KR20130104551A - Water-soluble perylene compounds having light interception and shift wavelength and process for producing the same - Google Patents

Abstract

PURPOSE: A water soluble perylene compound which is able to block and convert a light wavelength is provided to block rays which are unnecessary for photosynthesis and to help the growth of plants by converting a green wavelength into an effective wavelength, thereby improving productivity. CONSTITUTION: A water soluble perylene compound which is able to block and convert a light wavelength is denoted by a chemical formula 1 or 4. The water soluble perylene compound is dissolved in a polar solvent selected among water, dichloromethane, methanol, chloroform, and acetonitrile. A method for preparing the compound of chemical formula 1 comprises the steps of: substituting with an aromatic compound of chemical formula 3 in N,N'-di(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide of chemical formula 2 to prepare a perylene compound of chemical formula 4; and introducing an electrolyte of chemical formula 5 to the intermediate of chemical formula 4.

Description

WATER-SOLUBLE PERYLENE COMPOUNDS HAVING LIGHT INTERCEPTION AND SHIFT WAVELENGTH AND PROCESS FOR PRODUCING THE SAME}

The present invention relates to a novel water-soluble perylene compound having a light wavelength blocking and switching function and a method for preparing the same, and more particularly to N, N'-di (2,6-diisopropylphenyl) -1,7- After introducing an aromatic compound derivative into dibromoperylene-3,4,9,10-tetracarbodiimide, and then giving ionicity to the aromatic compound, it has solar selection blocking and light shift characteristics; At the same time, the present invention relates to a water-soluble perylene compound having a light wavelength blocking and switching function, and a method for producing the same, having water solubility.

In general, agricultural film has a general function such as light transmittance, warmth, invincibility or anti-fog property, so as to protect the crops from the environment outside the plastic house and to produce a high yield of agricultural products stably.

In particular, in order to promote photosynthesis of crops, a function of selectively absorbing light in a red region that effectively affects photosynthesis among visible rays of sunlight is required. This is because visible light contains red light that helps the photosynthesis of plants, but also green light that interferes with the plant's photosynthesis, which can selectively absorb light and shift the green light to wavelengths effective for photosynthesis. There is an urgent need for the development of additives having an additive.

In other words, only the light in the green area that interferes with photosynthesis of visible light is selectively blocked to absorb as little as possible, and the light in the remaining areas must be absorbed and used for energy production. At the same time, there is also a need for a function of shifting light from a small amount of absorbed green to red light (620 to 680 nm) to aid photosynthesis.

On the other hand, as a solution for solving the above problems, Patent Document 1 is known in the art for a functional agricultural film having light selective transmittance, Patent Document 2 and Patent Document 3 is known for agricultural films containing an ultraviolet absorber. However, the above patents are directed to a technology for imparting such functionality by forming compounds such as near-infrared absorbing dyes and fluorescent dyes for light conversion in an appropriate composition range, and is not a study on the development of direct additive compounds.

Therefore, the present inventors have completed the present invention by developing an additive compound that blocks the wavelength of the green light region that causes the degradation of photosynthesis and transforms it into the wavelength of other regions other than green light.

Patent Document 1: Republic of Korea Patent Publication No. 10-2009-0085941 (functional agricultural film having light selective transmission) Patent Document 2: Korean Unexamined Patent Publication No. 2000-42841 (Polyolefin-based agricultural film composition with excellent near-ultraviolet ray blocking property) Patent Document 3: Republic of Korea Patent Publication No. 10-0458015 (Production method of agricultural polyolefin film)

The present invention relates to N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboximide

Selectively block green light that degrades photosynthesis by substituting aromatic derivatives on both sides of (N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide) A water-soluble perylene compound having a light wavelength blocking and converting function, which is prepared by shifting a small amount of absorbed green wavelengths into a red wavelength which is effective for photosynthesis, thereby preventing the growth of crops, and a preparation thereof It provides a method.

This invention makes the water-soluble perylene compound which has a light wavelength blocking and switching function represented by following [Formula 1] as a problem solving means.

[Formula 1]

[In Formula 1, R ¹ Are each independently aromatic compounds, preferably phenol and pyridine compounds.

And this invention makes the manufacturing method of the water-soluble perylene compound which has the light wavelength blocking and switching function represented by the said [Formula 1] including the following step into another problem solving means.

(i) N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboximide represented by the following [Formula 2] Substituted reaction of the aromatic compound represented by the following [Formula 3] to (N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide) To prepare a perylene compound represented by:

[Reaction Scheme 1]

[Formula 2] [Formula 3] [Formula 4]

[In Reaction Scheme 1, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound].

(ii) preparing a perylene compound represented by the following [Formula 1] by introducing an electrolyte represented by the following [Formula 5] to the intermediate represented by the above [Formula 4].

 [Reaction Scheme 2]

[Formula 4] [Formula 5] [Formula 1]

[In Reaction Scheme 2, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound, and each X is independently an electrolyte, preferably sulfuric acid, hydrochloric acid, methyl iodide, sodium hydroxide].

The present invention provides an aromatic compound derivative which is an electron donating group in N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboximide By blocking the green wavelengths and shifting the light-absorbed green wavelengths to the red wavelengths, light rays unnecessary for photosynthesis are blocked, and the light-absorbed green wavelengths are transformed into wavelengths effective for photosynthesis to help plant growth. It can be importantly used as an agricultural greenhouse material to improve productivity, improve productivity, and in particular, its low solubility in water, which is a disadvantage of light blocking and converting compounds, is improved, so that it can be widely applied in various fields. .

Water-soluble perylene compound having a wavelength blocking and switching function according to the present invention and a method for producing the same according to the present invention for achieving the above effect will be described only parts necessary to understand the technical configuration of the present invention, the description of other parts of the present invention It should be noted that it will be omitted so as not to distract the subject matter.

The present invention is characterized by a water-soluble perylene compound having a light wavelength blocking and switching function represented by the following [Formula 1].

[Formula 1]

[In Formula 1, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound].

The perylene compound represented by the above [Formula 1] according to the present invention is N, N'-di (2,6-diisopropylphenyl) -1,7-di (phenoxy) perylene-3,4,9 , 10-tetracarboxylic acid bisimide, N, N'-di (2,6-diisopropylphenyl) -1,7-di (3-pyridoxy) perylene-3,4,9,10-tetra Carboxylic Acid Bisimide, N, N'-di (2,6-diisopropylphenyl) -1,7-di (4-sulfonylphenoxy) perylene-3,4,9,10-tetracarboxyl Acid bisimide and N, N'-di (2,6-diisopropylphenyl) -1,7-di [3- (N-methyl-pyridinium) oxy] perylene-3,4,9, One species is selected from the group consisting of 10-tetracarboxylic acid bisimide.

Colors appear in various ways by being absorbed, reflected or transmitted by the selected wavelength as the energy radiated from the light source strikes the object. In order to modify the wavelength of excitation and emission in a compound that absorbs, excites, and emits an existing measurement wavelength, an electron donor and an electron acceptor must be provided to control the difference in the electron band.

On the other hand, the perylene compound has a high thermal stability and optical stability, but there is little solubility in water or organic solvents, there is a limit to the wide use. In order to improve this in the present invention by using an electrolyte to give ionicity by maximizing solubility.

The perylene compound represented by the above [Formula 1] according to the present invention not only has the light blocking and conversion characteristics of the existing light conversion pigments, but also imparts ionicity by reacting with an electrolyte to improve solubility in a solvent.

In the present invention, the perylene compound represented by the above [Formula 1] has high solubility in an organic solvent, particularly a polar solvent. The polar solvent is preferably one or more selected from water, dichloromethane, chloroform, methanol or acetonitrile.

In addition, the intermediate represented by the following [Formula 4] prepared in step (i) in the method for producing a perylene compound represented by the above [Formula 1] also belongs to the novel perylene compound according to the present invention, the physical properties of As will be apparent from the following examples.

 [Formula 4]

[In Formula 4, R ¹ Are each independently aromatic compounds, preferably phenol and pyridine compounds.

In the present invention, the aromatic compound derivative introduced as the electron donating group is an aromatic compound represented by the following [Formula 3].

(3)

[In Formula 3, R ¹ Are each independently aromatic compounds, preferably phenol and pyridine compounds.

In the present invention, the material introduced to impart ionicity is an electrolyte represented by [Formula 5].

[Chemical Formula 5]

[In Formula 5, X is each independently an electrolyte, preferably sulfuric acid, hydrochloric acid, methyl iodide, sodium hydroxide].

On the other hand, the water-soluble perylene compound having a light wavelength blocking and switching function according to the present invention is a water-soluble perylene compound represented by [Formula 1] through the process of the following [Scheme 1] to [Scheme 2].

Hereinafter, a method for preparing a water-soluble perylene compound having a light wavelength blocking and switching function according to the present invention will be described below.

(i) N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboximide represented by the following [Formula 2] Preparing a perylene compound represented by the following [Formula 4] by substitution reaction of the aromatic compound represented by the following [Formula 3]:

[Reaction Scheme 1]

[Formula 2] [Formula 3] [Formula 4]

[In Reaction Scheme 1, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound].

N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracar represented by the above [Formula 2] in [Scheme 1] Reaction by adding a bodiimide (N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide) and the aromatic compound derivative represented by the above [Formula 3] Let's do it. In this case, dimethyl formalamide was used as a solvent and K ₂ CO ₃ was used as a catalyst. Aromatic compound derivatives provide the basis for being shifted as electron donating groups.

[Formula 4] prepared as described above is very difficult to purify the reaction solution after distillation under reduced pressure, the precipitated crystals are washed with chloroform and obtained through filtration drying process, followed by column chromatography (using silica, developing solvent; dichloro) Methane) separation and purification to obtain a perylene compound represented by the above [Formula 4].

(ii) preparing a perylene compound represented by the following [Formula 1] by introducing an electrolyte represented by [Formula 5] to the intermediate represented by [Formula 4] prepared in (i):

 [Reaction Scheme 2]

[Formula 4] [Formula 5] [Formula 1]

[In Reaction Scheme 2, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound, and each X is independently an electrolyte, preferably sulfuric acid, hydrochloric acid, methyl iodide, sodium hydroxide].

The electrolyte was placed in the intermediate represented by the above [Formula 4] and stirred for a long time at room temperature using a mechanical bar. The reaction introduced with the electrolyte has a base to increase the reactivity with water by having ions in the electron donor.

The reaction compounds reacted in [Scheme 1] to [Scheme 4] above are preferably reacted in an equivalent weight equivalent, but the amount of the reaction compound may be appropriately adjusted as necessary.

Hereinafter, the content of the present invention will be described in detail with reference to the following examples, and the present invention is not necessarily limited to the following examples.

1. Synthesis of Perylene Compounds

(Example 1)

After installing a thermometer, a stirrer and a reflux condenser in a three-necked reactor, N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10- After dissolving 5.9 mmol of tetracarbodiimide in 200 ml of dimethylformamide, 29 mmol of phenol and 29 mmol of K ₂ CO ₃ were added thereto, and the mixture was heated and stirred at 110 ° C. for 6 hours. The reaction solution was cooled to room temperature, washed with 500 ml of 2M hydrochloric acid aqueous solution, filtered, and dried. The obtained material was separated and purified through column chromatography (silica, developing solvent: dichloromethane) to obtain 34.0% of a purple solid. Obtained in yield.

(Example 2)

1.9 mmol of the intermediate obtained in the above (Example 1) and 4 ml of sulfuric acid were added to the reactor, followed by stirring at room temperature for 24 hours using a magnetic bar. Then, water was added, filtered, and dried to obtain a purple solid in a yield of 56.0%.

(Example 3)

After installing a thermometer, a stirrer and a reflux condenser in a three-necked reactor, N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10- After dissolving 5.9 mmol of tetracarbodiimide in 200 ml of dimethylformamide, 29 mmol of hydropyridine and 29 mmol of K ₂ CO ₃ were added thereto, and the mixture was heated and stirred at 110 ° C. for 6 hours. The reaction solution was cooled to room temperature, washed with 500 ml of 2M aqueous hydrochloric acid solution, filtered, and dried. The obtained material was separated and purified through column chromatography (silica, developing solvent: dichloromethane) to give 32.0% of a red solid. Obtained in yield.

(Example 4)

In the reactor, 0.92 mmol of the intermediate obtained in the above (Example 3) and 4.6 mmol of methyl iodide were added to 100 ml of methanol and stirred at 85 ° C. for 24 hours using a magnetic bar. Then water was added, strained and dried to give a red solid in a yield of 60.0%.

[Table 1] summarizes the structure and production yield of the perylene compound prepared by the method of Examples 1 to 4.

division rescue Yield (%) Example 1

56.0 Example 2

34.0 Example 3

32.0 Example 4

60.0

2. Identification of New Perylene Compounds

The compounds of Examples 1 to 4 of Table 1 were prepared using a 600 MHz nuclear magnetic resonance spectrometer (600 MHz Agilent NMR System), an infrared spectrometer (FT-IR spectrometers), and gel permeation chromatography. The perylene compound was identified as follows.

Example 1 Compound

1 H-NMR (δ, CD ₂ Cl ₂ ) 8.12 (s, 4H), 7.33 (t, ³ J = 7.5 Hz, 2H), 7.24-7.08 (m, 12H), 7.02 (t, ³ J = 7.5 Hz, 4H), 6.93 (d, ³ J = 7.5 Hz, 8H), 2.601 (sept, ³ J = 6.9 Hz, 4H), 1.03 (d, ³ J = 6.9 Hz, 24H). FT-IR (cm ⁻¹ , KBr pellet) 3066 (Aromatic CH), 2962 (CH ₃ ), 2362 (NC = O), 1586, 1508, 1487 (BENZENE RING), 959 (-CH = CH-). Molecular weight: number average molecular weight (Mn) 1932 g / mol, mass average molecular weight (Mw) 2854 g / mol. Melting point> 400 ℃.

Example 2 compound

1 H-NMR (δ, CD ₂ Cl ₂ ) 7.914 (s, 4H), 7.59 (d, ³ J = 8.8 Hz, 8H), 7.17 (t, ³ J = 7.6 Hz, 2H), 6.88 (d, ³ J = 8.8 Hz, 8H), 2.45 (sept, ³ J = Hz, 4H), 0.85 (d, ³ J = Hz, 24H). FT-IR (cm ^-1 , KBr pellet) 3066 (Aromatic CH), 2962 (CH ₃ ), 2362 (NC = O), 1586, 1508, 1487 (BENZENE RING), 1066 (SO ₄ ), 959 (-CH = CH-). Molecular weight: number average molecular weight (Mn) 1952 g / mol, mass average molecular weight (Mw) 2870 g / mol. Melting point> 400 ℃.

Example 3 Compound

1 H-NMR (δ, CD ₂ Cl ₂ ) 8.29 (d, ³ J = 6.3 Hz, 4H), 8.28 (s, 4H), 8.14 (s, 4H), 7.35 (t, ³ J = 7.9 Hz, 2H) , 7.30-7.27 (m, 4H), 7.19 (d, ³ J = 7.9 Hz, 4H), 7.17 (d, ³ J = 8.2 Hz, 4H), 2.58 (sept, ³ J = 6.6 Hz, 4H), 1.03 (d, ³ J = 6.6 Hz, 24H). FT-IR (cm ^-1 , KBr pellet) 3066 (Aromatic CH), 2962 (CH ₃ ), 2362 (NC = O), 1593 (PYRIDINE), 1586, 1508, 1487 (BENZENE RING), 959 (-CH = CH-). Molecular weight: number average molecular weight (Mn) 1881 g / mol, mass average molecular weight (Mw) 2839 g / mol. Melting point> 400 ℃.

Example 4 Compound

1 H-NMR (δ, CD ₂ Cl ₂ ) 9.22-9.01 (m, 2H), 8.78-8.42 (m, 12H), 8.12-7.97 (m, 2H), 7.88-7.68 (m, 2H), 7.57-7.33 (m, 8H), 4.47-4.40 (s, 12H), 2.91-2.69 (m, 4H), 1.15-1.11 (m, 24H). FT-IR (cm ^-1 , KBr pellet) 3066 (Aromatic CH), 2962 (CH ₃ ), 2362 (NC = O), 1593 (PYRIDINE), 1586, 1508, 1487 (BENZENE RING), 959 (-CH = CH-). Molecular weight: Number average molecular weight (Mn) 1962 g / mol, Mass average molecular weight (Mw) 2882 g / mol. Melting point> 400 ℃.

3. Experiment for Checking Physical Properties of Perylene Compounds

The perylene compound synthesized in Examples 1 to 4 and the perylene compound [N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3, which is a fluorescent dye as a control, 4,9,10-tetracarboximide (N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide) It carried out by the following method.

end. Spectroscopic properties

Perylene compounds were measured for absorption wavelengths using a UV-bis spectrophotometer (Jasco), and excitation and emission wavelengths were measured using a PL & EL spectrometer (F-4500 spectrometer). The results are shown in Table 2 below.

I. Dissolution characteristics

The dissolution characteristics of the perylene compound in the organic solvent were measured and shown in Table 2 below. The organic solvent used at this time is water, dichloromethane, methanol, chloroform, acetonitrile. 0.002 g of each compound was added to 30 ml of the solvent, dissolved for 1 hour using a sonicator, and when placed at room temperature, the dissolution characteristics were measured and compared with each other. For solvents with very high solubility, it is '++', for partially dissolved solvents, '+', for solvents with high solubility but different color after dissolution, and for '-' and In each case, '-' is indicated.

division Spectroscopic Properties (in CH ₂ Cl ₂ ) Dissolution characteristics Absorption wavelength
(nm) Wavelength
(nm) Emission wavelength
(nm) water Dichloromethane Methanol Croro
Form Aceto
Nitrile Example 1 393,505,535 393,505,
535 568,619 + ++ - ++ + Example 2 393,508,540 393,508,
540 571,623 ++ ++ - ++ + Example 3 387,455,484,518 387,455,484,518 543,577 + ++ ++ ++ ++ Example 4 399,468,503,560 399,468,503,560 592 ++ ++ ++ ++ ++ Control group 454,485,
518 455,484
518 538,575 - ++ ++ ++ ++

As shown in Table 2, the perylene compound of Examples 1 to 4 absorbs 393 to 560 nm of light and emits 538 to 623 nm of light. Similar.

The solubility of the perylene compound according to Examples 1, 2, 3, and 4 according to the present invention was very low in solubility in water as compared with the conventional fluorescent dyes. It was confirmed to have.

All. Specific Wavelength Blocking and Shift Characteristics

The wavelength blocking rate and shift rate of the perylene compound in the 520 nm to 580 nm ranges were measured and shown in the following [Table 3].

division % Block ¹⁾ % Conversion ²⁾ Example 1 40.8 20.9 Example 2 55.9 11.7 Example 3 56.8 12.4 Example 4 48.0 9.6 Control group 46.4 3.49 Note 1) The visible light blocking rate is measured using a UV-vis spectrometer (V-679 spectrophotometer, Jasco).
After measuring the transmittance (T%), obtain the visible light blocking rate expressed by. In this case, the transmittance is calculated as follows. The wavelength band spacing is 10nm and multiply by the weighting factor of the wavelength band. The weighting coefficients for each wavelength band shall be as specified in KS L 2514.
Note 2) Wavelength shift rate measurement is based on the UV-vis spectrometer (V-679 spectrophotometer, Jasco) and the absorption wavelength is measured by PL & EL spectrometer (F-4500 spectrometer). Calculated as the ratio of absorption and emission wavelengths in the selected region, and calculated as the emission ratio in the 620-680 nm region to the absorption ratio in the 520-580 nm region.

As shown in Table 3, the blocking rates of Examples 1 to 4 were 40.8 to 56.8% and the shift rate was 3.49 to 20.9%.

As can be seen from the above results, the perylene compound according to the present invention exhibits similar spectroscopic characteristics as compared with conventional fluorescent dyes, and has low solubility in water, which is a disadvantage of the existing materials, and is widely applicable in various fields. I could see that.

The present invention described above is not necessarily limited only to the above configuration, and various modifications can be made without departing from the technical spirit of the present invention.

Claims (6)

Water-soluble perylene compound having a light wavelength blocking and switching function represented by the following [Formula 1]:

[Formula 1]

[In Formula 1, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound].
Water-soluble perylene compound having a light wavelength blocking and switching function represented by the following [Formula 4]:

[Chemical Formula 4]

[In Formula 4, R ¹ Are each independently aromatic compounds, preferably phenol and pyridine compounds.
The method of claim 1,
The perylene compound represented by [Formula 1] is N, N'-di (2,6-diisopropylphenyl) -1,7-di (phenoxy) perylene-3,4,9,10-tetra Carboxylic Acid Bisimides, N, N'-di (2,6-diisopropylphenyl) -1,7-di (3-pyridoxy) perylene-3,4,9,10-tetracarboxylic acid bis Mead, N, N'-di (2,6-diisopropylphenyl) -1,7-di (4-sulfonylphenoxy) perylene-3,4,9,10-tetracarboxylic acid bisimide, And N, N'-di (2,6-diisopropylphenyl) -1,7-di [3- (N-methyl-pyridinium) oxy] perylene-3,4,9,10-tetracar A water-soluble perylene compound having an optical wavelength blocking and switching function, wherein the perylene compound represented by the above [Formula 1] according to the present invention is N, N'-. Di (2,6-diisopropylphenyl) -1,7-di (phenoxy) perylene-3,4,9,10-tetracarboxylic acid bisimide, N, N'-di (2,6- Diisopropylphenyl) -1,7-di (3-pyridoxy) perylene-3,4,9 , 10-tetracarboxylic acid bisimide, N, N'-di (2,6-diisopropylphenyl) -1,7-di (4-sulfonylphenoxy) perylene-3,4,9,10 -Tetracarboxylic acid bisimide, and N, N'-di (2,6-diisopropylphenyl) -1,7-di [3- (N-methyl-pyridinium) oxy] perylene-3, One species is selected from the group consisting of 4,9,10-tetracarboxylic acid bisimide.
. 4. The method according to any one of claims 1 to 3,
The water-soluble perylene compound is a water-soluble perylene compound having a light wavelength blocking and switching function, characterized in that dissolved in a polar solvent.
5. The method of claim 4,
The polar solvent is water, dichloromethane, methanol, chloroform or water-soluble perylene compound having a light wavelength blocking and switching function, characterized in that at least one selected from acetonitrile.
A method for producing a water-soluble perylene compound having a light wavelength blocking and switching function represented by [Formula 1] comprising the following steps.

(i) N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboximide represented by the following [Formula 2] (N, N'-di (2,6-diisopropylphenyl) -1,7-dibromoperylene-3,4,9,10-tetracarboxdiimide) is substituted with an aromatic compound represented by [Formula 3] to the following [Formula 4] To prepare a perylene compound represented by:

[Reaction Scheme 1]

[Formula 2] [Formula 3] [Formula 4]

[In Reaction Scheme 1, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound].

(ii) preparing a perylene compound represented by the following [Formula 1] by introducing an electrolyte represented by [Formula 5] to the intermediate represented by [Formula 4] prepared in (i):

[Reaction Scheme 2]

[Formula 4] [Formula 5] [Formula 1]

[In Reaction Scheme 2, R ¹ are each independently an aromatic compound, preferably a phenol, a pyridine compound, and each X is independently an electrolyte, preferably sulfuric acid, hydrochloric acid, methyl iodide, sodium hydroxide].