution (2.0 ml) under a nitrogen stream. (1) (822 mg, 2.0 mmol) and silver oxide (463 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration.

Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield yellow oil (yield: 764).

The residue was subjected to a column chromatography, and separated by hexane-ethyl acetate (3:2) to give a colorless viscous oil (493 mg). This was recrystallized from ethanol to give colorless crystals (3) (436 mg, 96%). The analysis results of the obtained product were as follows. Colorless needles (Ethanol), mp 105-106 ° C. (lit. mp 108-109 ° C) 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).

[Number 2]

-36.9 (c 1.00, CHCl ₃ ). 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-methylnonylphenyltetra-O-ethylidene-β-D-glucopyranoside (4)

【化8】

2,3,4,6-tetra-O-ethenyl-α-D-bromoglucopyranose was added to p-hydroxybenzaldehyde (123 mg, 1.0 mmol) in quinoline solution (2.0 ml) under a nitrogen stream. (1) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration.

Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a pale oil.

The residue was subjected to a column chromatography to give a colorless viscous oil (417 mg) eluting with hexane-ethyl acetate (3:2). This was recrystallized from ethanol to give colorless needle crystals (4) (375 mg, 83%). The analysis results of the obtained product were as follows. Colorless needles (Ethanol), mp 147-148 ° C. (lit. mp 149-150 ° C) IR (KBr) 1754, 1694 (C=O), 1236, 1056 cm ^-1 (OC=O). ¹ H NMR (270 MHz , CDCl ₃ ) δ2.05 (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; , 5.37%

[Synthesis Example 4] Synthesis of 2-methylmercaptophenyltetra-O-ethinyl-β-D-galactopyranoside (6)

【化9】

2,3,4,6-tetra-O-ethylindenyl-α-D-bromopentahydrate was added to a quinoline solution (2.0 ml) of o-hydroxybenzaldehyde (124 mg, 1.0 mmol) under a nitrogen stream. Sugar (galactopyranosylbromide) (5) (822 mg, 2.0 mmol) and silver oxide (463 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration.

Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield white oil (yield: 747 mg).

The residue was subjected to a column chromatography, and was separated by hexane-ethyl acetate (3:2) to give a colorless viscous oil (652 mg). This was recrystallized from hexane-diethyl ether (7:2) to give colorless crystals (6) (454 mg, 98%). The analysis results of the obtained product were as follows. 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 (270MHz, CDCl ₃ ) δ 2.03 (3H, s, CH ₃ ), 2.07 (6H, s, CH ₃ ), 2.21. 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] ⁺ ).

[Number 3]

-12.4 (c 1.00, CHCl ₃ ). 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-methylnonylphenyltetra-O-ethylidene-β-D-galactosylpyrene (7)

【化10】

2,3,4,6-tetra-O-ethylindenyl-α-D-bromopentamethylene bromide was added to a quinoline solution (2.0 ml) of m-hydroxybenzaldehyde (122 mg, 1.0 mmol) under a nitrogen stream. Sugar (5) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration.

Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield yellow oil (yield: 751 mg).

The residue was subjected to a column chromatography, and separated by hexane-ethyl acetate (3:2) to give a colorless viscous oil (445 mg). This was recrystallized from hexane-diethyl ether (7:2) to give colorless crystals (7) (381 mg, 85%). The analysis results of the obtained product were as follows. 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 (270MHz, 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).

[Number 4]

-11.2 (c 1.00, CHCl ₃ ). 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-methylnonylphenyltetra-O-ethylidene-β-D-galactosylpyrene (8)

【化11】

2,3,4,6-tetra-O-ethylindolyl-α-D-bromopentalin was added to a quinoline solution (2.0 ml) of p-hydroxybenzaldehyde (123 mg, 1.0 mmol) under a nitrogen stream. Sugar (5) (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield yellow oil (725 mg). The residue was subjected to a column chromatography to give a colorless viscous oil (436 mg) eluting with hexane-ethyl acetate (3:2). This was recrystallized from hexane-diethyl ether (7:2) to give colorless crystals (8) (392 mg, 87%). The analysis results of the obtained product were as follows. 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 (270MHz, 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 ) Δ20.59(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).

[Number 5]

-2.5 (c 1.00, CHCl ₃ ). 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-ethinyl-β-D-glucosideoxy)benzaldehyde (9)

【化12】

Add 4,4-dihydroxymethyl-α-D-bromoglucopyranose (1) to 2,4-dihydroxybenzaldehyde (138 mg, 1.0 mmol) in quinoline solution (1,3 mg) under a nitrogen stream (1233 mg) 3.0 mmol) and silver oxide (495 mg, 3.0 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with benzene (60 ml), and the insoluble material was separated by filtration. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to yield yellow oil (1085 mg) as residue. The residue was subjected to a column chromatography to give a yellow viscous oil (801 mg) by hexane-ethyl acetate (3:2). This was extracted with diethyl ether (30 ml), and the insoluble yellow oil (105 mg) was filtered. Next, the extract was concentrated to give a white viscous oil (733 mg, 92%). This was recrystallized from hexane-ethanol (3:1) to give colorless crystals (9) (680 mg, 85%, mp 179-180 ° C). The analysis results of the obtained product were 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-ethinyl-β-D-glucosideoxy)benzaldehyde (10)

【化13】

To a solution of 3,5-dihydroxybenzaldehyde (69 mg, 0.5 mmol) in quinoline (2 ml) was added tetrakis-O-acetamido-α-D-glucopyranose (1) (613 mg, under a nitrogen stream). 1.5 mmol) and silver oxide (347 mg, 1.5 mmol) were stirred at room temperature for 75 minutes. After completion of the reaction, extraction was carried out with chloroform (50 ml), and the insoluble material was separated by filtration. Next, the extract was washed five times with 1% hydrochloric acid (20 ml), and then washed with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried (MgSO4)iel The residue was subjected to chromatography on a column chromatography, eluting with hexane-ethyl acetate (3:2) to afford white solid (301mg). This was recrystallized from ethanol to give colorless needle crystals (10) (241 mg, 60%, mp 113-114 ° C). The analysis results of the obtained product were 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), 907cm ^-1 (CH). ¹ H NMR (270MHz CDCl ₃ ) δ2.04 (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-parade (2,3,4,6-tetra-O-ethinyl-β-D-glucosyloxy)benzaldehyde (11)

【化14】

4-O-Ethyl-α-D-bromoglucopyranose (1) was added to a solution of 2,4,6-trihydroxybenzaldehyde (77 mg, 0.5 mmol) in quinoline (3 ml) under a nitrogen stream ( 924 mg, 2.25 mmol), and silver oxide (519 mg, 2.25 mmol) were stirred at room temperature for 2 hours. After completion of the reaction, extraction was carried out with benzene (50 ml), and the insoluble material was separated by filtration. Next, the extract was washed 10 times with 1% hydrochloric acid (20 ml), and then washed 10 times with a 1% aqueous sodium hydrogencarbonate solution (20 ml). The organic layer was dried (MgSO4), evaporated, evaporated The residue was subjected to a column chromatography to give a white viscous oil (407 mg) by eluting with hexane-ethyl acetate (2:3). This was recrystallized from ethanol to give a white powder (11) (367 mg, 64%, mp 225-226 ° C). The analysis results of the obtained product were 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 (270MHz 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] Manufacture of C60 derivatives [Example 1] Synthesis of C60 (13) having 2-(tetra-O-ethinyl-β-D-glucopyranosyloxy)phenyl-substituted pyrrolidine

【化15】

O-methylmercaptophenyl 2,3,4,6-tetra-O-ethenyl group obtained in Synthesis Example 1 was added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol) under a nitrogen stream. β-D-glucopyranoside (2) (181 mg, 0.4 mmol) and creatinine (36 mg, 0.4 mmol) were removed while using a Dean-Stark apparatus while heating and refluxing for 8 hours.

The dark brown solid (537 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (105 mg, 36%) was separated by EtOAc (EtOAc:EtOAc) Further, the dark brown solid was dissolved in benzene (4 ml), and the mixture was evaporated to ethyl ether (20 ml) and evaporated to give a dark brown solid (13) [228 mg, 48% (74%). The analysis results of the obtained product were as follows. Dark brown solid, mp>300°C.Relative ratio of diastereomers determined by ¹ H NMR: 2/3IR (KBr) 2952, 2784 (CH), 1760 (C=O), 1226, 1040 (OC=O), 756 ( CH), 526 cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz, CDCl ₃ ) δ 1.96 (1.2H, s, CH ₃ ), 2.02, 2.03 (each 1.2H, s, CH ₃ ), 2.05 (3.6 H, 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 1ml/min) retention time 2.56min.

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

【化16】

The m-methylphenylphenyl 2,3,4,6-tetra-O-ethenyl group obtained in Synthesis Example 2 was added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol) under a nitrogen stream. β-D-glucopyranoside (3) (181 mg, 0.4 mmol) and creatinine (37 mg, 0.4 mmol) were removed using a Dean-Stark apparatus while heating under reflux for 8 hours.

The dark brown solid (502 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (98 mg, 34%) was separated by EtOAc (EtOAc:EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). The analysis results of the obtained product were as follows. Brown solid, mp>300°C.Relative ratio of diastereomers determind by ¹ H NMR: 8/7IR (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 ) λ max nm (log ε) 431 (3.59). HPLC (ODS, CHCl ₃ , flow rate 1 ml/min) retention time 2.61 min.

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

【化17】

The p-formylphenyl 2,3,4,6-tetra-O-ethenyl-β obtained in Synthesis Example 3 was added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol) under a nitrogen stream. -D-glucopyranoside (4) (181 mg, 0.4 mmol) and creatinine (36 mg, 0.4 mmol) were removed using a Dean-Stark apparatus while heating under reflux for 8 hours.

The dark brown solid (533 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (135 mg, 47%) was separated by EtOAc (EtOAc) (EtOAc) Further, the dark brown solid was dissolved in benzene (4 ml), and then evaporated to ethyl ether (20 ml) to give a dark brown solid (17) [158 mg, 33% (76%)]. The analysis results of the obtained product were as follows. Brown solid, mp>300°C.IR(KBr) 2950(CH), 1758(C=O), 1226,1038(OC=O), 526cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz, CDCl ₃ ) Δ2.03, 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 (67.8MHz, 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 ), 145.75, 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 ) λ max nm (log ε) 431 (3.68). HPLC (ODS) , CHCl ₃ , flow rate 1 ml/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-ethinyl-β-D-galactoseoxy) phenyl-substituted pyrrolidine

【化18】

O-methylmercaptophenyl 2,3,4,6-tetra-O-ethenyl group obtained in Synthesis Example 4 was added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol) under a nitrogen stream. β-D-galactose picoside (6) (181 mg, 0.4 mmol) and creatinine (36 mg, 0.4 mmol) were removed using a Dean-Stark apparatus while heating under reflux for 8 hours.

The dark brown solid (574 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (88 mg, 31%) was separated by EtOAc (EtOAc) (EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). The analysis results of the obtained product were as follows. Brown solid, mp>300°C.Relative ratio of diastereomers determind by ¹ H NMR: 3/2IR(KBr) 2946,2782(CH), 1752(C=O), 1216,1073,1042(COC),526cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz, 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), 12 9.25 (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, 141.33, 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), 140.55, 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 ) λ max nm ( Log ε) 257 (5.09), 333 (4.44), 431 (3.59). HPLC (ODS, CHCl ₃ , flow rate 1 ml/min) retention time 2.59 min.

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

【化19】

The m-methylphenylphenyl 2,3,4,6-tetra-O-ethenyl group obtained in Synthesis Example 5 was added to a dry p-hydrazine solution (200 ml) of C60 (289 mg, 0.4 mmol) under a nitrogen stream. β-D-galactose picoside (7) (181 mg, 0.4 mmol) and creatinine (36 mg, 0.4 mmol) were removed using a Dean-Stark apparatus while heating under reflux for 8 hours.

The dark brown solid (574 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (125 mg, 43%) was isolated by chromatography eluting with EtOAc (EtOAc:EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). The analysis results of the obtained product were as follows. Brown solid, mp>300°C.Relative ratio of diastereomers determind by ¹ H NMR: 1/1IR (KBr) 1754 (C=O), 1218, 1075, 1046 (COC), 526 cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz, 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 (2H, m, Ar-H), 7.40-7.81 (1H, m, Ar-H). ¹³ C NMR (67.8MHz, CDC1 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 2.58min.

[Example 6] Synthesis of C60(23) having 4-(tetra-O-ethinyl-β-D-galiperoseoxy)phenyl-substituted pyrrolidine

【化20】

The p-formylphenyl 2,3,4,6-tetra-O-ethenyl group obtained in Synthesis Example 6 was added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol) under a nitrogen stream. β-D-galactose sputum (8) (181 mg, 0.4 mmol) and creatinine (36 mg, 0.4 mmol) were removed using a Dean-Stark apparatus while heating under reflux for 8 hours.

The dark brown solid (513 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (109 mg, 38%) was isolated by chromatography eluting with EtOAc (EtOAc:EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). 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=9.5Hz,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 1.00 ml/min) retention time 2.58 min.

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

【化21】

The precursor (9) (319 mg, 0.4 mmol) obtained in Synthesis Example 7 and creatinine (36 mg, 0.4 mmol) were added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol). The Dean-Stark unit removes water while heating to reflux for 8 hours. The dark brown solid (704 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (95 mg, 33%) was separated by EtOAc (EtOAc:EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). EtOAc (EtOAc) The analysis results of the obtained product were 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), 526cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz CDCl ₃ ) δ 1.94 (1.5H, s, CH ₃ ), 2.02 (1.5H, s, CH3), 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 (1.5 H, 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-ethinyl-β-D-glucopyranosyloxy)-substituted pyrrolidine

【化22】

The precursor (10) (319 mg, 0.4 mmol) obtained in Synthesis Example 8 and creatinine (35 mg, 0.4 mmol) were added to a dry p-hydrazine solution (200 ml) of C60 (288 mg, 0.4 mmol). The Dean-Stark unit removes water and heats it back for 8 hours. The dark brown solid (731 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (99 mg, 34%) was isolated by chromatography eluting with EtOAc (EtOAc:EtOAc) After the dark brown solid was dissolved in EtOAc (4 mL), EtOAc (EtOAc:EtOAc) The analysis results of the obtained product were 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), 526cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz 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=9.6Hz, 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] C60 (29) having 2,4,6-paran (2,3,4,6-tetra-O-ethinyl-β-D-glucopyranosyloxy)-substituted pyrrolidine Synthesis

【化23】

The precursor (11) (344 mg, 0.3 mmol) obtained in Synthesis Example 9 and creatinine (27 mg, 0.3 mmol) were added to a dry p-hydrazine solution (200 ml) of C60 (216 mg, 0.3 mmol). The Dean-Stark unit removes water while heating to reflux for 8 hours. The dark brown solid (621 mg) obtained by concentration of the reaction mixture under reduced pressure was applied to a column chromatography. The C60 (60 mg, 28%) was separated by EtOAc (EtOAc) (EtOAc) The dark brown solid was dissolved in EtOAc (4 mL). EtOAc (EtOAc) The analysis results of the obtained product were as follows. Relative ration of diastereomers determind by ¹ H NMR: 8/7 Brown solid, mp 174-176 ° C. IR (KBr) 2950, 2780 (CH), 1758 (C=O), 1609, (C=C), 1220, 1040 (OC=O), 907(CH) 526cm ^-1 (C ₆₀ ). ¹ H NMR (270MHz 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 (1.4 H, 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) Time 2.37min.

[2] Solubility test of C60 derivatives [Comparative Example 1]

10 mg of PCBM was taken out, and dichloroethane (hereinafter referred to as DCE) was gradually added thereto, and the dissolved concentration (% by mass) was calculated. Even if 0.99 g of DCE (1 mass% solution) was added to the PCBM, it could not be completely dissolved.

[Embodiment 10]

The solubility test was carried out in the same manner as in Comparative Example 1, except that the C60 compound (13) obtained in Example 1 was used. As a result, all of them were dissolved when 0.2033 g of DCE was added. The concentration at this time was calculated to be 4.69 mass%.

[Example 11]

The solubility test was carried out in the same manner as in Comparative Example 1, except that the C60 compound (19) obtained in Example 4 was used. As a result, it was completely dissolved when 0.4083 g of DCE was added. The concentration at this time was calculated to be 2.39% by mass.

The results of the above Comparative Example 1, Examples 10 and 11 were collectively summarized in Table 1 below. As shown in Table 1, it was found that the C60 compound having a monosaccharide residue was extremely excellent in solubility in an organic solvent as compared with PCBM.

[3] Evaluation of the film-forming surface of C60 derivatives [Comparative Example 2]

Add DCE to the PCBM to modulate 0.01g/ml of varnish. After passing this varnish through a 0.2 μm filter, the PCBM was formed on the ITO substrate by a spin coating method (1000 rpm, 20 sec.), and then fired at 100 ° C for 1 hour to form a film.

For the obtained film, a film formation surface was observed using a laser scanning conjugate focal length microscope (manufactured by LaserTech, Inc., real-time scanning laser microscope, 1LM21D), and a scanning probe microscope (Nano Navi L-manufactured by SII Nano Technology Co., Ltd.) was used. Trace II) Evaluation of the surface roughness and the shape of the film. The results of the laser scanning conjugate focal length micrographs of the film formation surface of the PCBM are shown in Fig. 1. The results of the 2D film formation surface of the PCBM are shown in Fig. 2. The results of the 3D film formation surface of the PCBM are shown in Fig. 3.

As shown in Fig. 1, it was confirmed that agglomerates appeared in the PCBM film. Further, the surface roughness at this time was 216.2 nm as measured by AFM. As shown in Figs. 2 and 3, it was confirmed that the concavities and convexities of the aggregate were considerably large on the surface of the film.

[Embodiment 12]

To the C60 compound (13) obtained in Example 1, DCE was added to prepare a varnish of 0.01 g/ml. Using this varnish, a film was formed under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness: 40.3 nm). The results of the laser scanning conjugate focal length micrographs of the film formation surface shown in Fig. 4 and the 2nd dimensional film formation surface are shown in Fig. 5 and the results of the 3rd dimensional film formation surface are shown in Fig. 6.

As shown in Fig. 4, no aggregates as seen in Comparative Example 1 were observed in the microscope photograph. Further, the average surface roughness at this time was 3.66 nm as measured by AFM. As shown in FIGS. 5 and 6, it was found that the unevenness was observed on the surface of the film, which was considerably smaller than that of Comparative Example 1. This unevenness is considered to be the unevenness caused by the moisture in the atmosphere at the time of firing being dried on the surface of the film. Based on these results, by using the C60 compound (13), it is apparent that a film which is better than PCBM can be obtained.

[Example 13]

To the C60 compound (13) obtained in Example 1, DCE was added to prepare a varnish of 0.01 g/ml. The varnish was passed through a 0.2 μm filter, and then formed on a ITO substrate by a spin coating method (1000 rpm, 20 sec.) in a glove box (under a nitrogen atmosphere). Thereafter, the film was fired at 100 ° C for 1 hour in a vacuum to form a film (film thickness: 39.0 nm). The obtained film was evaluated for surface roughness and shape of the film. The results of the formation of the two-dimensional film formation surface on the surface of the film formation of Fig. 7 and the third dimension are shown in Fig. 8. As shown in Figs. 7 and 8, by firing in a vacuum, the unevenness disappeared without being affected by moisture, and it was apparent that a film having a more excellent film formation surface was obtained. Further, the average surface roughness at this time was 0.63 nm as measured by AFM.

[Embodiment 14]

To the C60 compound (19) obtained in Example 4, DCE was added to prepare a varnish of 0.01 g/ml. Using this varnish, a film was formed under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness: 43.0 nm). The results of the laser scanning conjugate focal length micrographs of the film formation surface shown in Fig. 9 and the 2nd dimensional film formation surface are shown in Fig. 10 and the results of the 3rd dimensional film formation surface are shown in Fig. 11.

As shown in Figs. 9 to 11, it was found that the film of Example 12 and the same surface properties were obtained. Further, the average surface roughness at this time was 7.84 nm as measured by AFM.

[Example 15]

To the C60 compound (19) obtained in Example 4, DCE was added to prepare a varnish of 0.01 g/ml. The varnish was passed through a 0.2 μm filter, and then formed on a ITO substrate by a spin coating method (1000 rpm, 20 sec.) in a glove box (under a nitrogen atmosphere). Thereafter, the film was fired in a vacuum at 100 ° C for 1 hour to form a film (film thickness: 42.9 nm). The surface roughness and the shape of the film were evaluated for the obtained film. The results of the formation of the 2-dimensional film formation surface on the surface of the film formation of Fig. 12 and the third dimension are shown in Fig. 13. As shown in Figs. 12 and 13, by firing in a vacuum, it was apparent that no film was affected by moisture, and it was found that a film having a more excellent film formation surface was obtained. Further, the average surface roughness at this time was 1.28 nm as measured by AFM.

[Example 16]

To the C60 compound (25) obtained in Example 7, DC resin was added to prepare a 1% by mass varnish. Using this varnish, a film was formed under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness: 68.6 nm). The results of the respective two-dimensional film formation surfaces are shown in Fig. 14 and the results of the three-dimensional film formation surface are shown in Fig. 15.

As shown in Figs. 14 and 15, a film having the same surface properties as in Example 12 was obtained. Further, the average surface roughness at this time was 2.75 nm as measured by AFM.

[Example 17]

The C60 compound (27) obtained in Example 8 was added with DCE to prepare a 1% by mass varnish. Using this varnish, a film was formed under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness: 72.1 nm). The results of the results of the two-dimensional film formation surface on the surface of the film formation of Fig. 16 and the third dimension are shown in Fig. 17.

As shown in Figs. 16 and 17, a film having the same surface properties as in Example 12 was obtained. Further, the average surface roughness at this time was 25.3 nm as measured by AFM.

[Embodiment 18]

The C60 compound (29) obtained in Example 9 was added with DCE to prepare a 1% by mass varnish. Using this varnish, a film was formed under the same conditions as in Comparative Example 2, and the film formation surface was evaluated (film thickness: 72.1 nm). The results of the respective two-dimensional film formation surfaces are shown in Fig. 18 and the results of the three-dimensional film formation surface are shown in Fig. 19.

As shown in Figs. 18 and 19, a film having the same surface properties as in Example 12 was obtained. Further, the average surface roughness at this time was 5.53 nm as measured by AFM.

The average surface roughness of the film obtained in the above Comparative Example 2 and Examples 12 to 18 is shown in Table 2. As shown in Table 2, by using the C60 compounds (13), (19), (25), (27), and (29), it was apparent that a film having a film formation surface superior to PCBM was obtained. Further, it has been found that by baking in a vacuum, irregularities due to moisture can be prevented, and film formation can be performed more smoothly.

[4] Determination of mobility [Embodiment 19]

The substrate was a tantalum substrate with a thermal oxide film having a thickness of 300 nm. The gate electrode uses a dome-shaped gold electrode having a channel length L = 25 μm and a channel width W = 76 mm. The surface of SiO _{2 was} subjected to hexamethyldioxane (HMDS) treatment.

The C60 compound (19) obtained in Example 4 was dissolved in dichloromethane, and a 0.02 g/ml varnish was prepared in the atmosphere. This varnish was dropped on a substrate through a filter of Φ = 0.2 μm in a glove box, and spin-coated at 1500 rpm for 20 sec. The n-type organic semiconductor layer was formed by directly drying it on a hot plate at 100 ° C for 1 hour.

The measuring box was held in a glove box so that the FET was not exposed to the atmosphere, and a vacuum was formed to evaluate the characteristics of the transistor. The evaluation results are shown in Fig. 20.

In general, the drain current I _D in the saturated state can be expressed by the following formula. That is, the mobility μ of the organic semiconductor can be obtained by taking the square root of the absolute value of the drain current I _D as the vertical axis and the slope of the graph when the gate voltage V _G is plotted on the horizontal axis.

I _D = WCμ(V _G -V _T ) ² /2L

In the above formula, W is the channel width of the transistor, L is the channel length of the transistor, C is the electrostatic capacitance of the gate insulating film, V _T is the threshold voltage of the transistor, and μ is the mobility. The mobility μ of the C60 compound (19) was 5.00 × 10 ^-4 cm ² /Vs when calculated based on this formula. The on/off ratios of the threshold voltages are each, 13.6V, 10 ⁵ ~ 10 ⁶ . As is apparent from this, the C60 compound (19) having a smooth film surface can be driven as an n-type semiconductor.

[Example 20]

The substrate was a tantalum substrate with a thermal oxide film having a thickness of 300 nm. The gate electrode uses a dome-shaped gold electrode having a channel length L = 25 μm and a channel width W = 76 mm. The untreated SiO ₂ surface was used directly.

The C60 compound (13) obtained in Example 1 was dissolved in dichloromethane, and a 0.02 g/ml varnish was prepared in the atmosphere. This varnish was dropped on a substrate through a filter of Φ = 0.2 μm in a glove box, and spin-coated at 1500 rpm for 20 sec. The n-type organic semiconductor layer was formed by directly drying it on a hot plate at 100 ° C for 1 hour.

The measuring box was held in a glove box, and the FET was placed in the atmosphere without being exposed to the atmosphere, and then a vacuum was formed to evaluate the characteristics of the transistor. The evaluation results are shown in Fig. 21. The electron mobility of the C60 compound (13) was calculated to be 6.73 × 10 ^-4 cm ² /Vs based on the above formula, and the on/off ratios of the threshold voltages were each 38.4 V and 10 ⁵ to 10 ⁶ . As is apparent from this, the C60 compound (13) having a smooth film surface can be driven as an n-type semiconductor.

Fig. 1 is a view showing a laser scanning conjugate focal length microscope photograph of a film formation surface of a PCBM film produced in Comparative Example 2.

Fig. 2 is a view showing a 2-dimensional film formation surface of a PCBM film produced in Comparative Example 2.

Fig. 3 is a view showing a 3-dimensional film-forming surface of a PCBM film produced in Comparative Example 2.

Fig. 4 is a view showing a laser scanning conjugate focal length microscope photograph of a film formation surface of a film produced in Example 12.

Fig. 5 is a view showing a 2-dimensional film formation surface of a film produced in Example 12.

Fig. 6 is a view showing a three-dimensional film formation surface of a film produced in Example 12.

Fig. 7 is a view showing a 2-dimensional film formation surface of a film produced in Example 13.

Fig. 8 is a view showing a three-dimensional film formation surface of a film produced in Example 13.

Fig. 9 is a view showing a laser scanning conjugate focal length microscope photograph of a film formation surface of a film produced in Example 14.

Fig. 10 is a view showing a 2-dimensional film formation surface of a film produced in Example 14.

Fig. 11 is a view showing a 3-dimensional film-forming surface of a film produced in Example 14.

Fig. 12 is a view showing a 2-dimensional film formation surface of a film produced in Example 15.

Fig. 13 is a view showing a three-dimensional film formation surface of a film produced in Example 15.

Fig. 14 is a view showing a 2-dimensional film formation surface of a film produced in Example 16.

Fig. 15 is a view showing a three-dimensional film formation surface of a film produced in Example 16.

Fig. 16 is a view showing a 2-dimensional film formation surface of a film produced in Example 17.

Fig. 17 is a view showing a three-dimensional film formation surface of a film produced in Example 17.

Fig. 18 is a view showing a 2-dimensional film formation surface of a film produced in Example 18.

Fig. 19 is a view showing a three-dimensional film formation surface of a film produced in Example 18.

Fig. 20 is a view showing the transistor characteristics of the element produced in Example 19.

Fig. 21 is a view showing the transistor characteristics of the element produced in Example 20.

Claims (12)

An n-type semiconductor characterized by being composed of a fullerene compound represented by the following formula (1), [wherein, R ¹ to R ⁵ each independently represent a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or an inositol residue) group, and R ⁶ represents an alkyl group having 1 to 5 carbon atoms; however, R ¹ At least one of ~R ⁵ is the aforementioned OR ⁷ group]. The n-type semiconductor according to claim 1, wherein the monosaccharide residue is a butyral residue, a pentose residue or a hexose residue. The n-type semiconductor according to claim 1, wherein the monosaccharide residue is allosyl, arabinosyl, erythrosyl, fructosyl, and half. Galactosyl, glucosyl, gulosyl, lyxosyl, mannosyl, ribosyl, sialic acid residues, sorbosyl , tagalosyl, talosyl or xylosyl. The n-type semiconductor according to any one of claims 1 to 3, wherein the aforementioned monosaccharide residue or inositol residue has a hydroxyl group At least one of them is protected by a protecting group. The n-type semiconductor according to claim 4, wherein the protecting group is an alkyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a methoxymethyl group or a 2-tetrahydropyranyl group. , ethoxyethyl, ethenyl, trimethylethenyl, benzindenyl, trimethyldecyl, triethyldecyl, t-butyldimethylalkyl, triisopropyldecyl Or t-butyldiphenyldecylalkyl. A varnish comprising the n-type semiconductor and the organic solvent according to any one of claims 1 to 5, wherein the n-type semiconductor is dissolved in an organic solvent. An n-type organic semiconductor thin film obtained by the varnish as claimed in claim 6 of the patent application. An n-type organic semiconductor thin film comprising the n-type semiconductor according to any one of claims 1 to 5. An organic semiconductor device comprising the n-type organic semiconductor thin film according to item 7 or item 8 of the patent application. A field effect transistor characterized by having an n-type organic semiconductor thin film as described in claim 7 or 8. An organic thin film solar cell characterized by comprising an n-type organic semiconductor thin film as described in claim 7 or 8. A fullerene compound characterized by being represented by the following formula (2), [wherein, R ¹ to R ⁵ each independently represent a hydrogen atom or OR ⁷ (R ⁷ represents a monosaccharide residue or an inositol residue) group, and R ⁶ represents an alkyl group having 1 to 5 carbon atoms; however, R ¹ ~ At least two of R ⁵ are the aforementioned OR ⁷ groups].