KR20130095455A - METHOD OF PREPARING FULLERENE DERIVATIVES USING PHOTOADDITION REACTION OF TERTIARY α-SILYLAMINE AND FULLERENE - Google Patents

Abstract

PURPOSE: A manufacturing method of fullerene derivatives is provided to reduce the reaction time, to have a suitable equivalent ratio, to be able to introduce various functional groups, and to have a high yield of products. CONSTITUTION: A manufacturing method of fullerene derivatives comprises a step of synthesizing fullerene derivatives by reacting with addition of silyl-amines represented by Chemical formula 2 to a compound represented by Chemical formula 1. In Chemical formulas, A is a fullerene derivative selected from substituted or non-substituted C60, C70, C72, C76, C78 or C84; R1, R2 and R3 are, respectively, substituted or non-substituted (C1-30) alkyl, (C6-30) aryl, or (C4-30) heteroaryl; R4 and R5 are, respectively, substituted or non-substituted (C1-30) alkyl, (C6-30) aryl, (C1-30) alkyl substituted with alpha-silyl tertiary amino, or (C4-C30) heteroaryl.

Description

Method of preparing fullerene derivatives using photoaddition reaction of tertiary α-silylamine and fullerene}

The present invention relates to a method for preparing a fullerene derivative through a photoaddition reaction of tertiary α-silylamines, and more particularly, to an α-silyl substituted tertiary amine electron donor-excited state electron acceptor system. It relates to a method for producing a fullerene derivative through the electron transfer induced light addition reaction of.

Fullerene (C ₆₀ ) is a sp ² hybrid orbital with all carbon atoms in the molecule, and electrons distributed in p-orbitals that do not participate in sigma bonds are delocalized throughout the molecular surface. Formed to absorb large areas of visible light and to allow free electron transfer on the fullerene surface. In addition, in order to satisfy the spherical aromaticity according to Hukel's law, two or more electrons can be received and accordingly the reduction voltage (-0.51V vs SCE, benzonitrile) in the ground state tends to accept the electrons. It is a molecule that is very large and easily accepts electrons from an electron supplying body, and is expected to play a role as an electron acceptor.

Fullerene (C ₆₀ ) derivatives are n-type organic semiconductors and materials with very high applicability, especially as electron acceptor materials for organic solar cells, and are the most important materials in the recent development of efficient organic solar cell devices. It is a highly interested substance.

Recently, the importance of the solution process has been greatly increased as a method of manufacturing a low cost organic photovoltaic device, but due to the low solubility of the fullerene in the organic solvent, it is necessary to manufacture the device in the solution process using the fullerene. There are technical limitations and the photon-to-electric conversion efficiency (η = (J _sc ⅹV _oc ⅹFF) / P _in ) _in organic solar cells is based on the highest occupied molecular orbital (HOMO) energy of the electron supply and the lowest occupied molecular of the electron acceptor. Obrbital) As it grows in proportion to the energy difference (Voc = LUMO (receptor) -HOMO (supplier)), efforts have been made to increase the LUMO energy level of fullerene molecules through chemical structure changes of fullerene molecules used as electron acceptors. have.

One such effort is to bring about an increase in the LUMO energy of fullerenes by causing an addition reaction to the fullerene molecule and reducing the degree of conjugation of p-bonds on the surface of the fullerene molecule after the addition reaction. Many researchers have tried to synthesize and develop derivatives that have the advantages of fullerene (high electron affinity and electron mobility) and increased solubility and high LUMO in organic solvents. For example, PCBM ([6,6] ] -phenyl-C61-butyric acid methyl ester) derivatives are known.

As a method of synthesizing fullerene derivatives including PCBM, it is mainly selected to use cycloaddition reaction by nucleophile by heating in solution state, but the synthesis of reactants having functional groups to be introduced into fullerene is simple. In many cases, it is necessary to use an unstable reactor such as an azaide (N ₃ ) group, and also, in many cases, the reaction reagent used to introduce a functional group is not high in fullerene reactivity with the reaction reagents. It should be added in excess (20 equivalents) and reacted at high temperature. In the example reactions, the reaction time is as long as 12 hours or more, and the yield of the product is generally not high.

In order to solve the above problems, the present invention aims to provide a method for producing a fullerene derivative having a short reaction time, an equivalent ratio is suitable, various functional groups can be introduced, and a high yield of the product.

It is another object of the present invention to provide a fullerene derivative compound having a short reaction time, an equivalent ratio, suitable for introducing various functional groups, and a high yield of a product.

Another object of the present invention is to provide an organic electronic device to which the fullerene derivative compound is applied.

In order to achieve the above object,

Provided is a method for preparing a fullerene derivative, which is synthesized by adding and reacting a silyl-amine represented by Formula 2 to a compound represented by Formula 1.

[Formula 1]

(2)

Where

A is selected from substituted or unsubstituted C60, C70, C72, C76, C78 or C84 as a fullerene derivative,

R1, R2, and R3 are each independently a substituted or unsubstituted (C1-C30) alkyl group, (C6-C30) aryl group or (C4-C30) heteroaryl group,

R4 and R5 are each independently a substituted or unsubstituted (C1-C30) alkyl group, an (C6-C30) aryl group, an alkyl group substituted with a (C1-C30) α-silyl tertiary amino group, or a (C4-C30) heteroaryl Qi.

To achieve these and other objects,

Provided is a fullerene compound prepared by a method for producing a fullerene derivative, which is synthesized by addition reaction of the silyl-amines represented by the formula (2) to the compound represented by the formula (1).

According to another aspect of the present invention,

Provided is an organic electronic device comprising a fullerene compound prepared by a method for producing a fullerene derivative, which is synthesized by adding and reacting a silyl-amine substituent represented by Formula 2 to a compound represented by Formula 1.

According to the present invention, the electron transfer photochemical reaction of the fullerene electron acceptor-α-silyl electron donor system enables the synthesis of new fullerene derivatives in a more efficient and higher yield. In addition, various functional groups may be introduced into the nitrogen atom substituents (R ₄ and R ₅ ) of the aminomethyl group (aminomethyl: -CH ₂ NR ₄ R ₅ ) introduced into the fullerene molecule. Therefore, since various functional groups can be introduced to nitrogen atoms, it is possible to synthesize substituted fullerene derivatives having functional groups having electron deficient sites or functional groups rich in electrons.

1 illustrates an electron transfer photoaddition mechanism between fullerene and α-silyl substituted tertiary amine molecules according to an embodiment of the present invention.
2 shows the synthesis of α-silylsubstituted tertiary alkylamine molecules in accordance with one embodiment of the present invention.
Figure 3 illustrates the photochemical addition reaction between fullerene and α-silyl substituted tertiary alkylamine molecules according to one embodiment of the present invention.
Figure 4 illustrates the effect of solvent ethanol on the electron transfer photochemical addition reaction of fullerene and α-silyl tertiary amine according to an embodiment of the present invention.
FIG. 5 shows the effect of dissolved oxygen on the electron transfer photochemical addition reaction of fullerene and α-silyl tertiary amine according to one embodiment of the present invention.
6 shows UV-Vis absorption spectra of fullerene derivatives synthesized according to one embodiment of the present invention.
FIG. 7 illustrates the synthesis of tertiary hydrogenated aminomethyl fullerene derivatives through electron transfer induced photochemical reactions and their applicability as a dyad solar cell according to one embodiment of the present invention.
8 illustrates the applicability of a hydrogenated aminomethyl fullerene as a dyad solar cell in accordance with one embodiment of the present invention.
FIG. 9 shows the synthesis of 1-alkyl-2-aminomethyl fullerene and 1-substituted alkyl-2-aminomethyl fullerene derivatives using hydrogenated aminomethyl fullerene derivatives according to the embodiment of FIG. 3 and their applicability as solar cell materials. Illustrated.
FIG. 10 is a diad type of 1-alkyl-2-aminomethyl fullerene and 1-substituted alkyl-2-aminomethyl fullerene derivatives using a diad-type material of hydrogenated aminomethyl fullerene obtained according to one embodiment of FIGS. 7 and 8. Material synthesis and application as solar cell is shown.
11 to 13 illustrate a method for synthesizing a fullerene derivative prepared according to the prior art manufacturing method.

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

The present invention has developed a novel electron transfer induced photoaddition reaction capable of efficiently synthesizing various fullerene derivatives which are widely used as electron acceptors of organic solar cell devices.

In the preparation method of the present invention, electron transfer photochemical reaction of a fullerene electron acceptor-α-silyl tertiary amine electron donor system is used. In particular, unlike conventional methods, α-silyl substituted electron sources such as α-silyl tertiary dialkylamine or α-silyl tertiary arylalkylamine compound are used as the electron source.

The present invention provides a method for preparing a fullerene derivative, which is synthesized by addition of a silyl-amine represented by Formula 2 to a compound represented by Formula 1.

[Formula 1]

(2)

Wherein A may be selected from substituted or unsubstituted C60, C70, C72, C76, C78 or C84 as a fullerene derivative, wherein R1, R2, and R3 are each independently substituted or unsubstituted (C1- C30) alkyl group, (C6-C30) aryl group or (C4-C30) heteroaryl group, R4 and R5 are each independently a substituted or unsubstituted (C1-C30) alkyl group, (C6-C30) aryl group, (C1 Or a (C4-C30) heteroaryl group substituted with a -C30) α-silyl tertiary amino group.

R 4 and R 5 may each independently be substituted with a hydroxyl group, an amino group, a carboxyl group, an ester group, a halogen group or an α-silyl tertiary amino group. R 4 and R 5 may each independently be substituted with an aromatic group, an aromatic oligomer, or a dendrimer.

In the reaction of the present invention, the reaction equivalent weight of the material represented by Formula 1 and Formula 2 may be 1: 1.2 to 1: 5.0, and preferably, the reaction may be performed under light irradiation (eg, visible light irradiation). Benzene, toluene, benzonitrile, tetrahydronaphthalene, decalin, carbon disulfide, anisole, chlorobenzene, It may be one or more selected from the group consisting of a mixed solvent of 1,2-dichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, xylene.

The reaction time for synthesizing the fullerene derivative of the present invention is preferably 5 minutes to 240 minutes.

According to one embodiment of the present invention, α-silyl substituted tertiary alkylamines represented by Formula 2 may be represented by the following formula. n is 1 to 9, m may be in the range of 1 to 4, G is a compound substituted with one or more substituents of H, CH ₃ , OCH ₃ , F, Cl.

The fullerene and its derivatives according to the present invention have a strong absorption band in the visible light region (> 620 nm) in addition to the normal photochemical reaction using high energy ultraviolet rays (200 nm to 400 nm). It has the advantage of being able to absorb visible light efficiently, and to cause a reaction by using a light source or solar energy in the visible light region.

Electron transfer photochemistry using α-silyl electron donors reactions provide high chemical efficiency and a method for regioselectively generating α-carbon radicals. . Scheme 1 shows electron transfer photochemical reaction of α-silyl substituted electron source.

[Reaction Scheme 1]

The α-silyl substituted electron supply molecule used as an electron source in Scheme 1 transfers electrons very rapidly to an excited state electron acceptor reached by receiving light energy, thereby generating an α-silyl substituted electron source radical cation. derived radical cation, which is then desilylated by a selective attack of the resulting nucleophilic silylophile, which is converted into α-carbon radicals with high chemical efficiency.

Light energy absorbed by electron transfer photochemical reaction acts as an enhanced driving force for electron transfer, and hetero atom sites such as oxygen atom, sulfur atom and nitrogen atom with n-electron (unshared electron) acting as electron supply site. The α-silyl substituted electron donors substituted with a silyl group at the α-position of the olefin moiety having a p-electron allow chemiselectively and regioselectively to generate α-heteroatomic substituted carbon radicals.

Increasing the HOMO energy level of the electron-supply molecule resulting from the effect of electronegativity (C, 2.5; Si, 1.8) lower than the carbon atoms of silicon atoms by introducing silicon atoms into the α-position of the heteroatom electron-supply molecule The reduction in oxidation potential allows the α-silyl substituted electron supply molecule to act as a better electron source.

In addition, in the α-heteroatom-substituted silyl radical cation generated after electron transfer, the half-filled radical cation 2p-orbital of radiacl cation overlaps the free d-orbital of the silicon atom to α-silyl The group stabilizes radical cations. This overlap greatly increases the cation charge distribution on the silicon electrons with low electronegativity, so that the α-heteroatom-substituted silyl radical cation is selectively desilylated by the selective attack of the nucleophilic prolysyl family, and the α-heteroatom is selectively selected. To be finally converted to a substituted carbon radical.

The bonding force between carbon-hydrogen is stronger than that of carbon-silicon (C-Si, 89.4 kcal / mol; CH, 104.8 kcal / mol), and α-dehydrogenation in α-heteroatom-substituted silyl radical cations generated after electron transfer α-desilyllation occurs more quickly than deprotonation, and methanol and ethanol are common solvents containing oxygen atoms (Si-O, 127 kcal / mol) that have a strong bond to silicon. By proceeding the reaction in an alcoholic solvent including a so that the nucleophilic desilylation process by the oxygen atoms of the solvent occurs exclusively so that the α-carbon radicals are generated selectively.

According to the present invention, it is possible to generate α-carbon radicals with high chemical efficiency and regioselectivity together with chemical properties of excited fullerenes having higher electron affinity by absorbing very high electron affinity of fullerene and visible ray light. Based on the electron transfer chemical reactivity of α-silyl substituted electron donors, it has been shown that it can provide an electron transfer photoaddition reaction capable of synthesizing new fullerene derivatives in high yield and chemical efficiency.

In addition, the electron transfer photochemical reaction of the fullerene electron acceptor-α-silyl electron donor system is more efficient and higher yield than the previously reported method for synthesis of fullerene derivatives. In addition, the present invention shows that there is an advantage in that various functional groups can be introduced into the nitrogen atom of aminomethyl group introduced into the fullerene molecule through this reaction. The advantage of the reaction that can introduce various functional groups to the substituents of the nitrogen atom (R ₄ and R ₅ ) allows the synthesis of substituted fullerene derivatives having a functional group having an electron deficient site or an electron-rich functional group site. .

By introducing various functional groups using this reaction, it is expected to provide a way to change the LUMO energy level of fullerene derivatives in various ways, and thus it is expected to be useful for developing new electron acceptor materials for solar cells. In addition, the synthesis method using this reaction is more efficient and higher than that of the fullerene derivative synthesis method previously reported by electron transfer photochemical reaction of fullerene electron acceptor-α-silyl electron donor system. The yield allows the synthesis of new fullerene derivatives.

In addition, various functional groups may be introduced into substituents (R ₄ and R ₅ ) attached to nitrogen atoms of aminomethyl groups (aminomethyl) introduced into the fullerene molecule through the preparation method of the present invention. Various functional groups can be introduced into the substituents of nitrogen atoms, thereby allowing the synthesis of substituted fullerene derivatives having functional groups with electron deficient sites or functional groups rich in electrons. By utilizing the high chemical selectivity and regioselectivity of the silyl-substituted electron sources, the full range of functional groups that can be stably and unchanged during the reaction conditions can be largely used to easily obtain fullerene derivatives having a secondary synthetic scaffold. You can get it.

Organic reaction knob functional groups (e.g., hydroxy groups, amino groups, halogen groups (halo, X = I, Br, Cl), carboxyl groups (-) in the substituent of the methylamino group nitrogen atom introduced into the fullerene molecule COOR), etc.) to allow fullerene electron acceptor-electron donor dyads, such as porphyrine molecules or electron supply molecules, such as polyarene materials, to be bound through sigma bonds. It is possible to efficiently provide important synthetic intermediates that can be used in the synthesis of new organic solar cell materials or semiconductor materials such as fullerene electron acceptor-electron donor-electron donor triads.

1 illustrates an electron transfer photoaddition mechanism between fullerene and α-silyl substituted tertiary amine molecules according to an embodiment of the present invention. Referring to FIG. 1, fullerene ( 1 ) and α-silyl substituted tertiary amine ( 2 ) are dissolved in a toluene-ethanol mixed solvent consisting of a toluene solvent capable of dissolving fullerene ( 1 ) and an ethanol solvent containing an oxygen atom. The mixture is irradiated with light having a wavelength of 330 nm or more using a Hanovia medium pressure mercury lamp and a uranium filter to irradiate the photochemical reaction. Fullerene molecules with strong absorption bands in the ultraviolet region of more than 330 nm to visible light are absorbed and excited in a singlet excited state, followed by a fast interphase transition process (interval transition photon efficiency, φ _ISC = 1). Will be converted to a triplet excited state ( 1 ^{* 3} ). The triplet excited fullerene thus produced rapidly transfers electrons from the α-silyl-substituted tertiary amine molecule to form a fullerene radical anion intermediate ( 3 ) and an α-silyl-substituted tertiary amine molecule. is converted to the radical cation (α-silyl tertiary amine cation radical) intermediate (4).

The α-tertiary amine radical cation is then desilylated by nucleophilic attack of ethanol in the solvent to be converted to the α-amino methyl radical ( 5 ), which is a fullerene anion radical ( 3 ) generated during the electron transfer process. And a radical-radical coupling reaction produces a tertiary aminomethyl substituted fullerene anion ( 6 ), which is an anionic intermediate from the solvent molecule ethanol or silylated ethanol cation intermediate ( 7 ). Receiving a hydrogen cation (proton) can produce the final 1,2-light addition product, hydro (aminomethyl) fullerene ( 8 ).

The α-silylsubstituted tertiary amines used as electron source were subjected to the SN ₂ reaction between trimethylsilylmethyl iodide (Me ₃ SiCH- ₂ I) and the corresponding secondary amine molecules (S _N 2 reaction). ) Can be synthesized in high yield. α-silyl substituted tertiary alkylamine is chemically stable and can be easily synthesized in a general organic chemistry laboratory, and can be synthesized and stored and stored for a long time.

In FIG. 1, two substituents, R ₁ and R ₂ , which are bonded to the nitrogen atom of the α-silyl substituted tertiary amine molecule, may introduce functional groups in accordance with the purpose of changing the structure to be introduced into the final aminomethyl group-added fullerene product molecule. have. Fullerene derivatives synthesized through electron transfer photoaddition between fullerene-α-silyl substituted tertiary amines can have many kinds of structural changes, and the derivatives can be applied as organic solar cells and semiconductor materials.

According to the production method according to the present invention, the α-silyl tertiary amines used as the electron supplyer have a lower oxidation voltage than the tertiary amines in which the silyl group is not substituted, thereby acting as a more efficient electron supplyer. It is an important step in the reaction mechanism to rapidly de-silify by the attack of an oxygen solvent such as ethanol of the α-silyl substituted radical cation intermediate generated after electron transfer. The result is a photoaddition reaction that can have high chemical selectivity and regioselectivity, and therefore is a new 1-hydrogen-2- (aminomethyl) fullerene (1-hydro) with faster, more efficient and higher yield than conventional fullerene derivative synthesis methods. 2- (aminomethyl) fullerene) derivatives can be synthesized.

In addition, as a substituent of nitrogen atom of aminomethyl group introduced into fullerene, a new fullerene derivative which is difficult to be obtained by the method of synthesizing fullerene derivative chemically by easily introducing various functional groups which can stably and without change during photoaddition reaction conditions. Can be synthesized.

These various structural changes can provide a way to vary the LUMO energy level of the fullerene derivatives in a variety of ways, and the secondary synthetic scaffold functional group (hydroxy group or amino group) (amino), halogen (X = I, Br, Cl), carboxyl) substituents can be introduced as a substituent of the amine nitrogen to synthesize a new kind of organic solar cell materials and organic semiconductor materials It is possible to provide a method for providing a synthetic intermediate capable of doing so.

Fullerene electron acceptor-electron supply diads are made possible by the use of a secondary synthetic scaffold functional group to bond electron supply molecules such as porphyrine molecules or polyarylene materials through sigma bonds. It can be usefully used for developing new electron acceptor materials for solar cells such as acceptor-electron donor dyads, fullerene electron acceptor-electron donor-electron donor triads, and the like.

Novel 1-hydro-2- (aminomethyl) fullerene derivatives obtained by electron transfer photoaddition at high yields have a potassium t-position of hydrogen at the 1-position added to these derivatives. It can be deprotonated by treatment with a strong base such as butoxide so that anions of these fullerene derivatives can be easily generated and reacted with electrophilic reagents such as alkyl halides to react with 1-alkyl-2-aminomethyl fullerene or 1- It can be used to generate substituted alkyl-2-aminomethyl fullerenes, which can be useful for developing new electron acceptor materials for organic solar cells.

Example

Experimental Method

^The product was identified by ¹ H (300 MHz) NMR and ¹³ C-NMR (75 MHz) spectra, and the chemical internal shift was determined by CDCl ₃ (or CDCl ₃₎ : CS ₂ = 1: 1) is expressed in ppm from the reference.

The photoreaction was carried out under a nitrogen stream using a 450 W Hanovia medium vapor pressure mercury lamp, a uranium filter (<330 nm) and a quartz immersion well. After the reaction, the liquid was distilled under reduced pressure and separated using silica gel column chromatography. All reaction reagents used were commercially available. The mass of the product was confirmed by high resolution mass spectrum (HRMS) using fast atom bombardment mass spectromentry (FAB-mass).

Synthetic example

Example 1

Alphasilyl Dihexylamine , N- ( Trimethylsilyl ) methyl -N, N-dihexylamine (α- Silyl dihexylamine , N- (trimethylsilyl) methyl-N, N-dihexylamine, Me ₃ SiMe ₃ CH ₂ N (C ₆ H ₁₁ ) ₂ Synthesis of 9

Dihexylamine (10.0 ml, 47 mmol) and potassium carbonate (K ₂ CO ₃ ) (13.0 g, 93 mmol) were added to an acetonitrile solvent (100 ml), followed by trimethylsilylmethyl iodide (Me ₃ SiCH ₂ I) (2.0 g, 9.34 mmol) was added dropwise at room temperature and refluxed for 12 hours. The solution was concentrated under reduced pressure, extracted with hexane, dried over sodium sulfate (Na ₂ SO ₄ ), filtered, concentrated under reduced pressure and separated by silica gel column chromatography (ethyl acetate: hexane = 1: 10). A liquid product α-silyl tertiary amine 9 (2.12 g, 84%) was obtained.

¹ H NMR (300MHz, CDCl ₃ ): δ 0.03 (s, 9H, Me ₃ Si), 0.88 (t, J = 6.9 Hz, 6H), 1.16-1.30 (m, 12H), 1.32-1.44 (m, 4H ), 1.90 (s, 2H), 2.32 (t, J = 7.2 Hz, 4H); ¹³ C NMR (75 MHz, CDCl ₃ ): δ -1.21, 14.08, 22.70, 26.81, 27.21, 31.94, 45.92, 57.56; FAB-HRMS: m / z calcd for C ₁₆ H ₃₈ NSi, (M + H ⁺ ), 272.2768; found 272.2774

Example 2

N- ( Trimethylsilyl ) methyl -N-2- (2- Hydroxyethoxy ) Ethylamine (N- (trimethylsilyl) methyl-N-2- (2-hydroxyethoxy) ethylamine, Me ₃ SiCH ₂ NHC ₂ H ₄ OC ₂ H ₄ OH Synthesis of 10

2- (2-ethyoxy) ethanol (5.7 g, 54.4 mmol) and potassium carbonate (K ₂ CO ₃ ) (18.9 g, 136 mmol) in acetonitrile solvent (200 ml) ) And then trimethylsilyl iodide (Me ₃ SiCH ₂ I) (9.7 g, 45.3 mmol) was added dropwise at room temperature and refluxed for 12 hours. The solution was concentrated under reduced pressure, extracted with ethyl acetate, dried over sodium sulfate (Na ₂ SO ₄ ), filtered, and concentrated under reduced pressure. The yellow liquid obtained by simple distillation was purified as a transparent liquid product α-silyl secondary amine 10 ( 8.7 g, 84%).

¹ H NMR (300 MHz, CDCl ₃ ): δ -0.05 (s, 9H), 1.97 (s, 2H), 2.70 (t, J = 5.1 Hz, 2H), 3.46 (t, J = 5.1 Hz, 2H), 3.51 (t, J = 5.1 Hz, 2H), 3.58 (t, J = 5.1 Hz, 2H); ¹³ C NMR (75 MHz, CDCl ₃ ): δ -2.74, 39.72, 53.32, 61.31, 69.20, 72.31

Example 3

N- ( Trimethylsilyl ) methyl -N- (2- Hydroxyethoxyethyl -(2-ethyl) Hexylamine (N- (trimethylsilyl) methyl-N- (2-hydroxyethoxy) ethyl- (2-ethyl) hexylamine, Me ₃ SiCH ₂ N (CH ₂ CH (CH ₂ CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂₎ (CH ₂ CH ₂ OCH ₂ CH ₂ OH)) 11

To acetonitrile solvent (100 ml) was added α-silyl secondary amine 10 (2.0 g, 10.5 mmol) and potassium carbonate (K ₂ CO ₃ ) (5.78 g, 41.8 mmol), followed by 2-ethylhexyl bromide ( 2- (ethyl) hexyl bromide) (4.0 g, 20.9 mmol) was added dropwise at room temperature and refluxed for 12 hours. The solution was concentrated under reduced pressure, and the filtrate was extracted with dichloromethane (CH ₂ Cl ₂ ), dried over sodium sulfate (Na ₂ SO ₄ ), filtered and concentrated under reduced pressure, followed by silica gel column chromatography (ethyl acetate: hexane = 1: 5) to give a liquid product α-silyl tertiary amine 11 (1.8 g, 57%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 0.04 (s, 9H), 0.82-0.91 (m, 6H), 1.20-1.32 (m, 7H), 1.34-1.44 (m, 2H), 1.58 (br, 1H ), 1.94 (s, 2H), 2.18 (d and diastereotopic, J = 6.6 Hz, 1.8 Hz, 2H), 2.54 (t and diastereotpic, J = 6 Hz, 1.8 Hz, 2H), 3.54 (t, J = 6 Hz, 2H), 3.56 (t, J = 4.5 Hz, 2H), 3.71 (t, J = 4.5 Hz 2H); ¹³ C NMR (75 MHz, CDCl ₃ ): δ -1.20, 10.79, 14.11, 23.19, 24.36, 28.91, 31.18, 37.47, 41.52, 57.33, 61.91, 63.24, 69.48, 72.15; FAB-HRMS: m / z calcd for C ₁₆ H ₃₆ NO ₂ Si, (M-H ⁺ ), 302.2521; found 302.2520

Example 4

N- ( Trimethylsilyl ) methyl -N, N- Bisethoxycarbonylmethylamine  (N- (trimethylsilyl) methyl-N, N-bisethoxycarbonylmethylamine), Me ₃ SiCH ₂ N ( CH ₂ COOC ₂ H ₅ ) ₂ Synthesis of 12

Diethyl iminodiacetate (4ml, 23.3mol) and potassium carbonate (K ₂ CO ₃ ) (9.3g, 67.0mmol) were added to acetonitrile solvent (50ml), followed by trimethylsilyliodine ( Me ₃ SiCH ₂ I) (5.74 g, 26.8 mmol) was added dropwise at room temperature and refluxed for 12 hours. The solution was concentrated under reduced pressure, extracted with ethyl acetate, dried over sodium sulfate (Na ₂ SO ₄ ), filtered and concentrated under reduced pressure (silica gel column chromatography) (ethyl acetate: hexane = 1: 10). Separated into a liquid product α-silyl tertiary amine 12 (1.8 g, 31%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 0.04 (s, 9H), 1.23 (t, J = 7.2 Hz, 6H), 2.30 (s, 2H), 3.50 (s, 4H), 4.13 (q, J = 7.2 Hz, 4H); ¹³ C NMR (75 MHz, CDCl ₃ ): δ -1.84, 14.07, 45.59, 57.87, 60.00, 170.89; FAB-HRMS: m / z calcd for C ₁₂ H ₂₆ NO ₄ Si, (M + H ⁺ ), 276.1626; found 276.1631

Example 5

Photoaddition , Hydrogenation Aminofullerene , C ₆₀ ( CH ₂ N ( C ₆ H ₁₁ ) ₂ Synthesis of H (13)

C ₆₀ (100 mg, 0.139 mmol) and α-silyl tertiary amine 9 (150 mg, 0.555 mmol) were dissolved in 10% ethanol-toluene solvent (200 ml) and purged under N ₂ stream for one hour, followed by uranium Light irradiation was performed for 5 minutes using a uranium filter. The solution was concentrated under reduced pressure, and the brown solid obtained was separated by silica gel column chromatography (toluene: hexane = 1: 10) to give a brown solid product, hydrogenated aminomethyl fullerene 13 (60% conversion, 71 mg, 92%).

¹ H NMR (300MHz, CDCl ₃ : CS ₂ = 1: 1)): δ 0.94 (t, J = 6.9 Hz, 6H), 1.26-1.28 (m, 4H), 1.37-1.45 (m, 8H), 1.48-1.54 (m, 4H), 1.78-1.88 (m, 4H), 3.12 (t, 2H, J = 7.2 Hz), 4.43 (s, 2H, C ₆₀ CH ₂ N), 6.88 (s, 1H, C ₆₀ H ); ¹³ C NMR (75 MHz, CDCl ₃ : CS ₂ = 1: 1)): δ 14.22, 22.94, 27.38, 27.79, 32.05, 55.72, 58.20 (C ₆₀ C H ₂ N), 67.65 ( C ₆₀ H), 69.77 ( C ₆₀ CH ₂ N), 135.68 ( _{C 60, 2C), 136.14 (} C 60, 2C), 139.90 (C 60, 2C), 140.14 (C 60, 2C), 141.50 (C 60, 2C), 141.54 (C 60, 2C), 141.75 (C 60 , 2C), 141.93 (C ₆₀ , 2C + 2C), 142.23 (C ₆₀ , 2C), 142.45 (C ₆₀ , 2C), 142.96 (C ₆₀ , 2C), 143.14 (C ₆₀ , 2C), 144.40 (C ₆₀ , 2C), 144.57 (C ₆₀ , 2C), 145.23 (C ₆₀ , 2C + 2C), 145.28 (C ₆₀ , 2C + 2C), 145.74 (C ₆₀ , 2C), 146.01 (C ₆₀ , 2C), 146.07 ( C ₆₀ , 2C), 146.23 (C ₆₀ , 2C), 146.81 (C ₆₀ , 2C), 147.17 (C ₆₀ , 2C + 2C + 2C), 145.49 (C ₆₀ , 2C), 155.59 (C ₆₀ , 2C); FAB-HRMS: m / z calcd for C ₇₃ H ₃₀ N (M + H ⁺ ), 920.2373; found 920.2378

Example 6

Photoaddition Hydrogenated Aminomethyl Fullerene , C ₆₀ CH ₂ N (CH ₂ CH (CH ₂ CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ (CH ₂ CH ₂ OCH ₂ CH ₂ Synthesis of OH)) H (14)

C ₆₀ (100 mg, 0.139 mmol) and α-silyl tertiary amine 11 (170 mg, 0.555 mmol) were dissolved in 10% ethanol-toluene solvent (200 ml) and after purging the solution for 1 hour under N ₂ stream Light was irradiated for 5 minutes using a uranium filter. The solution was concentrated under reduced pressure, and the brown solid obtained was separated by silica gel column chromatography (ethyl acetate: toluene = 1: 20) to give a brown solid product, hydrogenated aminomethyl fullerene 14 (77% conversion, 60 mg, 62%). %) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 0.92 (t, J = 6.9, 3H), 0.99 (t, J = 7.2, 3H), 1.32-1.50 (m, 6H), 1.62-1.72 (m, 2H) , 1.78-1.86 (m, 2H), 2.96 (d, J = 6.9 Hz, 2H), 3.36 (t, J = 6 Hz, 2H), 3.67 (t, J = 4.5 Hz, 2H), 3.77-3.82 (m , 2H), 3.91 (t, J = 6 Hz, 2H), 4.51 (s, 2H, C ₆₀ CH ₂ N), 6.81 (s, 1H, C ₆₀ H ); ¹³ C NMR (75 MHz, CDCl ₃ ): δ 11.16 (CH ₂ CH (CH ₂ C H ₃ ) C ₄ H ₇ ), 14.24 (CH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ CH ₂ C H ₃ ) , 23.39 (CH ₂ CH ( C H ₂ CH ₃ ) C ₄ H ₇ ), 24.74 (CH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ C H ₂ CH ₃ ), 29.33 (CH ₂ CH (C ₂ H ₅ ) CH ₂ C H ₂ CH ₂ CH ₃ ), 31.61 (CH ₂ CH (C ₂ H ₅ ) C H ₂ CH ₂ CH ₂ CH ₃ ), 38.44 (CH ₂ C H (C ₂ H ₅ ) C ₄ H ₇ ), 55.51 ( C H ₂ CH (C ₂ H ₅ ) C ₄ H ₇ ), 58.34 (C ₆₀ C H ₂ N), 61.31 ( C H ₂ CH ₂ OCH ₂ CH ₂ OH), 62.02 (CH ₂ CH ₂ OCH ₂ C H ₂ OH), 67.70 (1 C, C ₆₀ H), 70.05 (1 C, C ₆₀ CH ₂ N), 70.93 (CH ₂ C H ₂ OCH ₂ CH ₂ OH), 72.36 (CH ₂ CH ₂ O C H ₂ CH ₂ OH), 135.91 (1C, C ₆₀ ), 135.97 (1C, C ₆₀ ), 136.25 (1C, C ₆₀ ), 126.28 (1C, C ₆₀ ), 139.93 (2C, C ₆₀ ), 140.29 ( 2C, C ₆₀ ), 141.62 (2C, C ₆₀ ), 141.68 (2C, C ₆₀ ), 141.85 (2C, C ₆₀ ), 142.03 (2C, C ₆₀ ), 142.05 (2C, C ₆₀ ), 142.29 (2C, _{C 60), 142.32 (2C,} C 60), 142.58 (2C, C 60), 143.08 (2C, C 60), 143.26 (2C, C 60), 144.56 (2C, C 60), 144.70 (2C, C 60 ), 145.34 (2C, C ₆₀ ), 145.38 (2C + 2C, C ₆₀ ), 145.43 (2C, C ₆₀ ) , 145.88 (2C, C ₆₀ ), 146.15 (2C, C ₆₀ ), 146.22 (2C, C ₆₀ ), 146.37 (2C, C ₆₀ ), 147.03 (2C, C ₆₀ ), 147.24 (2C, C ₆₀ ), 147.38 (2C, C ₆₀ ), 154.50 (2C, C ₆₀ ), 155.49 (2C, C ₆₀ )

Example 7

Photoaddition Hydrogenated amino fullerene C ₆₀ ( CH ₂ N ( CH ₂ COOC ₂ H ₅ ) ₂ Synthesis of H (15)

C ₆₀ (100 mg, 0.139 mmol) and α-silyl tertiary amine 12 (150 mg, 0.555 mmol) were dissolved in 10% ethanol-toluene solvent (200 ml) and purged for 1 hour under N ₂ stream, followed by uranium filter light) was irradiated for 2 hours using a filter). The solution was concentrated under reduced pressure and the brown solid obtained was separated by silica gel column chromatography (toluene) to obtain a brown solid addition product, hydrogenated aminomethyl fullerene 15 (56% conversion, 10 mg, 17%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 1.35 (t, J = 7.2 Hz, 6H), 4.24 (s, 4H), 4.30 (q, J = 7.2 Hz, 4H), 4.80 (s, 2H, C ₆₀ CH ₂ N), 7.09 (s, 1 H, C ₆₀ H); FAB-HRMS: m / z calcd for C ₆₉ H ₁₈ NO ₄ (M + H ⁺ ), 924.1230; found, 924.1236

Comparative Example 1

Dissolve C ₆₀ (288mg, 0.4mmol) and 4-methoxy- N, N -dimethylaniline (1.2g, 8.0mmol) in toluene (500mL) and place it in a pyrex container for 6 hours using a 400W high pressure mercury lamp. Was investigated. The reaction mixture was then separated using column chromatography (silica gel) (toluene / hexane = 1: 9) and GPC (solvent; chloroform) to give reaction mixture a (9.1%) and b (11.2%). Synthesis method according to Comparative Example 1 is briefly shown in FIG.

a : ¹ H-NMR (CDCl ₃ , 500 MHz): δ 7.21 (d, J = 9.2 Hz, 2H), 6.96 (d, J = 9.2 Hz, 2H), 6.55 (s, 1H), 5.27 (s, 2H), 3.82 (s, 3H), 3.47 (s, 3H ); ¹³ C-NMR (CDCl ₃ , 125 MHz): δ 154.8, 153.9, 152.5, 147.33, 147.29, 147.11, 147.08, 146.38, 146.35, 146.2, 146.1, 145.8, 145.5, 145.41, 145.35, 144.61, 144.56, 144.5, 143.2 , 142.60, 142.57, 142.2, 142.1, 142.0, 141.8, 141.73, 141.65, 140.3, 140.1, 136.3, 135.6, 115.2, 114.9, 68.8, 68.1, 58.2, 55.8, 42.1

b : ¹ H-NMR (CDCl ₃ , 500 MHz): δ 8.03 (s, 1H), 7.18 (d, J ), 8.8 Hz, 1H), 7.05 (d, J ) 6.1 Hz, 1H), 4.68 (s , 2H), 3.85 (s, 3H), 3.34 (s, 3H); ¹³ C-NMR (CDCl ₃ , 125 MHz): δ 153.7, 147.8, 147.7, 146.49, 146.46, 146.23, 146.20, 146.0, 145.8, 145.53, 145.45, 145.42, 145.35, 144.8, 144.7, 143.2, 142.7, 142.3, 142.2 , 142.1, 142.0, 141.7, 141.6, 140.4, 137.7, 116.0, 114.2, 112.9, 68.4, 67.0, 64.5, 55.7, 40.7

Comparative Example 2

Methyl-4-benzoylbutylate-p-tosylhydrazone (1.50 g, 4 mmol) and pyridine (30 mL) were added to a three-necked round bottom flask, followed by addition of sodium methoxide (NaOMe, 225 mg, 4.16 mmol). Stir for minutes. C ₆₀ (1.44 g, 2 mmol) dissolved in 1,2-dichlorobenzene (100 mL) was added to the mixed solution, and the mixture was heated at 65 to 70 ° C for 22 hours. The reaction mixture can be concentrated to 70 mL followed by column chromatography (silica gel) (chlorobenzene) to give the fullerene derivative compound (634.2 mg, 58%). A synthesis method according to Comparative Example 2 is briefly shown in FIG. 12.

¹ H-NMR (CS ₂ ) major isomer (95%): 7.87 (d, J = 7.5 Hz, 2H; o -Harom), 7.50 (m, 2H; m -H arom), 7.37 (m, 1H; p - Harom), 3.50 (s, 3H; O CH 2), 2.01 (t, J = 7.5 Hz, 2H; CH 2 CO 2 Me), 1.58 (m, 2H; PhC CH 2), 1.37 (m, 2H; CH ₂ CH ₂ CO ₂ Me). Minor isomer (about 5%): 7.19 (m, 2H, m -H arom), 7.10 (m, 1H; p -H arom), 7.01 (d, J = 9 Hz, 2H; o -H arom), 3.78 (m, 2H; PHC CH ₂ ), 3.53 (s, 3H; O CH ₃ ), 2.35 (t, J = 8 Hz, 2H; CH ₂ CO ₂ Me), 1.90 (m, 2H; CH ₂ CH ₂ CO ₂ Me).

¹³ C-NMR (CS ₂ ; 125 MHz; d (CS ₂ ) = 192.50 ppm): 171.94 (CO ₂ ), 147.39, 146.21, 145.19, 144.81, 142.47, 142.17, 141.95, 141.35, 141.03, 140.52, 139.70, 139.65 , 138.83, 138.21, 137.93, 136.59, 135.02, 130.67, 128.8 (Ph C _{2 , 3} ), 127.83 (Ph C _{2 , 3} ), 60.94 (Ph C ), 51.04 (OCH ₃ ), 35.58 (PhC C ), 33.67 ( C C0 ₂ ), 20.14 ( C CCO ₂ ).

Comparative Example 3

C ₆₀ (283 mg, 0.39 mmol) and 4-cyanophenyl azide (1115 mg, 7.74 mmol) were dissolved in 1,2-dichlorobenzene (20 mL) and stirred at room temperature for 10 days while blocking light. Acetonitrile (150 mL) is added to the reaction mixture to separate the resulting fullerene precipitate. The precipitates were collected, washed with acetonitrile and then separated by dark chromatography (153 mg, 54%) using column chromatography (alumina N) (toluene / acetonitrile = 99: 1). This intermediate (38 mg, 0.044 mmol) was dissolved in toluene (44 mL) and irradiated with light for 19 hours. You can observe the yellow solution turning into a red solution while irradiating light. After light irradiation, the solid in the mixture solution is filtered and the solution is concentrated. Acetonitrile (50 mL) was added to the concentrated solution (10 mL), and the resulting precipitate was filtered off and the precipitate was separated using column chromatography (silica gel) (toluene / hexane = 1: 1) to give a dark brown fullerene derivative. (18 mg, 49%) was obtained. A synthesis method according to Comparative Example 3 is briefly shown in FIG. 13.

¹ H-NMR (360 MHz; CS2 / (D6) acetone 10: 1) 8 = 7.80 (m, 4H, Ph) ppm. 13 C NMR (90.5 MHz; CS2 / (D6) acetone 10: 1): 8 = 149.41,145.79, 145.69, 145.45, 145.31, 145.08, 145.00, 144.46, 144.34, 144.20, 143.67, 143.63, 143.37, 142.68, 142.58, 141.58, 141.58 , 141.19, 133.68, 122.38, 118.00, 109.04, 83.48.

Evaluation and Results

2 illustrates the synthesis of fullerene and α-silylsubstituted tertiary alkylamine molecules in accordance with various embodiments of the present invention. Referring to FIG. 2, compound 9 having n -hexyl group introduced therein was synthesized, and a 2-ethylhexyl group having an ethyl group as hexyl group was introduced as a substituent of amine nitrogen to increase solubility and amorphousness. Α-silyl tertiary alkylamine compound 11 in which an ethoxyethanol group having a hydroxyl group (-OH), which can act as a reaction scaffold, is substituted with an amine nitrogen atom, and an ethoxycarbonyl group (-COOEt) is amine Α-silyl tertiary alkylamine compound 12 substituted with two nitrogen atoms of may be synthesized.

The electron transfer photoaddition reaction between fullerene and α-silyl tertiary alkylamines 9 , 11 and 12 was carried out using a 450W Hanovia medium vapor pressure mercury lamp to emit light in the entire UV-Vis region. The uranium filter removes light with a wavelength shorter than 330 nm, allowing fullerenes to absorb light in the ultraviolet and visible ranges above 330 nm.

Reaction time and yield

The reaction solvent is toluene which has high solubility in fullerene and does not absorb light of wavelengths above 330 nm as a main solvent and an oxygen atom-containing protic solvent ethanol (eg, to promote nucleophile assisted desilylation). : 10%) is used to dissolve the fullerene and α-silyl tertiary alkylamines 9 , 11 , 12 using a mixed solvent to form a reaction solution. The reaction solution was purged with nitrogen gas for about 1 hour to remove oxygen gas in the reaction solution before the photoaddition reaction. Reacting α-silyl tertiary amine electron supply molecule was used 4 equivalents based on 100 mg of fullerene. The reaction time, conversion, and chemical yield of the photochemical addition reaction between the fullerene and α-silyl substituted tertiary amine molecules performed are shown in Table 1 below.

donor α-aminofullerene Reaction time (min) Conversion Rate (%) yield(%) 9 Example 5 5 60 92 11 Example 6 5 77 62 12 Example 7 120 51 10

Figure 3 illustrates the photochemical addition reaction between fullerene and α-silyl substituted tertiary alkylamine molecules according to one embodiment of the present invention. Specifically, Figure 3 shows the synthesis of the fullerene derivatives 13-15.

Referring to FIG. 3 and Table 1, the photochemical reaction between the fullerene and the α-silyl substituted tertiary amine molecules proceeded very efficiently so that 60 to 77% of the fullerenes reacted in a very short time of about 5 minutes were reacted with aminomethyl group. The addition products 13 and 14 in which the and hydrogen atoms were added at the 1 and 2-positions of the fullerene were respectively produced in high yields of 92% and 62%.

However, the fullerene reaction with α-silylsubstituted tertiary amine 12 (conversion of 51% reactant in 120 min reaction) proceeded somewhat slower than the reaction with amines 9 and 11, and the yield of addition product 15 was also lower (10%). . However, the rate of progress of this reaction is still very efficient compared to other methods used to synthesize fullerene derivatives.

Meanwhile, the equivalents, solvents, reaction times and yields according to the fullerene production method synthesized according to Comparative Example 1 are shown in Table 2 below.

equivalent weight menstruum Reaction time (h) yield(%) Comparative Example 1 1 equivalent of fullerene, 20 equivalents of tertiary amine electron source without α-silyl substituent toluene 6 a = 9.1
b = 11.2
(Mix mixture) Comparative Example 2 1 equivalent of fullerenes, 2 equivalents of substituents Pyridine 22-24 50 ~ 58 Comparative Example 3 1 equivalent of fullerene, 20-30 equivalent of azide substituent 1,2-dichlorobenzene, 1,1,2,2-tetrachloroethane (used in heating reactions),
Toluene (used in photoreaction) Several days (heating) + 24 (light irradiation) 49-63

In Comparative Examples 1 to 3, a large amount of 2 to 20 equivalents of amine was used as the electron supplier due to the photoaddition reaction with the fullerene using the derivative having low oxidation voltage as the electron supplier without introducing the silyl group, and the long reaction was 6 hours to several days. It took time, and the chemical yield of the hydrogenated aminomethyl fullerene derivative was as low as 20-63%.

Compared with the results of Comparative Examples 1 to 3, it can be seen that the reaction according to the present invention using α-silyl substituted tertiary amines as electron donors shows much higher efficiency in the synthesis of hydrogenated aminomethyl fullerene derivatives.

The electron supply body used in the reaction of the present invention has an effect of the silyl group substituted at the α-position of the electron supplying portion, so that the electron supplying body has a lower oxidation voltage, thereby effectively donating electrons at a high speed. In addition, the α-silyl-substituted tertiary amine radical cation generated after electron transfer is very rapidly desilylated due to nucleophilic axylyl attack of solvent ethanol molecules and is converted into α-radical, thus eliminating an electron supply having no substituted silyl group. It can be evaluated to proceed much more efficiently than the similar reaction used.

Effect of Solvents and Dissolved Oxygen

Figure 4 illustrates the effect of the solvent on the electron transfer photochemical addition reaction of fullerene and α-silyl tertiary amine according to an embodiment of the present invention.

The photoaddition reaction between fullerene-α-silylsubstituted tertiary amines begins with the absorption of light energy by fullerene molecules and electron transfer from the α-silylsubstituted tertiary amines to fullerene triplet excited state. The α-silyl substituted tertiary amine radical cation generated after electron transfer is rapidly desilylated by a nucleophilic axylyl attack of an ethanol molecule containing an oxygen atom to be converted into a tertiary amine radical. Therefore, the rapid desilylation process by the attack of the ethanol molecule, which is an oxygen atom-containing protic solvent molecule, determines the overall efficiency of the photoaddition reaction. In order to confirm the role of ethanol in the reaction solution which is expected to play an important role in the photoaddition reaction mechanism, the effect of solvent on the photoaddition reaction between fullerene-α-silyl substituted tertiary amines was investigated.

To determine the effect of 10% ethanol solvent added to the reaction solvent, the reaction rate of the reaction solution consisting of a toluene solution containing 10% ethanol and a 100% toluene solution containing no ethanol under a nitrogen gas stream was measured. Compared. As a result, as shown in FIG. 4, the 10% ethanol-toluene reaction solution proceeds rapidly by light irradiation, and the reaction is completed after 12 minutes of light irradiation time, while the 100% toluene reaction solution without ethanol is 12 reaction time. The reaction shows little progress after the minute. These experimental results can confirm that an alcohol solvent such as ethanol, a solvent containing an oxygen atom, must be used as a reaction solvent for an efficient reaction.

FIG. 5 shows the effect of dissolved oxygen on the electron transfer photochemical addition reaction of fullerene and α-silyl tertiary amine according to one embodiment of the present invention.

The reactants of the photochemical reaction solution of fullerene and α-silyl dihexylamine ( 9 ) were purged with oxygen gas and irradiated with light, while the same reaction solution was photochemically reacted with nitrogen gas. The conversion rate was compared. Α-amino fullerene produced by reacting a solution containing the same amount of α-silyl dihexylamine ( 9 ) based on fullerene (20 mg) in a Pyrex test tube (blocking light of wavelength less than 290 nm) every 2 minutes at a short wavelength (365 nm). The proportion of α-silyl dihexylamine ( 9 ) remaining in the solution without reacting with the amount of was determined using ¹ H-NMR spectrum.

Experimental results on the effect of oxygen gas in the photochemical reaction, as shown in FIG. 5, the solution reacted with oxygen gas and photochemically reacted with air was flowed with nitrogen while the reactants remained almost unreacted after 12 minutes of reaction time. In the reaction in which the oxygen gas dissolved in the reaction solution was removed, the reactants reacted rapidly, indicating that the reaction was almost completed in 12 minutes. The experimental results show that the photoaddition reaction between fullerene-α-silyl-substituted tertiary amines occurs through the triplet excited state of fullerenes, and the oxygen gas molecules in the reaction solution are converted to nitrogen or argon gas to obtain an efficient photoaddition reaction. It can be confirmed that the airflow should be removed.

UV  Absorption Spectrum Results

6 shows UV-Vis absorption spectra of fullerene derivatives synthesized according to one embodiment of the present invention. Fullerene-a-silylsubstituted tertiary amine 9 , 11 , 12 The additive product hydrogenated aminomethyl fullerenes 13 , 14 , and 15 produced through the photochemical reaction were easily removed and purified by silica gel chromatography after removing the solvent used in the reaction after distillation under reduced pressure. The structures of these photoaddition products 13 , 14 , 15 are ¹ H- and ¹³ C- NMR And it was determined using high resolution FAB-mass spectrum data. Referring to FIG. 6, the addition of aminomethyl groups and hydrogen atoms added to these separated products at the 1 and 2 positions of fullerene was observed in the UV-visible absorption spectra of these additive products. This was confirmed by the presence of a sharp absorption peak near 430 nm.

FIG. 7 illustrates the synthesis of tertiary hydrogenated aminomethyl fullerene derivatives through electron transfer induced photochemical reactions and their applicability as a dyad solar cell according to one embodiment of the present invention. 8 shows the applicability of a hydrogenated aminomethyl fullerene as a dyad solar cell according to a specific embodiment of the present invention. 9 is a synthesis of 1-alkyl-aminomethyl fullerene and 1-substituted alkyl-aminomethyl fullerene derivatives using a tertiary hydrogenated aminomethyl fullerene derivatives through electron transfer induced photochemical reaction and to solar cell materials according to an embodiment of the present invention. The applicability is shown. FIG. 10 is a synthesis and embodiment of a 1-alkyl-aminomethyl fullerene and a 1-substituted alkyl-aminomethyl fullerine-type diad material using a dyad solar cell material of a hydrogenated aminomethyl fullerene according to a specific embodiment of the present invention. The applicability as battery material is shown.

Tertiary hydrogenated aminomethyl fullerenes having a hydroxyl group (hydroxyl, -OH) as a secondary synthetic scaffold having high conversion efficiency and chemical yield of photoaddition reaction and introduced into fullerene molecules Porphyrin derivative, TTF (tetrathiafulvalene) derivative, dendrimer derivative, aromatic oligomer, aniline derivative, and ferrocene The direct connection of the ester (-COO-) to the carboxyl group (-COOH) of the ferrocene derivatives will be able to synthesize a new solar cell material of the dyad or triad type.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. It is therefore to be understood that the embodiments described above are intended to be illustrative, but not limiting, in all respects.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

Claims (11)

Method for preparing a fullerene derivative, characterized in that the synthesis by the addition of the silyl-amine represented by the formula (2) to the compound represented by the formula (1):
[Formula 1]

(2)

In this formula,
A is selected from substituted or unsubstituted C60, C70, C72, C76, C78 or C84 as a fullerene derivative,
R1, R2, and R3 are each independently a substituted or unsubstituted (C1-C30) alkyl group, (C6-C30) aryl group or (C4-C30) heteroaryl group,
R4 and R5 are each independently a substituted or unsubstituted (C1-C30) alkyl group, an (C6-C30) aryl group, an alkyl group substituted with a (C1-C30) α-silyl tertiary amino group, or a (C4-C30) heteroaryl Qi.
The method of claim 1,
Wherein R4 and R5 are each independently a portion of the reactor is substituted with a hydroxyl group, amino group, carboxyl group, ester group, halogen group or α-silyl tertiary amino group.
The method of claim 1,
R 4 and R 5 are each independently a terminal group is substituted with an aromatic arene, aromatic oligomer or dendrimer method of producing a fullerene derivative.
The method of claim 1,
Benzene, toluene, benzonitrile, tetrahydronaphthalene, decalin, carbon disulfide, anisole, chlorobenzene, A method for producing a fullerene derivative, characterized in that at least one selected from the group consisting of 1,2-dichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, and a mixed solvent of xylene is used.
The method of claim 1,
The reaction time in the synthesis is a method for producing a fullerene derivative, characterized in that 5 minutes to 240 minutes.
The method of claim 1,
Formula 2 is a method for producing a fullerene derivative, characterized in that represented by the following formula:

In this formula,
n may be in the range of 1 to 9, m may be in the range of 1 to 4, and G may be substituted with one or more substituents of H, CH ₃ , OCH ₃ , F, and Cl.
The method of claim 1,
Method of producing a fullerene derivative, characterized in that the reaction equivalent of the material represented by the formula (1) and formula (2) is 1: 1.2 ~ 1: 5.0.
The method of claim 1,
The reaction is a method for producing a fullerene derivative, characterized in that under light irradiation.
A fullerene compound prepared by the process according to any one of claims 1 to 8.
An organic electronic device comprising the fullerene compound according to claim 9.
The method of claim 10,
The organic electronic device is an organic electronic device, characterized in that selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic memory and an organic transistor.

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