KR20040090230A - Highly Efficient Light-harvesting Dendritic Materials & Their Synthetic Methods - Google Patents

Abstract

PURPOSE: A dendrimer type light harvesting antenna compound for optical amplification is provided to maximize the light harvesting effect through efficient energy transfer. Further, solvent and moisture which cause nonradiative transition can be removed from the rare earth complex used thereto. CONSTITUTION: The dendrimer type light harvesting antenna compound with high efficiency comprises the compounds of formula 1, wherein R is selected from the compounds of formula 2; each X1 and X2 is any one selected from CH3, CO2H, CH2Br, NO2, NH2, OCH3 and OH.

Description

High-efficiency dendrimer-type condensing antenna compound and its manufacturing method {Highly Efficient Light-harvesting Dendritic Materials & Their Synthetic Methods}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high efficiency dendrimer-type condensing antenna compound and a method of manufacturing the same as an optical amplifying optical antenna material. The present invention relates to a compound represented by the following chemical formula and a method for preparing the same to develop a new plan view wave type optical amplified material by maximizing light harvesting effect by energy transfer by synthesizing a light antenna material. These compounds regulate the light emission wavelength of photoantenna through molecular design in consideration of energy level of rare earth compound and induce efficient energy transfer to rare earth complex compound, and also rare earth metal to prevent limitation of pumping laser of optical amplification device. It is a dendrimer-type light collecting material for efficiently exciting ions.

The present invention relates to a novel planar waveguide photoantenna compound for optical planar wave amplification, which excludes the penetration of solvents and water, which causes efficient energy transfer of rare earth ions and non-luminescent transition. This is to compensate for the inefficient energy transfer and reduction of the light intensity of rare earth ions, which are fundamental problems of the aryl ether-based optical antenna of the conventional organic optical amplification material.

The concentration of Er ⁺³ doped in the conventional optical silica is about 100-1000 ppm, and if it is higher than that, the non-luminescence process mainly occurs due to the interaction between the Er ⁺³ ions, thereby rapidly decreasing the optical amplification efficiency. For this reason, high gain optical amplification is not possible by doping Er ⁺³ to silica optical fiber, and thus it is difficult to expect about 30 dB of optical amplification in the form of a planar waveguide integrated circuit. As a new material for solving such a problem and implementing a planar waveguide optical amplification device, a material having a rare earth ion doped into a polymer has attracted attention. Optically amplified polymer materials are currently being studied in advanced countries such as Japan, the United States, and Europe to develop planar waveguide optical amplified materials in which a rare earth ion complex compound is doped into a polymer medium. The polymer amplification device is an optical fiber amplification device doped with organic dye at a concentration of about 1 ppm in a PMMA polymer fiber core medium, first published by Keio University in 1993, and the optical device is 50 cm in length and relatively long. Very good amplification characteristics in dB. However, since the light emission process is caused by spontaneous light emission, and the light amplification time is short, it cannot be used in the planar waveguide optical amplification device. To overcome this problem, the team presented a photo-amplified polymer device by doping rare earth metal with amplification effect to PMMA polymer fiber.

Recently, Kuzyk and colleagues at the University of Texas (Austin) in the United States announced the fabrication of a very short optical amplification device with a spin coating method of 2.2 cm by doping Nd ⁺³ on a water-soluble polymer, photolime gel, with an amplification wavelength of 1.06 µm. The gain was relatively good at 8.5 dB. Philips, the Netherlands, filled a Teflon capillary with a MA-based lauryl methacrylate monomer, and then doped the rare earth metal Eu ⁺³ and polymerized it to develop an optical amplification device in the form of a very short polymer optical fiber of about 1.5 cm. The amplification gain was reported as 4.1 dB.

Recently, as the interest of organic light amplification materials has increased in doping rare earth ions to a polymer or an inorganic compound, studies on optical antennas due to a light collecting effect have been actively conducted to efficiently excite rare earth ions.

Frechet and Kawa's team attempted to suppress the light-collecting effect and non-luminescent transition by coordinating rare earth ions using an aryl ether dendron. (Chem. Mater., 1998, 10, 286) This is because dendrimer-type photoantennas form complexes, which partially inhibit solvent or water infiltration, but the optical antenna material absorbs at high energy, causing spectroscopic overlap with rare earth ions. The degree of condensation could not be maximized due to efficient energy transfer. In order to be applied as an optical amplification material due to the light condensing effect, the absorption and emission wavelength of optical antenna materials according to the energy level of rare earth ions and the spectral overlap between optical antennas and rare earth ions through molecular design, and rare earth complex compounds of supramolecular form This suggests that the overall structure of the system should be controlled.

In order to solve the above problems, the present invention maximizes the light collection effect, which is the principle of natural photosynthesis by molecular engineering, in order to maximize the inefficient light collection effect of the conventional optical antenna, solvent and water causing the non-luminescent transition of the rare earth complex It is a technical object of the present invention to provide a new high efficiency dendrimer-type light collecting antenna compound and a method for producing the same, which do not penetrate. To maximize the condensing effect, the absorption wavelength region of the outer optical antenna (320-340 nm) and the absorption wavelength region of the inner optical antenna (270-350 nm in the case of naphthalene) increase the degree of spectroscopic overlap and transfer energy. The phenomenon was maximized. The chemical structure containing naphthalene (360-520 nm) and anthracene (380-540 nm) having the light emission wavelength region of the innermost optical antenna is characterized by the absorption wavelength region of ions of rare earth metals (395 nm for europium; absorption wavelength region of erbium). 365-520 nm) has a high degree of spectroscopic overlap, so that the energy transfer is good, the molecular design to increase the luminescence intensity of rare earth ions.

In order to achieve the above object, the present invention relates to a highly efficient dendrimer-type condensing antenna compound having a structure of the following formula that can efficiently excite the rare earth complex compound to maximize the condensing effect and a method of manufacturing the same.

These compounds and preparation methods have been described in more detail in the Examples, and these compounds and their preparation methods will be readily understood by those skilled in the art from the description, and the present invention is directed to only the compounds described by Examples. Those skilled in the art will readily appreciate that they are not limited.

[Formula 1]

X ₁ and X ₂ are each _one selected from CH ₃ , CO ₂ H, CH ₂ Br, NO ₂ , NH ₂ , OCH ₃ , OH.)

[Formula 2]

[Formula 3]

[Formula 4]

Hereinafter, the present invention will be described in detail through examples.

The reagent used in the present invention was used as follows, but those skilled in the art can easily select and use other products as necessary.

Dichloromethane, ethyl alcohol, THF, acetone, potassium carbonate, anhydrous magnesium sulfate, NaOH, HCl, NaHCO ₃ was used by Dongyang Chemical. And naphthalene, 4-bromoanisol, 4-bromotoluene, n-butyllithium (1.6 M in hexane), trimethylborate, tetra (kistri-phenylphosphine) palladium (0)), Pd / C, methyl-3,5-dihydroxybenzoate, 9,10-dibromoanthracene, p -bromonitrobenzene, n-bromosuccisin Imide (NBS), benzylperoxide (BPO), BBr ₃ , 18-crown-6, zinc chloride (1 M solution in diethyl ether), DMSO-d ₆ , chloroform-d, CBr ₄ , triphenylphosphine ( PPh ₃ ) and LiAlH ₄ were purchased from Aldrich, and bromine and CCl ₄ were used by Junsei. The above reagents were used without any purification.

The prepared intermediates and compounds were all confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR. ¹ H-NMR was recorded using a Varian 300 spectrometer, and all chemical mobility was reported in ppm with respect to tetramethylsilane, an internal standard. IR spectra were measured on KBr pellets using a Perkin-Elmer Spectrometer. UV-Vis absorption spectrum was measured in solution of Shimadzu's UV-2401PC, and the emission spectrum was measured in solution using Edinburgh's FS920.

Example 1:

Method for preparing 1-bromonaphthalene (1)

In a round flask, naphthalene (1 molar ratio) is added, the temperature is dissolved at 120 ° C., and bromine (1 molar ratio) is slowly added dropwise. The reaction is reacted at 120 ° C. for 4 hours and the temperature is lowered to room temperature. The resulting mixture is separated via vacuum distillation. Yield 89%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.33 (bd, 1H), 7.90-7.30 (m, 6H); ¹³ C-NMR (CDCl ₃ , ppm): δ 135.20, 132.55, 130.47, 128.85, 128.51, 127.95, 127.67, 127.25, 126.73, 123.42

[Chemical Scheme 1]

Example 2:

Method for preparing 1,4-dibromonaphthalene (2) and 1,5-dibromonaphthalene (3)

Bromine (3.71 mL, 72.44 mmol) is slowly added dropwise to the solution of 1-bromonaphthalene (10 g, 48.29 mmol) at 120 ° C. The mixture solution is stirred for 3 hours and then cooled to room temperature. Unreacted bromine is removed with an aqueous NaOH solution and extracted with CH ₂ Cl ₂ . Separate 1,4-dibromonaphthalene and 1,5-dibromonaphthalene using a sublimation apparatus.

1,4-dibromonaphthalene (2), ¹ H-NMR (CDCl ₃ , ppm): δ 8.25-7.62 (m, 4H), 7.61 (s, 2H); mp 80 ℃

1,5-dibromonaphthalene (3), ¹ H-NMR (CDCl ₃ , ppm): δ 8.20 (d, 2H), 7.79 (d, 2H), 7.38 (t, 2H); ¹³ C-NMR (CDCl ₃ , ppm): δ 132.85, 130.71, 127.21, 127.13, 122.86; mp 130 ℃ (lit. 131 ℃)

[Chemical Scheme 2]

Example 3:

Method for preparing 4- (4-methoxyphenyl) -1-bromonaphthalene (A-1)

This compound was synthesized using the well known Suzuki coupling method. In a 100 mL two-necked shlenk flask equipped with condenser, tetrakis (triphenylphosphine) palladium with 1,4-dibromonaphthalene (4 g, 14.0 mmol), 4-methoxyphenyl boronic acid (2.34 g, 15.4 mmol) and a catalyst (0) (0.485 g, 3 mol%, 0.42 mmol) was dissolved in 20 mL of toluene and stirred for 10 minutes, and 14 mL (2 molar ratio) of 2M Na ₂ CO ₃ aqueous solution was added, followed by 48 at 100 ° C. under nitrogen stream. Stir at reflux for hours. After the reaction is completed, the mixture is extracted with diethyl ether, and the organic layer is washed with brine and water. After drying over anhydrous magnesium sulfate, it is filtered. The solvent obtained is removed under reduced pressure, separated by column chromatography (silica, nucleic acid), and then dried under vacuum. Yield is 75%.

¹ H-NMR (CDCl ₃ , ppm): S 8.31 (d, 1H), 7.90 (d, 1H), 7.81 (d, 1H), 7.60 (t, 1H), 747 (t, 1H), 7.38 (d , 2H), 7.24 (d, 1H), 7.03 (d, 2H), 3.93 (s, 3H)

[Chemical Scheme 3]

Example 4:

Method for preparing 5- (4-methoxyphenyl) -1-bromonaphthalene (B-1)

Synthesis was carried out in the same manner as in Example 3. Yield 72%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.50 (d, 1H), 8.01 (d, 1H), 7.94 (d, 1H), 7.77 (t, 1H), 7.62 (d, 1H), 7.53 (d , 2H), 7.38 (t, 1H), 7.05 (d, 2H), 3.92 (s, 3H)

[Chemical Scheme 4]

Example 5:

Method for preparing 9- (4-methoxyphenyl) -10-bromoanthracene (C-1)

Synthesis was carried out in the same manner as in Example 3. After separation by column chromatography (silica, CH ₂ Cl ₂ / hexane), it is dried under vacuum. Yield 72%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.60 (d, 2H), 7.73 (d, 2H), 7.58 (t, 2H), 7.38 (t, 2H), 7.32 (d, 2H), 7.13 (d , 2H), 3.95 (s, 3H)

[Chemical Scheme 5]

Example 6:

Method for preparing 1- (4-methylphenyl) -4- (4-methoxyphenyl) naphthalene (A-2)

A-1 (2.0 g, 6.40 mmol), p-tolylboronic acid (1.13 g, 8.30 mol) and Pd (PPh ₃ ) ₄ (0.22 g, 0.19 mmol) were dissolved in 15 mL of toluene, followed by 2M Na ₂ CO ₃ aqueous solution. Add. The mixed solution was stirred under reflux at 100 ° C. for 48 hours, and the temperature was decreased to room temperature. The mixture is extracted with diethyl ether and the solution is removed with a rotary evaporator. The product is washed several times with methanol and then vacuum dried. White solid, 95% yield.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 2H), 7.60-7.40 (m, 8H), 7.37 (d, 2H), 7.10 (d, 2H), 3.93 (s, 3H), 2.50 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 308 nm; Photoluminescence (λ _max , CHCl ₃ ): 386 nm

[Scheme 6]

Example 7:

Method for preparing 1- (4-methylphenyl) -5- (4-methoxyphenyl) naphthalene (B-2)

Synthesis was carried out in the same manner as in Example 6. White solid, yield 93%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 2H), 7.60-7.40 (m, 8H), 7.36 (d, 2H), 7.07 (d, 2H), 3.95 (s, 3H), 2.47 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 306 nm; Photoluminescence (λ _max , CHCl ₃ ): 385 nm

[Scheme 7]

Example 8:

Method for preparing 9- (4-methylphenyl) -10- (4-methoxyphenyl) anthracene (C-2)

Synthesis was carried out in the same manner as in Example 6. Yellow solid, yield 90%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 2H), 7.60-7.40 (m, 10H), 7.38 (d, 2H), 7.10 (d, 2H), 3.95 (s, 3H), 2.52 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 380 nm and 400 nm; Photoluminescence (λ _max , CHCl ₃ ): 430 nm

[Chemical Scheme 8]

Example 9:

1- (4-carboxyphenyl) -4- (4-methylphenyl) naphthalene ([A-2] -CO ₂ H) manufacturing method

A-2 (1.00 g, 3.08 mmol) and potassium permanganate (2.92 g, 18.50 mmol) were dissolved in 40 mL of a mixture of pyridine and water (7: 3), stirred at 120 ° C for 24 hours, and then the temperature was returned to room temperature. Get off. The byproduct MnO ₂ is filtered and hydrochloric acid is added to the reaction to pH 1. The solid formed is washed several times with water. Yield is 78%.

FT-IR (KBr, cm ⁻¹ ): 3200, 1682 (ν _{c = o} ), 1247 (ν _co ); ¹ H NMR (CDCl ₃ , ppm): S 8.07 (d, 2H), 7.92 (m, 2H), 7.55-7.40 (m, 8H), 7.13 (d, 2H), 3.86 (s, 3H)

[Scheme 9]

Example 10

1- (4-carboxyphenyl) -5- (4-methylphenyl) naphthalene ([B-2] -CO ₂ H) manufacturing method

Synthesis was carried out in the same manner as in Example 9. Yield 72%.

FT-IR (KBr, cm ⁻¹ ): 3200, 1683 (ν _{c = o} ), 1244 (ν _co ); ¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 2H), 7.65-7.43 (m, 8H), 7.36 (d, 2H), 7.11 (d, 2H), 3.85 (s, 3H)

[Chemical Scheme 10]

Example 11:

9- (4-carboxyphenyl) -10- (4-methylphenyl) anthracene ([C-2] -CO ₂ H) manufacturing method

Synthesis was carried out in the same manner as in Example 9. Yield is 82%.

FT-IR (KBr, cm ⁻¹ ): 3200, 1685 (ν _{c = o} ), 1244 (ν _co ); ¹ H NMR (CDCl ₃ , ppm): δ 8.05-7.41 (m, 2H), 7.60-92 (m, 10H), 7.380 (d, 2H), 7.10 (d, 2H), 3.95 (s, 3H)

[Chemical Scheme 11]

Example 12:

Method for preparing 4- (4-methoxyphenyl) naphthalene-1-boronic acid ([A-1] -BOH)

In a 200 mL two-necked shlenk flask equipped with a dropping funnel, A-1 (3.32 g, 10.6 mmol) was dissolved in THF (60 mL) and n- under nitrogen stream in a dry ice / acetone bath. Butyllithium (1.6 M solution in hexane) (8,61 ml, 13.78 mmol) is slowly added dropwise. After the reaction mixture was stirred at room temperature for 1 hour, trimethyl borate (2.61 mL, 23.32 mmol) was added at -78 ° C with a syringe, and then the reaction temperature was gradually raised to room temperature and stirred for about 14 hours. After the reaction was completed, 5 mL of HCl aqueous solution was added, the organic layer was washed with water, and extracted with diethyl ether. The obtained organic layer is dried over anhydrous magnesium sulfate and filtered. The resulting mixture was removed from the solvent under reduced pressure and then washed with nucleic acid to give a white solid product. Yield 56%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 8.41 (d, 1H), 8.39 (s, 2H), 7.81 (d, 1H), 7.74 (d, 1H), 7.50 (t, 1H), 7.43 (t, 1H), 7.37 (d, 2H), 7.34 (d, 1H), 7.09 (d, 2H), 3.85 (s, 3H)

[Chemical Scheme 12]

Example 13:

Process for preparing 5- (4-methoxyphenyl) naphthalene-1-boronic acid ([B-1] -BOH)

Synthesis was carried out in the same manner as in Example 12. Yield 45%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 8.59 (d, 1H), 8.41 (s, 2H), 7.91 (d, 1H), 7.86 (d, 1H), 7.66 (t, 1H), 7.57 (t, 1H), 7.51 (d, 2H), 7.48 (d, 1H), 7.07 (d, 2H), 3.85 (s, 3H)

[Chemical Scheme 13]

Example 14

Method for preparing 9- (4-methoxyphenyl) anthracene-10-boronic acid ([C-1] -BOH)

Synthesis was carried out in the same manner as in Example 12. Yield 63%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.69 (d, 2H), 8.38 (s, 2H), 7.62 (d, 2H), 7.48 (t, 2H), 7.33 (t, 2H), 7.31 (d , 2H), 7.19 (d, 2H), 3.98 (s, 3H)

[Chemical Scheme 14]

Example 15:

Method for preparing 1- (4-methoxyphenyl) -4- (4-nitrophenyl) naphthalene (A-3) (1)

This compound was synthesized using the well known Suzuki coupling method. In a 100 mL two-necked shlenk flask equipped with a condenser, [A-1] -BOH (2 g, 6.73 mmol), 4-bromonitrobenzene (1.125 g, 7.4 mmol) and Pd (PPh ₃ ) ₄ ( 0.233 g, 3 mol%, 0.2 mmol) was dissolved in 20 mL of toluene and stirred for 10 minutes, after adding 7.4 mL (2 molar ratio) of 2M Na ₂ CO ₃ aqueous solution. The mixture is stirred under reflux for 48 hours at a temperature of 100 ° C. under a nitrogen stream. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , and the organic layer was washed with brine and water. After drying over anhydrous magnesium sulfate, it is filtered. The solvent obtained is removed under reduced pressure, separated by column chromatography (silica, CH ₂ Cl ₂ / hexane), and then dried under vacuum.

Scheme 15

Method for preparing 1- (4-methoxyphenyl) -4- (4-nitrophenyl) naphthalene (A-3) (2)

The flask No. 1 in which A-1 (4.0 g, 12.77 mmol) was added to 20 mL of THF at a temperature of −78 ° C. was stirred for 5 minutes. N-butyllithium (1.6M solution in diethyl ether) (8.78 mL, 14.05 mmol) was slowly added dropwise to the reactor over 5 minutes, followed by stirring at this temperature for 30 minutes. Zinc chloride (1.0 M) (14.05 mL, 14.05 mmol) was slowly added dropwise over 10 minutes, followed by gradually raising the temperature to 0 ° C. Meanwhile, 4-bromonitrobenzene (2.838 g, 14.05 mmol) and Pd (PPh ₃ ) ₄ (0.738 g, 0.64 mmol) are dissolved in THF in another 100 mL flask 2 and stirred at room temperature for 20 minutes. Then, the solution of the flask 1 was slowly added dropwise to the flask 2 through a capillary tube and stirred at room temperature for 10 hours. The reaction solution is poured into CH ₂ Cl ₂ , washed several times with water, dried over anhydrous magnesium sulfate and filtered. The solvent thus obtained is removed under reduced pressure, separated by column chromatography (silica, CH ₂ Cl ₂ / hexane), and then dried under vacuum. Yield is 90%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.39 (d, 2H), 8.02 (m, 1H), 7.84 (m, 1H), 7.72 (d, 2H), 7.44-7.51 (m, 6H), 7.07 (d, 2H), 3.90 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 305 nm; Photoluminescence (λ _max , CHCl ₃ ): 380 nm

Scheme 15a

Example 16:

Method for preparing 1- (4-methoxyphenyl) -5- (4-nitrophenyl) naphthalene (B-3)

Synthesis was carried out in the same manner as in Example 15. Yield is 92%. (See Formula 15-1)

¹ H-NMR (CDCl ₃ , ppm): δ 8.41 (d, 2H), 7.72 (d, 2H), 7.62-7.40 (m, 8H), 7.09 (d, 2H), 3.90 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 304 nm; Photoluminescence (λ _max , CHCl ₃ ): 380 nm

Scheme 16

Example 17:

Method for preparing 9- (4-methoxyphenyl) -10- (4-nitrophenyl) naphthalene (C-3)

Synthesis was carried out in the same manner as in Example 15. Yield is 85%. (See Formula 15-1)

¹ H-NMR (CDCl ₃ , ppm): δ 8.50 (d, 2H), 7.80 (m, 2H), 7,70 (d, 2H), 7.56 (m, 2H), 7.44-7.34 (m, 6H) , 7.17 (d, 2 H), 3.98 (s, 3 H); UV-Vis absorption (λ _max , CHCl ₃ ): 395 nm; Photoluminescence (λ _max , CHCl ₃ ): 425 nm

Scheme 17

Example 18:

1- (4-bromomethylphenyl) -4- (4-methoxyphenyl) naphthalene ([A-2] -CH ₂ Preparation of Br)

NBS (1.427 g, 8.015 mmol) was added to 50 mL CCl ₄ under nitrogen stream, and stirred for 10 minutes. Then, A-2 (2.0 g, 6,165 mol) and a catalytic amount of BPO were added and stirred at reflux for 5 hours at 120 ° C. The mixture is cooled to room temperature, the byproduct succineimide is filtered off, washed several times with methanol and washed again with nucleic acid. White solid, yield 65%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.03 (m, 2H), 7.53-7.45 (m, 10H), 7.07 (d, 2H), 4.62 (s, 2H), 3.91 (s, 3H)

Scheme 18

Example 19:

1- (4-bromomethylphenyl) -5- (4-methoxyphenyl) naphthalene ([B-2] -CH ₂ Preparation of Br)

Synthesis was carried out in the same manner as in Example 18. Yield 68%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 2H), 7.60-7.35 (m, 10H), 7.09 (d, 2H), 4.61 (s, 2H), 3.90 (s, 3H)

Scheme 19

Example 20:

9- (4-bromomethylphenyl) -10- (4-methoxyphenyl) anthracene ([C-2] -CH ₂ Preparation of Br)

Synthesis was carried out in the same manner as in Example 18. Yield 71%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 2H), 7.53-7.45 (m, 12H), 7.12 (d, 2H), 4.63 (s, 4H), 3.91 (s, 3H)

Scheme 20

Example 21:

Process for the preparation of 1- (4-hydroxy) -4- (4-methylphenyl) naphthalene (A-4)

Dissolve A-2 (2.27 g, 7.01 mmol) in 60 mL CH ₂ Cl ₂ , lower the temperature to −78 ° C. under a nitrogen stream, and then slowly add BBr ₃ (1.99 mL, 21.03 mmol). The mixture is stirred at room temperature for 24 hours and neutralized with NaHCO ₃ . The product is extracted with chloroform and dried over anhydrous sodium sulfate, and then purified by column chromatography (silica, eluent, chloroform). The net profit rate is 94%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.64 (bs, 1H), 7.92 (m, 2H), 7.50-7.30 (m, 10H), 6.94 (d, 2H), 2.40 (s, 3H) ; MS (EI) m / z 310.0 (M +)

Scheme 21

Example 22:

Method for preparing 1- (4-hydroxy) -5- (4-methylphenyl) naphthalene (B-4)

Synthesis was carried out in the same manner as in Example 21. Yield is 92%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.63 (bs, 1H), 7.87 (m, 2H), 7.79 (d, 1H), 7.55-7.28 (m, 8H), 6.95 (d, 2H) , 2.42 (s, 3 H); MS (EI) m / z 310.0 (M +)

Scheme 22

Example 23:

Preparation of 9- (4-hydroxy) -10- (4-methylphenyl) anthracene (C-4)

Synthesis was carried out in the same manner as in Example 21. Yield is 95%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.66 (bs, 1H), 7.85 (m, 2H), 7.79 (d, 2H), 7.55-7.28 (m, 10H), 6.97 (d, 2H) , 2.45 (s, 3 H); MS (EI) m / z 360.0 (M +)

Scheme 23

Example 24:

Method for preparing 1- (4-hydroxy) -4- (4-nitrophenyl) naphthalene (A-5)

Synthesis was carried out in the same manner as in Example 21. Yield is 92%.

¹ H-NMR (CDCl ₃ , ppm): δ 9.65 (bs, 1H), 8.50 (d, 2H), 7,72 (d, 2H), 7.55-7.38 (m, 8H), 6.95 (d, 2H)

Scheme 24

Example 25:

Process for preparing 1- (4-hydroxy) -5- (4-methoxyphenyl) naphthalene (B-5)

Synthesis was carried out in the same manner as in Example 21. Yield is 85%.

¹ H-NMR (CDCl ₃ , ppm): δ 9.66 (ds, 1H), 8.39 (d, 2H), 7.9-7.8 (m, 2H), 7.72 (d, 2H), 7.44-7.51 (m, 6H) , 6.95 (d, 2 H)

Scheme 25

Example 26:

Process for the preparation of 9- (4-hydroxy) -10- (4-nitrophenyl) naphthalene (C-5)

Synthesis was carried out in the same manner as in Example 21. Yield is 90%.

¹ H-NMR (CDCl ₃ , ppm): δ 9.65 (ds, 1H), 8.50 (d, 2H), 7.70 (d, 2H), 7.62-7.50 (m, 4H), 7.44-7.34 (m, 6H) , 6.95 (d, 2 H)

Scheme 26

Example 27:

[A-2] 2-CO ₂ Manufacturing Method of Me

[A-2] -CH ₂ Br (1.82 g, 4.510 mmol), methyl 3,5-dihydroxybenzoate (0.37 g, 2.201 mmol), potasium carbonate (0.76 g, 5.50 mmol), 18-crown-6 (0.116 g, 0.44 mmol) is dissolved in 50 mL acetone and stirred at reflux at 70 ° C. for 48 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with dichloromethane. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed. The product is purified via column chromatography (silica, eluent, CH ₂ Cl ₂ ). White solid, yield 73%.

FT-IR (KBr, cm ⁻¹ ): 1721 (ν _{c = o} ), 1606, 1244 (ν _co ); ¹ H-NMR (CDCl ₃ , ppm): δ 7.99 (m, 4H), 7.58-7.41 (m, 22H), 7.07 (d, 4H), 7.04 (m, 1H), 5.21 (s, 4H), 3.95 (s, 3H), 3.91 (s, 6H)

Scheme 27

Example 28:

[B-2] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 27. Yield 84%.

FT-IR (KBr, cm ⁻¹ ): 1720 (ν _{c = o} ), 1606, 1244 (ν _co ); ¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.45 (m, 22H), 7.09 (d, 4H), 7.04 (m, 1H), 5.20 (s, 4H), 3.95 (s, 3H), 3.91 (s, 6H)

Scheme 28

Example 29:

[C-2] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 27. Yield is 88%.

FT-IR (KBr, cm ⁻¹ ): 1721 (ν _{c = o} ), 1606, 1243 (ν _co ); ¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.53-7.45 (m, 26H), 7.12 (d, 4H), 7.03 (m, 1H), 5.20 (s, 4H), 3.95 (s, 3H), 3.91 (s, 6H)

Scheme 29

Example 30:

[A-2] ₂ -CO ₂ Production method of H

[A-2] ₂ -CO ₂ Me (1.90 g, 2.34 mmol) and KOH (1.05 g, 18.70 mmol) were dissolved in 26 mL of a mixed solution of ethanol and water (10: 3), followed by stirring at 120 ° C. for 4 hours. The temperature is then lowered to room temperature. Hydrochloric acid is added to the reaction to bring the pH to 1. The solid formed is washed several times with water. Yield 93%.

FT-IR (KBr, cm ⁻¹ ): 3300, 1690 (ν _{c = o} ), 1246 (ν _co ); ¹ H NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.45 (m, 22H), 7.09 (d, 4H), 7.04 (m, 1H), 5.22 (s, 4H), 3.91 ( s, 6 H)

Scheme 30

Example 31:

[B-2] ₂ -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 30. Yield is 95%.

FT-IR (KBr, cm ⁻¹ ): 3300, 1692 (ν _{c = o} ), 1247 (ν _co ); ¹ H NMR (CDCl ₃ , ppm): δ 8.02 (m, 4H), 7.65-7.40 (m, 22H), 7.12 (d, 4H), 7.08 (m, 1H), 5.25 (s, 4H), 3.94 ( s, 6 H)

Scheme 31

Example 32:

[C-2] ₂ -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 30. Yield is 90%.

FT-IR (KBr, cm ⁻¹ ): 3200, 1690 (ν _{c = o} ), 1244 (ν _co ); ¹ H NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.53-7.45 (m, 26H), 7.12 (d, 4H), 7.03 (m, 1H), 5.22 (s, 4H), 3.91 ( s, 6 H)

Scheme 32

Example 33:

[A-4] ₂ -CO ₂ Manufacturing Method of Me

[A-2] ₂ -CO ₂ Me (1.50 g, 1.845 mmol) was dissolved in 100 mL CH ₂ Cl ₂ , cooled to -78 ° C under nitrogen stream, and BBr ₃ (1.05 mL, 11.071 mmol) was added slowly. do. The mixture is stirred at room temperature for 24 hours and neutralized with NaHCO ₃ .

The product is extracted with chloroform and dried over anhydrous magnesium sulfate, and then purified by column chromatography (silica, eluent, 2% MeOH / CHCl ₃ ). Yield 94%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.61 (bs, 2H), 7.92 (m, 4H), 7.58-7.41 (m, 22H), 7.04 (m, 1H), 6.97 (d, 4H) , 5.21 (s, 4 H), 3.95 (s, 3 H); MS (EI) m / z 784.0 (M +)

Scheme 33

Example 34:

[B-4] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 33. Yield is 96%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.60 (bs, 2H), 7.95 (m, 4H), 7.53-7.35 (m, 22H), 7.04 (m, 1H), 6.95 (d, 4H) , 5.21 (s, 4 H), 3.95 (s, 3 H); MS (EI) m / z 784.0 (M +)

Scheme 34

Example 35:

[C-4] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 33. Yield is 92%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 9.66 (bs, 2H), 8.05 (m, 4H), 7.50-7.30 (m, 26H), 7.05 (m, 1H), 6.95 (d, 4H) , 5.20 (s, 4 H), 3.95 (s, 3 H); MS (EI) m / z 884.0 (M +)

Scheme 35

Example 36:

Manufacturing Method of [G-2]-[A-4]

To 100 mL of acetone, add A-4 (2.90 g, 9.350 mmol), [G-2] -Br (8.31 g, 10.286 mmol), and potassium carbonate (12.9 g, 93.510 mmol), and reflux and stir at 70 ° C. for 24 hours. . The mixture is extracted with ether, dried over anhydrous sodium sulfate and purified via column chromatography (silica, eluent, CH ₂ Cl ₂ ). Yellow liquid with a yield of 92%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.92 (m, 2H), 7.50-7.30 (m, 30H), 6.95 (d, 2H), 6.70-6.51 (m, 9H), 5.02 (d, 14H) , 2.41 (s, 3 H); MALDI-TOF (M + Na) 1060; UV-Vis absorption (λ _max , CHCl ₃ ): 285 nm and 308 nm; Photoluminescence (λ _max , CHCl ₃ ): 390 nm

Scheme 36

Example 37:

([G-2]-[B-4]) Preparation Method

Synthesis was carried out in the same manner as in Example 36. Yield 94%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.90 (m, 2H), 7.79 (d, 2H), 7.55-7.28 (m, 28H), 6.94 (d, 2H), 6.70-6.50 (m, 9H) , 5.01 (d, 14 H), 2.41 (s, 3 H); MALDI-TOF (M + Na) 1060; UV-Vis absorption (λ _max , CHCl ₃ ): 284 nm and 308 nm; Photoluminescence (λ _max , CHCl ₃ ): 390 nm

Scheme 37

Example 38:

[G-2]-[C-4] Manufacturing Method

Synthesis was carried out in the same manner as in Example 36. Yield is 86%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.85 (m, 2H), 7.80 (d, 2H), 7.55-7.28 (m, 30H), 6.97 (d, 2H), 6.69-6.51 (m, 9H) , 5.01 (d, 4H), 2.41 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 402 nm, photoluminexcence (λ _max , nm, CHCl ₃ ): 435 nm

Scheme 38

Example 39:

Manufacturing Method of [G-2]-[A-4]

Synthesis was carried out in the same manner as in Example 9. Yield is 55%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 2H), 7.55-7.28 (m, 30H), 7.12 (d, 2H), 6.70-6.50 (m, 9H), 5.04 (d, 14H)

Scheme 39

Example 40:

Manufacturing Method of [G-2]-[B-4]

Synthesis was carried out in the same manner as in Example 9. Yield is 55%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.93 (m, 2H), 7.79 (d, 2H), 7.65-7.32 (m, 28H), 7.10 (d, 2H), 6.75-6.50 (m, 9H) , 5.01 (d, 14H)

Scheme 40

Example 41:

[G-2]-[C-4] -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 9. Yield is 55%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.88 (m, 2H), 7.85 (d, 2H), 7.55-7.30 (m, 30H), 7.05 (d, 2H), 6.69-6.51 (m, 9H) , 5.05 (d, 4H)

Scheme 41

Example 42:

[G-2]-[A-4] -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 18. Yield is 75%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.92 (m, 2H), 7.50-7.30 (m, 30H), 6.95 (d, 2H), 6.70-6.51 (m, 9H), 5.02 (d, 14H) , 4.60 (s, 2H)

Scheme 42

Example 43:

Method for preparing [G-2]-[B-4] -CH2Br

Synthesis was carried out in the same manner as in Example 18. Yield 68%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.87 (m, 2H), 7.79 (d, 2H), 7.55-7.28 (m, 28H), 6.94 (d, 2H), 6.70-6.50 (m, 9H) , 5.01 (d, 14H), 4.61 (s, 2H)

Scheme 43

Example 44:

[G-2]-[C-4] -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 18. Yield is 82%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.85 (m, 2H), 7.80 (d, 2H), 7.55-7.28 (m, 30H), 6.97 (d, 2H), 6.69-6.51 (m, 9H) , 5.01 (d, 14H), 4.61 (s, 2H)

Scheme 44

Example 45:

Manufacturing Method of [G-2]-[A-5]

Synthesis was carried out in the same manner as in Example 36. Yield is 90%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.50 (d, 2H), 7.72 (d, 2H), 7.55-7.38 (m, 28H), 6.95 (d, 2H), 6.70-6.50 (m, 9H) , 5.02 (d, 14 H); UV-Vis absorption (λ _max , CHCl ₃ ): 287 nm and 303 nm, photoluminescence (λ _max , CHCl ₃ ): 379 nm

Scheme 45

Example 46:

Manufacturing Method of [G-2]-[B-5]

Synthesis was carried out in the same manner as in Example 36. Yield 94%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.39 (d, 2H), 7.90-7.80 (m, 2H), 7.72 (d, 2H), 7.51-7.30 (m, 26H), 6.95 (d, 2H) , 6.70-6.50 (m, 9H), 5.01 (d, 14H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 302 nm; Photoluminescence (λ _max , CHCl ₃ ): 380 nm

Scheme 46

Example 47:

Manufacturing Method of [G-2]-[C-5]

Synthesis was carried out in the same manner as in Example 36. Yield is 95%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.51 (d, 2H), 7.70 (d, 2H), 7.62-7.50 (m, 4H), 7.48-7.30 (m, 26H), 6.95 (d, 2H) , 6.71-6.50 (m, 9H), 5.01 (d, 14H); UV-Vis absorption (λ _max , CHCl ₃ ): 287 nm and 394 nm; Photoluminescence (λ _max , CHCl ₃ ): 435 nm

Scheme 47

Example 48:

[G-2]-[A-5] -NH ₂ Manufacturing Method

Dissolve [G-2]-[A-5] (6.3 g 5.9 mmol) and 10% -Pd / C in CH ₂ Cl ₂ (50 mL) and ethanol (20 mL) in a pressurized hydrogen reactor. The reaction vessel is maintained at 40 psi hydrogen pressure and stirred at room temperature for 20 hours.

After the reaction is completed, the solvent is removed under reduced pressure after filtration of Pd / C. The concentrated material is separated by flash column chromatography (silica, hexane / ethyl acetate = 1/2) and then dried under vacuum.

¹ H-NMR (CDCl ₃ , ppm): δ 7.55-7.38 (m, 28H), 7.22 (d, 2H), 6.93 (d, 2H), 6.81 (d, 2H), 6.70-6.51 (m, 9H) , 5.02 (d, 14 H), 4.0-3.5 (b, 2H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 312 nm; Photoluminescence (λ _max , CHCl ₃ ): 393 nm

Scheme 48

Example 49:

[G-2]-[B-5] -NH ₂ Manufacturing Method

Synthesis was carried out in the same manner as in Example 48. Yield is 95%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.91-7.80 (m, 2H), 7.51-7.30 (m, 26H), 7.22 (d, 2H), 6.93 (d, 2H), 6.72-6.51 (m, 11H), 5.01 (d, 14H), 4.0-3.5 (b, 2H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 312 nm; Photoluminescence (λ _max , CHCl ₃ ): 392 nm

Scheme 49

Example 50:

[G-2]-[C-5] -NH ₂ Manufacturing Method

Synthesis was carried out in the same manner as in Example 48. Yield 91%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.62-7.50 (m, 4H), 7.46-7.30 (m, 26H), 7.20 (d, 2H), 6.95 (d, 2H), 6.81 (d, 2H) , 6.69-6.501 (m, 9H), 5.02 (d, 14H), 4.01-3.50 (b, 2H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 402 nm; Photoluminescence (λ _max , CHCl ₃ ): 435 nm

Scheme 50

Example 51:

[G-2]-[A-4] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 27. Yield is 90%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 7.92 (m, 4H), 7.58-7.31 (m, 42H), 7.04 (m, 1H), 6.97 (d, 4H), 6.7-6.5 (m, 9H), 5.21 (s, 4H), 5.01 (d, 14H), 3.95 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 286 nm and 309 nm; Photoluminescence (λ _max , CHCl ₃ ): 390 nm

Scheme 51

Example 52:

[G-2]-[B-4] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 27. Yield 94%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.35 (m, 42H), 7.04 (m, 1H), 6.70-6.51 (m, 13H), 5.21 (s, 4H) , 5.01 (d, 14 H), 3.94 (s, 3 H); UV-Vis absorption (λ _max , CHCl ₃ ): 285 nm and 308 nm; Photoluminescence (λ _max , CHCl ₃ ): 390 nm

Scheme 52

Example 53:

[G-2]-[C-4] ₂ -CO ₂ Manufacturing Method of Me

Synthesis was carried out in the same manner as in Example 27. Yield is 85%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.50-7.30 (m, 46H), 7.04 (m, 1H), 6.95 (d, 4H), 6.70-6.51 (m, 9H) , 5.21 (s, 4H), 5.0 (d, 14H), 3.95 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 287 nm and 405 nm; Photoluminescence (λ _max , CHCl ₃ ): 436 nm

Scheme 53

Example 54:

[G-2]-[A-4] ₂ -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 30. Yield is 95%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 8.02 (m, 4H), 7.63-7.35 (m, 42H), 7.14 (m, 1H), 7.10 (d, 4H), 6.75-6.52 (m, 9H), 5.25 (s, 4H), 5.03 (d, 14H)

Scheme 54

Example 55:

[G-2]-[B-4] ₂ -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 30. Yield 93%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.03 (m, 4H), 7.62-7.41 (m, 42H), 7.12 (m, 1H), 6.75-6.55 (m, 13H), 5.22 (s, 4H) , 5.01 (d, 14H)

Scheme 55

Example 56:

[G-2]-[C-4] ₂ -CO ₂ Production method of H

Synthesis was carried out in the same manner as in Example 30. Yield is 97%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.68-7.35 (m, 46H), 7.11 (m, 1H), 6.97 (d, 4H), 6.75-6.55 (m, 9H) , 5.25 (s, 4H), 5.10 (d, 14H)

Scheme 56

Example 57:

[A-2] ₂ -CH ₂ OH production method

[A-2] ₂ -CO ₂ Me (1.75 g, 2.152 mmol) is dissolved in THF (45 mL) and LiAlH ₄ (0.245 g, 6.458 mmol) is slowly added with stirring. When the addition is complete, the reaction mixture is stirred at room temperature for 1 hour. Appropriate amount of water is added to terminate the reaction and THF is removed under reduced pressure. Diethyl ether and water are further added, the organic layer is extracted, and the obtained organic layer is washed with water and brine. The organic layer is dried over anhydrous sodium sulfate, and then purified by column chromatography (silica, reaction by-products are removed with eluent 10% diethyl ether / CH ₂ Cl ₂ and purified once more with eluent diethyl ether). Yield is 80%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.99 (m, 4H), 7.58-7.41 (m, 22H), 7.07 (d, 4H), 7.04 (m, 1H), 5.21 (s, 4H), 4.75 (s, 2H), 3.91 (s, 6H)

Scheme 57

Example 58:

[B-2] ₂ -CH ₂ OH production method

Synthesis was carried out in the same manner as in Example 57. Yield is 81%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.45 (m, 22H), 7.09 (d, 4H), 7.04 (m, 1H), 5.20 (s, 4H), 4.75 (s, 2H), 3.91 (s, 6H)

Scheme 58

Example 59:

[C-2] ₂ -CH ₂ OH production method

Synthesis was carried out in the same manner as in Example 57. Yield is 79%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.53-7.45 (m, 26H), 7.12 (d, 4H), 7.03 (m, 1H), 5.20 (s, 4H), 4.75 (s, 2H), 3.91 (s, 6H)

Scheme 59

Example 60:

[A-2] ₂ -CH ₂ Preparation of Br

[A-2] Dissolve _2- CH ₂ OH (1.21 g, 1.541 mmol) and carbone tertrabromide (0.639 g, 1.927 mmol) in THF (15 mL). To this mixture triphenylphosphine (0.505 g, 1.927 mmol) is added. Under nitrogen stream, the mixture is stirred at room temperature for 20 minutes and the reaction is continued at 10 minute intervals until no starting material appears in TLC. After completion of the reaction, the mixture is poured into water, and the organic layer is extracted with methylene chloride (× 3). After drying over anhydrous magnesium sulfate, a white solid recrystallized from toluene / hexane (4/1) was obtained. Yield 91%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.99 (m, 4H), 7.58-7.41 (m, 22H), 7.07 (d, 4H), 7.04 (m, 1H), 5.21 (s, 4H), 4.41 (s, 2H), 3.91 (s, 6H)

Scheme 60

Example 61:

[B-2] ₂ -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 60. Yield 89%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.45 (m, 22H), 7.09 (d, 4H), 7.04 (m, 1H), 5.20 (s, 4H), 4.40 (s, 2H), 3.91 (s, 6H)

Scheme 61

Example 62:

[C-2] ² -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 60. Yield is 87%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.53-7.45 (m, 26H), 7.12 (d, 4H), 7.03 (m, 1H), 5.20 (s, 4H), 4.41 (s, 2H), 3.91 (s, 6H)

Scheme 62

Example 63:

[G-2]-[A-4] ₂ -CH ₂ OH production method

Synthesis was carried out in the same manner as in Example 57. Yield is 85%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 7.92 (m, 4H), 7.58-7.31 (m, 42H), 7.04 (m, 1H), 6.97 (d, 4H), 6.7-6.5 (m, 9H), 5.21 (s, 4H), 5.01 (d, 14H), 4.77 (s, 2H)

Scheme 63

Example 64:

[G-2]-[B-4] ₂ -CH ₂ OH production method

Synthesis was carried out in the same manner as in Example 57. Yield is 83%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.35 (m, 42H), 7.04 (m, 1H), 6.70-6.51 (m, 13H), 5.21 (s, 4H) , 5.01 (d, 14 H), 4.75 (s, 3 H).

Scheme 64

Example 65:

[G-2]-[C-4] ₂ -CH ₂ OH production method

Synthesis was carried out in the same manner as in Example 57. Yield is 81%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.50-7.30 (m, 46H), 7.04 (m, 1H), 6.95 (d, 4H), 6.70-6.51 (m, 9H) , 5.21 (s, 4H), 5.0 (d, 14H), 4.76 (s, 3H).

Scheme 65

Example 66:

[G-2]-[A-4] ₂ -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 60. Yield is 90%.

¹ H-NMR (DMSO-d ₆ , ppm): δ 7.92 (m, 4H), 7.58-7.31 (m, 42H), 7.01 (m, 1H), 6.97 (d, 4H), 6.7-6.5 (m, 9H), 5.21 (s, 4H), 5.01 (d, 14H), 4.40 (s, 2H)

Scheme 66

Example 67:

[G-2]-[B-4] ₂ -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 60. Yield 89%.

¹ H-NMR (CDCl ₃ , ppm): δ 7.95 (m, 4H), 7.53-7.35 (m, 42H), 7.04 (m, 1H), 6.70-6.51 (m, 13H), 5.21 (s, 4H) , 5.01 (d, 14H), 4.41 (s, 3H)

Scheme 67

Example 68:

[G-2]-[C-4] ₂ -CH ₂ Preparation of Br

Synthesis was carried out in the same manner as in Example 60. Yield is 92%.

¹ H-NMR (CDCl ₃ , ppm): δ 8.05 (m, 4H), 7.50-7.30 (m, 46H), 7. band (m, 1H), 6.95 (d, 4H), 6.70-6.51 (m, 9H), 5.21 (s, 4H), 5.0 (d, 14H), 4.39 (s, 3H)

Scheme 68

Example 69:

[A-2]-[C-2] Manufacturing Method

A-1 (0.5 molar ratio), C-1 (0.5 molar ratio), p-tolylboronic acid (1.2 molar ratio), and Pd (PPh ₃ ) ₄ (3 mol%) were synthesized in the same manner as in Example 6. The yield is 37% for A-2 and 42% for C-2.

¹ H-NMR (CDCl ₃ , ppm): δ 8.10-8.05 (m, 4H), 7.62-7.40 (m, 18H), 7.39-7.37 (dd, 4H), 7.10 (d, 4H), 3.95 (s, 3H), 3.93 (s, 3H), 2.53 (s, 3H), 2.50 (s, 3H); UV-Vis absorption (λ _max , CHCl ₃ ): 308 nm, 380 nm and 400 nm; Photoluminescence (λ _max , CHCl ₃ ): 385 nm and 430 nm

Scheme 69

In the present invention, by designing and synthesizing various optical amplification optical antennas using molecular engineering, the light condensing effect using efficient energy transfer and the effect of removing solvents and water causing non-luminescent transition from rare earth complex compounds can be expected.

Claims (4)

High efficiency dendrimer-type light collecting antenna compound having the following [Formula 1] that can maximize the energy transfer effect by the light collecting effect. [Formula 1] X ₁ and X ₂ are each selected from CH ₃ , CO ₂ H, CH ₂ Br, NO ₂ , NH ₂ , OCH ₃ , and OH . High efficiency dendrimer-type light collecting antenna compound having the following [Formula 2] that can maximize the energy transfer effect by the light collecting effect. [Formula 2] High efficiency dendrimer-type light collecting antenna compound having the following [Formula 3] to maximize the energy transfer effect by the light collecting effect [Formula 3] Light antenna compound for light amplification having the following [Formula 4] that can maximize the energy transfer effect by the light condensing effect [Chemical Structural Formula 4]