Dibenzo[g,p]chrysene derivatives

Abstract

4H-benzo[p]indeno[7,1,2-ghi]chrysen-4-one is synthesized, and the reactivity of the carbonyl group of this compound is clarified to synthesize 4,4'-(4H-benzo[p]indeno[7,1,2-ghi]chrysen-4,4-diyl)diphenol. [Solution] The present invention is based on the following formula: [C1] JPEG2026084409000037.jpg24115 This relates to compounds represented by [the specified formula / method].

Description

Technical Field

[0001] The present invention relates to dibenzo[g,p]chrysene derivatives, and particularly to dibenzo[g,p]chrysene compounds having a cardo-type bisphenol structure.

Background Art

[0002] 4,4'-Bibenzo[p]indeno[7,1,2-ghi]chrysenylidene has 12 six-membered rings and 2 five-membered rings, and is a fragment corresponding to a partial structure having 90% of the carbon atoms of buckminsterfullerene C60 (see the following chemical formula). It is a polycyclic aromatic hydrocarbon (PAHs) having a typical non-planar π-conjugated system structure and is an organic molecule with 54 carbon atoms. Since it is a fragment structure of C60, it is expected to have properties similar to those of organic electronics materials and organic semiconductor materials similar to C60. Also, since it is a partial structure of C60, it is expected to have various possibilities as carbon materials.

[0003]

Chem.

[0004] However, there has been no report on synthesis so far (as of September 17, 2024). When it comes to buckyballs or C60 fragments, coronylene (1966), torquene (1984), and sumanene (2*** are well-known.

[0005] The synthesis of 4,4'-bibenzo[p]indeno[7,1,2-ghi]chrysenylidene ideally involves the dimerization of the 27-carbon ketone 4H-benzo[p]indeno[7,1,2-ghi]chrysen-4-one. However, at present, 4H-benzo[p]indeno[7,1,2-ghi]chrysen-4-one has not been synthesized nor reported.

[0006]

Chem.

[0007] Patent Document 1 discloses dibenzochrysene compounds derived from the homodimerization of fluorenone, the highly symmetrical diketone bodies obtained therefrom, and phenolic tetrol compounds prepared therefrom. However, 4H-benzo[p]indeno[7,1,2-ghi]chrysen-4-one is not disclosed. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Patent Application No. 2024-100126 [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention aims to synthesize 4H-benzo[p]indeno[7,1,2-ghi]chrysen-4-one and to clarify the reactivity of the carbonyl group of the compound in order to synthesize 4,4'-(4H-benzo[p]indeno[7,1,2-ghi]chrysen-4,4-diyl)diphenol. [Means for solving the problem]

[0010] In other words, the present invention (1) is given by the following formula: [ka] It is a compound represented by [formula].

[0011] The present invention (2) is based on the following general formula: [ka] (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is hydrogen or a halogen group, and the two Xs may be the same or different. A is a halogen group, a hydroxyl group, or an alkyl ether group having 1 to 12 carbon atoms.) It is a compound represented by [formula].

[0012] The present invention (3) is given by the following formula: [ka] [ka] or [ka] This is the compound described in (2) of the present invention, represented by [formula].

[0013] The present invention (4) is based on the following general formula: [ka] (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is a hydrogen atom or a halogen group, and the two Xs may be the same or different.) It is a compound represented by [formula].

[0014] The present invention (5) is based on the following formula: [ka] [ka] or [ka] This is the compound described in (4) of the present invention, represented by [formula].

[0015] The present invention (6) is given by the following formula: [ka] It is a compound represented by [formula]. [Effects of the Invention]

[0016] The compound of the present invention is a dibenzo[g,p]chrysene compound having a cardioid bisphenol structure. Due to its cardioid structure, it is expected to exhibit a high refractive index, low Abbe number, and low birefringence. Furthermore, it can be introduced into the main chain or side chain of polymer compounds using hydroxyl groups, which not only leads to the simple creation of excellent electronic and optical materials but also to the creation of new carbon materials such as graphene fragment structures. [Modes for carrying out the invention]

[0017] The first compound of the present invention is given by the following formula: [ka] It is characterized by being represented as follows. The IUPAC name of the compound is 4,4'-(4H-benzo[p]indeno[7,1,2-ghi]chrysene-4,4-diyl)diphenol. Due to its cardo structure, a high refractive index, low Abbe number, and low birefringence can be expected. Furthermore, it can be introduced into the main chain or side chain of polymer compounds using the hydroxyl group, which will not only lead to the simple creation of excellent electronic and optical materials, but also to the creation of new carbon materials such as graphene fragment structures.

[0018] Here, dibenzo[g,p]chrysene has the following chemical formula [ka] This is a compound represented by [formula]. The substitution positions of each carbon are shown in the figure.

[0019] The first compound of the present invention can be synthesized according to the following scheme. Spiroketone 1 is synthesized using the cross-dimerization reaction of fluorenone previously invented by the present inventors (see Japanese Patent Publication No. 2023-070620). Subsequently, it is converted to the synthetic intermediates ester 2, carboxylic acid 3, acid chloride 4, ketone 5, dehalogenated product 6, and dealkylated product 7. Compound 8, the first compound of the present invention, is obtained by reacting the obtained dealkylated product 7 with phenol.

[0020] [ka] JPEG2026084409000016.jpg20115

[0021] Synthesis of Compound 1 The method for cross-dimerizing two fluorenone derivatives to synthesize compound 1, a spiroketone derivative, is not particularly limited, but a method carried out in the presence of a Lewis base reagent with high oxygen affinity, such as trialkyl phosphite, is preferred. The amount of the activating reagent, such as trialkyl phosphite, is preferably 2 equivalents or more. The reaction temperature is not particularly limited, but 90 to 200°C is preferred.

[0022] Synthesis of Compound 2 Compound 2 can be prepared by reducing Compound 1 with a reducing agent such as sodium borohydride or hydrogen, and then cyclizing it with an acidic reagent such as methanesulfonic acid, hydrochloric acid, dilute sulfuric acid, or a solid acid.

[0023] Synthesis of Compound 3 Compound 3 can be synthesized by hydrolyzing Compound 2 with an alkaline agent such as potassium tertial butyl, sodium tertial butyl, sodium hydroxide, or potassium hydroxide.

[0024] Synthesis of Compound 4 Compound 4 can be synthesized by converting the carboxyl group of compound 3 to an acid halide group using a halogenating agent such as thionyl chloride, phosphorus trichloride, or phosphorus pentachloride.

[0025] Synthesis of Compound 5 Compound 5 can be synthesized by cyclizing Compound 4 in the presence of a Lewis acid such as aluminum trichloride, boron trifluoride, iron trichloride, or zero-valent iron, or a Brønsted acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid, or trifluoroacetic acid to form a five-membered ring.

[0026] Synthesis of Compound 6 Compound 6 can be synthesized by dehalogenating compound 5 in an alcohol solvent such as 2-butanol with triphenylphosphine, a catalyst such as palladium acetate, and a basic reagent such as potassium carbonate.

[0027] Synthesis of Compound 7 Compound 7 can be synthesized by dealkylating compound 6 with a Lewis acid such as aluminum trichloride, boron tribromide, ethylaluminum dichloride, boron trifluoride, boron tribromide, iron trichloride, or zero-valent iron.

[0028] Synthesis of compound 8 Compound 8, the first compound of the present invention, can be synthesized by reacting compound 7 with a phenol compound under acidic conditions in the presence of a Brønsted acid such as methanesulfonic acid, toluenesulfonic acid, trifluoroacetic acid, hydrochloric acid, concentrated sulfuric acid, or dilute sulfuric acid.

[0029] The second compound of the present invention has the following general formula: [ka] (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is hydrogen or a halogen group, and the two Xs may be the same or different. A is a halogen group, a hydroxyl group, or an alkyl ether group having 1 to 12 carbon atoms.) It is characterized by being represented in this way.

[0030] R is an alkyl group having 1 to 12 carbon atoms, but an alkyl group having 1 to 6 carbon atoms is preferred. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. These alkyl groups may have a branched structure.

[0031] X is a halogen group, such as a fluoro group, chloro group, bromo group, or iodine group, among which the bromo group is preferred in terms of compound stability and availability of the reagent.

[0032] A is a halogeno group, a hydroxyl group, or an alkyl ether group having 1 to 12 carbon atoms. Examples of halogeno groups include a fluoro group, a chloro group, a bromo group, and an iodo group, with the chloro group being preferred in terms of compound stability and the availability of reagents. The alkoxy group having 1 to 12 carbon atoms preferably has 1 to 8 carbon atoms. These alkyl ether groups may have a branched structure. Examples include methyl ether group, ethyl ether group, n-propyl ether group, iso-propyl ether group, n-butyl ether group, 2-methylpropyl ether group, n-pentyl ether group, 2,2-dimethylpropyl ether group, n-hexyl ether group, n-heptyl ether group, n-octyl ether group, n-nonyl ether group, n-decyl ether group, n-undecyl ether group, n-dodecyl ether group, etc., and also examples include methyl ether group, ethyl ether group, n-propyl ether group, n-butyl ether group, 2-methylpropyl ether group, n-pentyl ether group, 2,2-dimethylpropyl ether group, n-hexyl ether group.

[0033] The second compound of the present invention is given by the following formula: [ka] [ka] or [ka] Compounds represented by are preferred.

[0034] The second compound of the present invention is an intermediate produced in the synthesis process of the first compound of the present invention, and can be synthesized by the synthesis methods of compounds 2 to 4 described in the synthesis method of the first compound of the present invention.

[0035] The third compound of the present invention has the following general formula: [ka] (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is a hydrogen atom or a halogen group, and the two Xs may be the same or different.) It is characterized by being represented in this way.

[0036] R is an alkyl group having 1 to 12 carbon atoms, but an alkyl group having 1 to 6 carbon atoms is preferred. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. These alkyl groups may have a branched structure.

[0037] X is a halogen group, such as a fluoro group, chloro group, bromo group, or iodine group, among which the bromo group is preferred in terms of compound stability and availability of the reagent. The second compound of the present invention is given by the following formula:

[0038] [ka] [ka] [ka] It is preferable.

[0039] The third compound of the present invention is an intermediate produced in the synthesis process of the first compound of the present invention, and can be synthesized by the synthesis methods of compounds 5 to 7 described in the synthesis method of the first compound of the present invention.

[0040] The fourth compound of the present invention is given by the following formula: [ka] The compound is characterized by being represented as shown. The compound can be synthesized using a cross-dimerization reaction of fluorenone and fluorenone having a -COA group (see Japanese Patent Publication No. 2023-070620).

[0041] The dibenzo[g,p]chrysene compound having a cardioid bisphenol structure according to the present invention is applicable to the fields of polymer materials, high heat-resistant resins, optical functional materials, electronic materials, organic electronics materials, chemical sensor materials, high-performance carbon materials, molecular nanocarbon materials, and graphene nanoribbon materials. Specifically, examples include low transmission loss substrate materials, raw materials for low dielectric and photoadhesive polyimide resins, lithography materials, resist materials, organic EL materials, resin materials such as adhesives, materials for super engineering plastics, organic semiconductor materials, materials for organic batteries, and flexible printed circuit boards. In particular, it can be applied as a hole transport material for thin-film transistors, a light-emitting element for organic light-emitting diodes, or a compound of their precursors. Furthermore, due to its high refractive index, it can be applied as a high refractive index material such as plastic lenses and as an optical material. [Examples]

[0042] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0043] In the examples, the water-restricted reactions were carried out under an argon or nitrogen atmosphere, and unless otherwise specified, the experiments were conducted under water-restricted conditions. The purchased anhydrous solvents and reagents were used without further purification to improve their purity. Merck silica 60F was used for thin-layer chromatography. 254Using silica gel 60 as column chromatography N (Manufactured by Kanto Chemical Co., Ltd.) was used. For high-resolution mass spectrometry (HRMS), either time-of-flight mass spectrometry (MALDI-TOF or LCMS-IT-TOF) or direct mass spectrometry (DART-MS) was used.

[0044] 1 H-NMR, 13 For the 1C-NMR spectra, a 5mm QNP probe was used, and measurements were taken at 400MHz and 100MHz, respectively. Chemical shift values ​​are shown as δ (ppm), and the reference values ​​in each solvent are as follows: 1 H-NMR: CHCl3 (7.26), CH2Cl2 (5.32), DMSO (2.50); 13 ¹

[0045] Compounds 1-8 were synthesized according to the following scheme. All were confirmed to be novel compounds using SciFinder. The structure of compound 7 was determined based on X-ray analysis. Compound 1 corresponds to the fourth compound of the present invention, compounds 2-4 to the second compounds of the present invention, compounds 5-7 to the third compounds of the present invention, and compound 8 to the first compound of the present invention.

[0046] [ka]

[0047] Example 1 (Synthesis of Compound 1) Under an argon atmosphere, the starting material methyl ester (12 g, 34 mmol), the starting material brominated (23 g, 69 mmol), and triisopropyl phosphite were added to a flask. This mixture was stirred overnight at an internal temperature of 110°C, then cooled to 60°C. Distilled water was added dropwise, and the temperature was raised again to 80°C. After stirring for several hours, the mixture was allowed to cool naturally to room temperature, diluted with toluene, and the organic layer was separated. Extraction was performed on the aqueous layer, and the combined organic layers were washed with saturated brine, dried with Glauber's salt, and vacuum-dried to obtain an orange oily substance. Purification by silica gel filtration column was performed to obtain 26 g (Quant.) of the target product as an orange solid.

[0048] Data for Compound 1 Data: Mp221-224℃; 1 HNMR(400MHz,CDCl3)8.27(d,J=8.4Hz,1H,H-5),8.07(d,J=2.0Hz,1H,H-1'),8.02(d,J=8.6Hz,1H,H- 4'),7.91(d,J=8.4Hz,1H,H-5'),7.90(dd,J=8.6Hz,2.0Hz,1H,H-3'),7.87(d,J=2.0Hz,1H,H-3),7.51 (dd,J=8.4,1.9Hz,1H,H-6'),7.41(dd,J=8.4,1.9Hz1H,H-6),7.16(d,J=2.0Hz,1H,H-1),6.93(d,J=1 .9Hz,1H,H-8),6.74(d,J=1.9Hz,1H,H-8'),4.04(s,3H,OCH3),1.23(s,9H,CH3),1.16(s,9H,CH3)ppm; 13CNMR (100 MHz, CDCl3) 195.1 (C-10’, C=O), 168.5 (CO2CH3), 151.9 (C-7), 150.6 (C-2), 147.5 (C-8a’), 146.3 (C-8a), 141.5 (C-3’), 138.6 (C-9a), 137.4 (C-5), 137.1 (C-10a’), 136.2 (C-4b), 131.5 (C-1’), 131.4 (C-8’), 131.2 (C-4a, C-4a’, two peaks are overlapped), 129.0 (C-4), 127.7 (C-1), 126.2 (C-5’), 126.0 (C-4b’), 125.6 (C-6’), 125.4 (C-7’), 125.2 (C-2’), 124.9 (C-8), 123.7 (C-3), 122.8 (C-6), 120.8 (C-4’), 67.9 (C-9), 52.3 (OCH3), 34.83 (C(CH3)3), 34.79 (C(CH3)3), 31.18 (CH3), 31.16 (CH3) ppm; MS (DART-TOFMS) m / z: 670 [M] + ; IR (neat): 2952, 1717 (C=O), 1677 (C=O), 1589, 1461, 1292, 1245, 1225, 1153, 810, 798, 742 cm -1 ; HRMS (DART-TOFMS) calcd for C 36 H 32 Br(79)2O3: 670.0718 [M] + , found; 670.0713; Anal. Calcd for C 36 H 32 Br2O3; C, 64.30; H, 4.80. Found: C, 64.44; H, 4.86.

[0049] Example 2 (Synthesis of Compound 2) Under an argon atmosphere, the starting material spiroketone (21 g, 31 mmol), toluene, and methanol were added to a flask and immersed in an oil bath heated to 45°C. Sodium borohydride (480 mg, 13 mmol) was slowly added, and the mixture was stirred for 30 minutes. Acetone was added to inactivate the excess reducing agent, and the mixture was allowed to cool naturally to room temperature. The organic layer was washed with water, transferred to a flask, and azeotropically removed with water. Then, methanesulfonic acid (0.02 mL, 0.31 mmol) was added, and the mixture was stirred for 30 minutes. After the reaction solution cooled naturally to room temperature, the organic layer was washed with saturated brine, dried with Glauber's salt, vacuum dried, and then concentrated to remove the reducing agent. The solution was purified by silica gel filtration column to obtain 20 g (93%) of the target product as an orange solid.

[0050] Data for Compound 2 Data: Mp331-334℃; 1 HNMR(400MHz,CDCl3)8.91(d,J=1.9Hz,1H,H-4),8.75(d,J=1.9Hz,1H,H-5),8.73(d ,J=1.9Hz,1H,H-12),8.56(d,J=1.8Hz,1H,H-13),8.51(d,J=8.8Hz,2H,H-8,H-9,two peaks are overlapped),8.04(d,J=8.6Hz,1H,H-16),7.87(d,J=1.9Hz,1H,H-2),7.79(dd,J=8.8,1.9Hz,1H,H-7),7.77(dd,J= 8.8,1.9Hz,1H,H-10),7.63(dd,J=8.6,1.8Hz,1H,H-15),4.01(s,3H,OCH3),1.48(s,9H,CH3),1.45(s,9H,CH3)ppm; 13CNMR(100MHz, CDCl3) 172.7 (C=O), 150.3 (C-14), 149.2 (C-3), 131.4 (C-7), 131.3 (C-8), 130.8 (C-4c), 130.4 (C-8a), 130.3 (C-12c), 129.9 (C-9), 129.6 (C-8b, C-12a, two peaks are overlapped), 129.3 (C-16a), 129.2 (C-4b), 129.1 (C-10), 128.7 (C-12b), 127.5 (C-16), 127.2 (C-1), 127.78 (C-4a), 127.76 (C-16b), 126.4 (C-5), 126.1 (C-12), 125.2 (C-2), 125.1 (C-15), 124.7 (C-4), 124.2 (C-13), 121.1 (C-6), 121.0 (C-11), 52.7 (OCH3), 35.2 (C(CH3)3), 35.1 (C(CH3)3), 31.31 (CH3), 31.27 (CH3) ppm; MS (DART-TOFMS) m / z: 654 [M] + ; IR (neat): 2961, 1727 (C=O), 1469, 1285, 1248, 1138, 879, 798 cm -1 ; HRMS (DART-TOF) calcd. for C 36 H 32 Br(79)2O2: 654.0769 [M] + , found: 654.0796. Anal. Calcd for C 36 H 32 Br(79)2O2; C, 65.87; H, 4.91. Found: C, 65.52; H, 4.84.

[0051] Example 3 (Synthesis of Compound 3) Potassium tertoxide (14 g, 130 mmol) and anhydrous tetrahydrofuran (200 mL) were added to a flask. The solution was cooled to 0°C, distilled water was added and stirred, and then the starting ester (20 g, 30 mmol) was added. The reaction solution was heated under reflux and stirred for 1 hour, and then the reaction was stopped by adding dilute hydrochloric acid at 0°C. The organic layer was separated by dilution with ethyl acetate, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried for sodium sulfate, concentrated to remove the medium, and vacuum dried to quantitatively obtain a nearly pure crude product as a yellowish-white solid. It was subjected to the next step without further purification.

[0052] Data for Compound 3 Data: 1 HNMR(400MHz,CDCl3)8.92(d,J=1.9Hz,1H,H-4),8.79(d,J=1.9Hz,1H,H-5),8.75(d,J=1.9Hz,1H ,H-12),8.57(d,J=1.8Hz,1H,H-13),8.53(d,J=8.9Hz,1H,H-9),8.52(d,J=8.8Hz,1H,H-8),8.32 (d,J=1.9Hz,1H,H-2),8.07(d,J=8.6Hz,1H,H-16),7.80(dd,J=8.9,1.9Hz,1H,H-10),7.79(dd,J =8.8,1.9Hz,1H,H-7),7.67(dd,J=8.6,1.8Hz,1H,H-15),1.51(s,9H,CH3),1.44(s,9H,CH3)ppm; MS (DART-TOF) m / z: 640[M] + ; IR(neat):2961,2571(OH),1669(C=O),1472,1395,1291,1257,1089,753cm -1 ; HRMS(DART-TOF)calcd.for C 35 H 30 Br(79)2O2[M] + :640.0607,found:640.0609.

[0053] Example 4 (Synthesis of Compound 4) Under an argon atmosphere, a few drops of DMF were added at room temperature to a solution of the starting carboxylic acid compound (20 g, 31 mmol) in thionyl chloride (100 mL, 1.4 mol). After stirring the reaction solution for 30 minutes, the medium was removed using an evaporator, and after vacuum drying, the crude product was quantitatively obtained as a brown solid. It was then subjected to the next step without further purification.

[0054] Data for Compound 4 Data: 1 HNMR(400MHz,CDCl3)8.92(d,J=1.9Hz,1H,H-4),8.81(d,J=1.8Hz,1H,H-5),8.69(d,J=1.9Hz,1H ,H-12),8.58(d,J=1.9Hz,1H,H-13),8.53(d,J=8.9Hz,1H,H-9),8.52(d,J=8.8Hz,1H,H-8),8.25 (d,J=8.6Hz,1H,H-16),7.99(d,J=1.9Hz,1H,H-2),7.82(dd,J=8.9,1.9Hz,1H,H-10),7.79(dd,J =8.8,1.8Hz,1H,H-7),7.71(dd,J=8.6,1.9Hz,1H,H-15),1.50(s,9H,CH3),1.45(s,9H,CH3)ppm; 13 CNMR(100MHz, CDCl3)172.4(C=O),151.9(C-3),149.8(C-14),135.8(C-4c),132.1(C-7),131.8(C-10),130.9(C-8), 130.83(C-9),130.76(C-8a),130.4(C-16),130.2(C-12c),130.1(C-1),129.84(C-8b),129.80(C-12a),129.7(C-16 a),129.4(C-5),129.1(C-2),126.8(C-4b),126.5(C-12b),126.3(C-12),126.1(C-4a),126.0(C-16b),125.8(C-4), 125.4(C-15),125.3(C-13),121.9(C-6),121.7(C-11),35.9(C(CH3)3),35.8(C(CH3)3),31.9(CH3),31.8(CH3)ppm; MS (DART-TOF) m / z: 623 [M-Cl]+ ; IR(neat):2959,1766(C=O),1591,1470,1395,1362,1205,1038,912,798,741,714cm -1 ; HRMS(DART-TOF)calcd.for C 35 H 29 Br(79)2O[M-Cl] + :623.0580, found:623.0559.

[0055] Example 5 (Synthesis of Compound 5) Under an argon atmosphere, the crude crystalline acid chloride obtained in Example 4 and anhydrous methylene chloride were added to a flask. This solution was cooled to 0°C, aluminum trichloride (4.2 g, 31 mmol) was added, and the mixture was stirred for 30 minutes. The reaction was then stopped using water. The organic layer was separated by dilution with methylene chloride, and the aqueous layer was extracted with chloroform. The combined organic layers were washed with saturated brine, dried with Glauber's salt, and then vacuum-dried to obtain 18 g (91%) of the crude product.

[0056] Data for Compound 5 Data: Mp327-329℃; 1 HNMR(400MHz,CDCl3)9.09(d,J=1.9Hz,2H,H-15),8.72(d,J=0.8Hz,2H,H-3),8.55(d,J=8.8Hz, 2H,H-12),8.02(d,J=0.8Hz,2H,H-1),7.82(dd,J=8.8,1.9Hz,2H,H-13),1.51(s,18H,CH3)ppm; 13 CNMR(100MHz,CDCl3)194.2(C-4,C=O),153.3(C-2),138.0(C-3a),133.5(C-15c),131.9(C-3a1),130.9(C-12),130.3(C-13),12 8.5(C-15b),128.3(C-1),127.7(C-11b),125.2(C-15),124.3(C-15a),121.7(C-3),121.6(C-14),36.4(C(CH3)),32.0(CH3)ppm; MS (DART-TOFMS) m / z: 623 [MH] + ; IR(neat):2953,1713(C=O),1453,1362,1200,1092,902,799,677cm -1 ; HRMS(DART-TOF)calcd.for C 35 H 29 Br(79)2O[MH] + :623.0585,found:623.0582; Anal.Calcd.for C 35 H 28 Br2O;C,67.32;H,4.52.Found:C,67.28;H,4.58.

[0057] Example 6 (Synthesis of Compound 6) Under a nitrogen atmosphere, triphenylphosphine (130 mg, 0.48 mmol), palladium(II) acetate (27 mg, 0.12 mmol), compound 5 (1.2 g, 2.0 mmol), and potassium carbonate (1.7 mg, 12 mmol) were added, followed by the addition of 2-butanol. The reaction solution was immersed in a 90°C oil bath and stirred overnight, then allowed to cool naturally to room temperature. After Celite filtration, the mixed solution was transferred to a separatory funnel, washed with water and saturated brine, dried to remove Glauber's salt, and vacuum-dried to obtain a brownish-green crude product. Filtration column purification using silica gel was performed to obtain 1.6 g (83%) of the target product as a bright yellow solid.

[0058] Data for Compound 6 Data: Mp321-323℃; 1 HNMR(400MHz,CDCl3)8.91(dd,J=7.5Hz,2.2Hz,2H,H-15),8.80(dd,J=7.9Hz,1.9Hz,2H,H-12),8.77(d,J=1.1Hz,2H,H-3),7.99(d, J=1.1Hz,2H,H-1),7.77(ddd,J=7.5Hz,7.0Hz,1.9Hz,2H,H-14),7.73(ddd,J=7.9Hz,7.0Hz,2.2Hz,2H,H-13),1.51(s,18H,CH3)ppm; 13 CNMR(100MHz,CDCl3)194.7(C=O),152.5(C-2),137.8(C-3a),133.2(C-3a1),130.5(C-12),130.4(C-15c),128.6(C-1),128.1 (C-11b),127.9(C-13),127.0(C-14),126.9(C-3),124.7(C-15b),123.7(C-15),120.9(C-15a),36.1(C(CH3)),31.8(CH3)ppm; MS (DART-TOFMS) m / z: 467 [MH] + ; IR(neat)2951,1713(C=O),1448,1362,1203,894,757,738cm -1 ; HRMS(DART-TOF)calcd.for C 35 H 31 O:467.2375[MH] + ,found:467.2347; Anal.Calcd for C 35 H 30 O:C,90.09;H,6.48.Found:C,90.11;H,6.54.

[0059] Example 7 (Synthesis of Compound 7) Under an argon atmosphere, aluminum trichloride (9.1 g, 68 mmol) was added to a suspension of compound 6 (1.6 g, 3.4 mmol) in anhydrous benzene. The reaction solution was stirred at 80°C for 2 hours, and after confirming the complete disappearance of the starting materials, the reaction was stopped by adding water at 0°C. The organic layer was separated, and the aqueous layer was extracted with toluene. The combined organic layers were washed with saturated brine, dried with sodium sulfate, and concentrated to remove the medium, yielding a crude product as a brownish-orange solid. Column purification using silica gel was performed with the crude product to obtain 1.6 g (84%) of the target product as an orange-yellow solid.

[0060] Data for Compound 7 Data:Rf value0.45(Hexane / CH2Cl2,1:2); Mp275-277℃; 1 HNMR(400MHz, CDCl3)8.90(dd,J=7.5,1.4Hz,2H,H-15),8.79(dd,J=7.5,1.4Hz,2H,H-12),8.76(d,J=8.3Hz,2H,H-1),7.87(d,J=6. 9Hz,2H,H-3),7.76(ddd,J=7.5,6.9,1.4Hz,2H,H-14),7.72(ddd,J=7.5,6.9,1.4Hz,2H,H-13),7.67(dd,J=8.3,6.9Hz,2H,H-2)ppm; 13 CNMR(100MHz, CDCl3)194.4.(C-4),140.2(C-3a1),133.5(C-3a),133.1(C-1),131.1(C-15c),130.7(C-11b),129 .6(C-3),128.7(C-12),128.2(C-15b),127.8(C-13),127.6(C-14),126.0(C-15a),124.3(C-2),122.8(C-15)ppm; MS (DART-TOFMS) m / z: 355 [MH] + ; IR(neat)1702(C=O),1599,1422,1025,914,727,714cm -1 ; HRMS (DART-TOF) calcd.for C 27 H 15 O:355.1123[MH] + ,found:355.1119; Anal.Calcd.for C 27 H 14 O:C,91.50;H,3.98.Found:C,91.43;H,3.97.

[0061] Example 8 (synthesis of compound 8) Under an argon atmosphere, phenol was added to a flask and stirred while immersed in a preheated oil bath. After confirming that the phenol was sufficiently dissolved, ketone compound 7 (800 mg, 2.25 mmol) and methanesulfonic acid (0.58 mL, 9.0 mmol) were added. After stirring for 1 hour, complete disappearance of the starting materials was confirmed, and the mixture was allowed to cool naturally to room temperature. After dilution with ethyl acetate, the mixture was transferred to a separatory funnel, washed with saturated brine, dried for sodium sulfate, concentrated with de-fluid, and vacuum dried to obtain a dark brown oily crude product. Column purification using silica gel was performed to obtain the target product as a yellowish-white solid in a yield of 410 mg (35% yield).

[0062] Data for Compound 8 Data: Mp>350℃; 1 HNMR(400MHz,CD3CN)9.03(dd,J=8.5,1.7Hz,2H,H-15),8.82(dd,J=8.5,1.8Hz,2H,H-12),8.68(d,J=8.2Hz,2H,H-1),7.77-7.67(m ,8H,H-2,H-3,H-13,H-14),7.12(dd,J=8.7,2.0Hz,4H,phenylH-3),6.86(s,2H,phenylOH),6.68(dd,J=8.7,2.0Hz,4H,phenylH-2); 13 CNMR(100MHz,DMSO-d6);156.2(phenylC-1),150.0(phenylC-4),135.2(C-12,C-2,twopeaksareoverlapped),129.9(C-13),129.7(C-14),128.8(phenylC-3,phenylC-5,two peaks are overlapped),128.4(C-3a),128.1(C-3a1),127.6(C-1),127.4(C-3),127.3(C-15c),125. 2(C-11b),125.0(C-11b),123.9(C-15b),122.9(C-15a),115.2(phenylC-2,phenylC-6,two peaks are overlapped),66.2(C-4); MS (DART-TOFMS) m / z: 525[M + H]+ ; IR(neat):3486(OH),3366(OH),3059,1606,1506,1426,1174,827,718,560cm -1 ; HRMS(DART-TOFMS)calcd.for C 39 H 25 O2:525.1855[M + H] + ,found:525.1855; Anal.Calcd for C 39 H 24 O2;C,89.29;H,4.61.Found:C,89.29;H,4.61. [Industrial applicability]

[0063] The compounds having a dibenzo[g,p]chrysene skeleton of the present invention are applicable to the fields of polymer materials, high heat-resistant resins, optical functional materials, organic electronic materials, chemical sensor materials, electronic materials, high-performance carbon materials, molecular nanocarbon materials, and graphene nanoribbon materials. Specifically, examples include low transmission loss substrate materials, raw materials for low dielectric and photoadhesive polyimide resins, lithography materials, resist materials, organic EL materials, resin materials such as adhesives, materials for super engineering plastics, organic semiconductor materials, materials for organic batteries, and flexible printed circuit boards. In particular, they can be applied as hole transport materials for thin-film transistors, light-emitting elements for organic light-emitting diodes, and their precursor compounds. Furthermore, they have a high refractive index and can be applied as high refractive index materials such as plastic lenses and optical materials.

[0064] The most important element of this invention is the novel synthesis of the first compound of the present invention, which is a heptacyclic C60 fragment, under liquid-phase conditions. Its main effects are as follows: (1) Because the synthesis method is a simple liquid-phase method, quantitative supply can be easily performed, and we are just one step away from the pseudo-C60 synthesis of C54. (2) The first compound of the present invention has a bisphenol cardi structure and is expected to have a high refractive index. Because it has a structure similar to bisphenol fluorene, it can be easily applied to commonly used polymer compounds.

Claims

1. The following formula: 【Chemistry 1】 A compound represented by the formula.

2. The following general formula: 【Chemistry 2】 (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is hydrogen or a halogen group, and the two Xs may be the same or different. A is a halogen group, a hydroxyl group, or an alkyl ether group having 1 to 12 carbon atoms.) A compound represented by the formula.

3. The following formula: 【Transformation 3】 【Chemistry 4】 or 【Transformation 5】 The compound according to claim 2, as represented by the following:

4. The following general formula: 【Transformation 6】 (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and the two Rs may be the same or different. X is a hydrogen atom or a halogen group, and the two Xs may be the same or different.) A compound represented by the formula.

5. The following formula: 【Transformation 7】 【Transformation 8】 or 【Chemistry 9】 The compound according to claim 4, as represented by the following:

6. The following formula: 【Chemistry 10】 A compound represented by the formula.

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