Compound having dibenzo[g,p]chrysene skeleton and method for producing the same

Abstract

To provide a compound having a dibenzo[g,p]chrysene skeleton and a method for producing the same, the compound including oxygen atom-containing functional groups directly linked to aromatic rings via oxygen atoms at the 2- and 7-positions, and having no substituents at the 10- and 15-positions.SOLUTION: The present disclosure relates to a compound having a dibenzo[g,p]chrysene skeleton, the compound having oxygen atom-containing functional groups directly bonded to aromatic rings via oxygen atoms at positions 2 and 7, and having no substituents at positions 10 and 15. The disclosure also relates to a method for producing the compound having a dibenzo[g,p]chrysene skeleton, including: (a) an acylation step of reacting a compound having a dibenzo[g,p]chrysene skeleton with no substituents at the 2-, 7-, 10, and 15-positions with an acyl halide compound to obtain a diketone compound; (b) an esterification step of oxidizing the obtained diketone compound with an oxidizing agent to obtain a diester compound; and (c) a hydrolysis step of hydrolyzing the obtained diester compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a dibenzo[g,p]chrysene skeleton and a method for producing the same. [Background technology]

[0002] Dibenzo[g,p]chrysene (hereafter abbreviated as DBC) is a compact, hexacyclic polycyclic aromatic hydrocarbon with a relatively small molecular weight. Its nonplanar π-conjugated system has been shown to have unique properties in solid-state physics. For example, it can enhance carrier transport, quantum yield, and excitation lifetime in specific crystalline states. However, DBC is not only poorly soluble in organic solvents, but its high symmetry also makes regioselective functionalization difficult. Therefore, producing the desired DBC derivatives has required multi-step synthesis and laborious separation and purification. While a highly productive process suitable for practical manufacturing would be ideal, no such example has been known.

[0003] Among DBC derivatives that are difficult to synthesize, a group of compounds with two hydroxyl groups at the 3- and 14-positions is known, as shown in the following scheme (Non-Patent Document 1). The hydroxyl groups not only facilitate the incorporation of the DCB skeleton into polymer compounds, but also allow the preparation of derivatives with various substituents, which are expected to function as orientation-directing groups for the hydroxyl groups. However, the only known single synthesis of DBC derivatives with two hydroxyl groups substituted at specific positions (synthesis without separation and purification procedures for structural isomers) is one in which the hydroxyl groups are bonded to the 3- and 14-positions.

[0004] [ka]

[0005] Compounds having two hydroxyl groups at the 2- and 7-positions, as shown in the following scheme, are also known (Non-Patent Document 2). However, they also have two alkyl groups with large steric hindrance at the 10- and 15-positions, which makes them more soluble in organic solvents. [ka]

[0006] The former method requires the removal of the t-butyl group, which is attached to the compound to make it soluble in organic solvents, while the latter method requires the removal of the n-butyl group, which is attached to make it soluble in organic solvents, making it extremely difficult. Therefore, the development of a more productive synthetic route is required. In light of this situation, the synthesis of novel compounds with two hydroxyl groups on the DBC nucleus and the development of a new synthetic route for them are urgent issues. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] T.Iwasawa,et al.,Tetrahedron 2023,143,133549. [Non-patent document 2] N. Yoshida,et al.,Tetrahedron Lett.2020,61,152406. Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to provide a compound having a dibenzo[g,p]chrysene skeleton which has oxygen atom-containing functional groups directly bonded to an aromatic ring via oxygen atoms at the 2- and 7-positions and which does not have substituents at the 10- and 15-positions, and a method for producing the compound. [Means for solving the problem]

[0009] The present inventors have investigated methods for synthesizing compounds having a dibenzo[g,p]chrysene skeleton and have found that when a compound having a dibenzo[g,p]chrysene skeleton that does not have substituents at the 2-, 7-, 10-, and 15-positions is reacted with an acyl halide compound, a diketone compound can be synthesized in which oxygen-containing functional groups directly bonded to an aromatic ring via oxygen atoms are selectively introduced only at the 2- and 7-positions, and that a diester compound can be prepared by oxidizing the diketone compound, thereby completing the present invention. Furthermore, the ester compound can be hydrolyzed and easily converted to a phenolic hydroxyl group.

[0010] That is, the present invention (1) relates to a compound having an oxygen atom-containing functional group directly bonded to an aromatic ring via an oxygen atom at the 2- and 7-positions and a dibenzo[g,p]chrysene skeleton having no substituents at the 10- and 15-positions.

[0011] The present invention (2) is a compound represented by the following chemical formula: [ka] ,or, [ka] The compound having a dibenzo[g,p]chrysene skeleton according to the present invention (1) is a compound represented by the following formula:

[0012] The present invention (3) also provides a method for producing a diketone compound by (a) reacting a compound having a dibenzo[g,p]chrysene skeleton that does not have substituents at the 2-, 7-, 10-, and 15-positions with an acyl halide compound; (b) an esterification step of oxidizing the obtained diketone compound with an oxidizing agent to obtain a diester compound; and (c) a hydrolysis step of hydrolyzing the obtained diester compound The present invention provides a method for producing a compound having a dibenzo[g,p]chrysene skeleton according to the present invention (1) or (2), comprising the steps of:

[0013] The present invention (4) is a method for producing a compound having a dibenzo[g,p]chrysene skeleton according to the present invention (3), in which the acyl halide compound is butanoic acid chloride and the oxidizing agent is m-chloroperbenzoic acid. [Effects of the Invention]

[0014] The dibenzo[g,p]chrysene compound of the present invention is a novel buckybowl compound that has oxygen-containing functional groups directly attached to the aromatic ring via oxygen atoms at the 2- and 7-positions, and has no substituents at the 10- and 15-positions. It can be introduced into the main chain or side chain of a polymer compound, which not only leads to the simple creation of excellent electronic materials but also holds promise for the chemical synthesis of new materials such as graphene fragment structures. DETAILED DESCRIPTION OF THE INVENTION

[0015] The compound of the present invention is characterized by having oxygen atom-containing functional groups directly bonded to an aromatic ring via oxygen atoms at the 2- and 7-positions, and a dibenzo[g,p]chrysene skeleton having no substituents at the 10- and 15-positions.

[0016] Here, dibenzo[g,p]chrysene has the following chemical formula: [ka] The compound is represented by the following formula: The substitution positions of each carbon are shown in the diagram.

[0017] Examples of the oxygen atom-containing functional group directly bonded to an aromatic ring via an oxygen atom include a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an alkenyl ether group, an alkynyl ether group, and an alkylcarboxyl group (oxyacyl group).

[0018] Examples of alkyl ether groups include linear or branched alkyl ether groups that may have a substituent. The alkyl ether group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Examples include methyl ether groups, ethyl ether groups, n-propyl ether groups, isopropyl ether groups, n-butyl ether groups, 2-methylpropyl ether groups, n-pentyl ether groups, 2,2-dimethylpropyl ether groups, n-hexyl ether groups, n-heptyl ether groups, n-octyl ether groups, n-nonyl ether groups, n-decyl ether groups, n-undecyl ether groups, and n-dodecyl ether groups. Preferred are methyl ether groups, ethyl ether groups, n-propyl ether groups, n-butyl ether groups, 2-methylpropyl ether groups, n-pentyl ether groups, 2,2-dimethylpropyl ether groups, and n-hexyl ether groups. The alkenyl ether group is a group having a double bond inside or at a terminal of the alkyl ether group, and the alkynyl ether group is a group having a triple bond inside or at a terminal of the alkyl ether group.

[0019] The polyoxyalkylene group is a substituent obtained by removing a hydrogen atom from the terminal of an alkylene diol homopolymer or copolymer. The introduction of such a substituent improves solubility in water or a water-soluble organic solvent. Examples of polyoxyalkylene include polyoxyethylene, polyoxypropylene, and polyoxybutylene. The degree of polymerization is preferably 4 to 450 for polyethylene glycol and 450 to 10,000 for polyethylene oxide.

[0020] Examples of the oxyacyl group include an oxyethanoyl group, an oxypropanoyl group, an oxybutanoyl group, and an oxyformyl group.

[0021] The compound of the present invention having a dibenzo[g,p]chrysene skeleton may have substituents at other positions as long as it has oxygen atom-containing functional groups directly bonded to an aromatic ring via oxygen atoms at positions 2 and 7 and does not have substituents at positions 10 and 15. Examples of such substituents include alkyl groups, allyl groups, aryl groups, alkenyl groups, alkynyl groups, halogeno groups, hydroxyl groups, alkyl ether groups, polyoxyalkylene groups, amide groups, and amino groups.

[0022] The number of carbon atoms in the alkyl group, alkenyl group, and alkynyl group is preferably 3 to 12, and more preferably 3 to 8. Examples include isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-butyl, 2,2-dimethylpropyl, n-pentyl, isohexyl, n-hexyl, isoheptyl, n-heptyl, isooctyl, n-octyl, isononyl, n-nonyl, isodecyl, n-decyl, isoundecyl, n-undecyl, isododecyl, and n-dodecyl. The alkenyl group is a group having a double bond inside or at the terminal of the alkyl group, and the alkynyl group is a group having a triple bond inside or at the terminal of the alkyl group.

[0023] The number of carbon atoms in the aryl group is preferably 6 to 14. Examples include a phenyl group, a naphthyl group, and an anthryl group.

[0024] Among the compounds having a dibenzo[g,p]chrysene skeleton, those having the following formula [ka] ,or, [ka] The former compound having a dibenzo[g,p]chrysene skeleton can be synthesized, for example, by the method for producing a compound having a dibenzo[g,p]chrysene skeleton of the present invention, which will be described below. The latter compound having a dibenzo[g,p]chrysene skeleton can be obtained as an intermediate in the method for producing a compound having a dibenzo[g,p]chrysene skeleton of the present invention.

[0025] The method for producing a compound having a dibenzo[g,p]chrysene skeleton of the present invention comprises the steps of: (a) an acylation step of reacting a compound having a dibenzo[g,p]chrysene skeleton that does not have substituents at the 2-, 7-, 10-, and 15-positions with an acyl halide compound to obtain a diketone compound; (b) an esterification step of oxidizing the obtained diketone compound with an oxidizing agent to obtain a diester compound; and (c) a hydrolysis step of hydrolyzing the obtained diester compound The present invention is characterized by comprising:

[0026] [Acylation step (a)] A diketone compound is synthesized by reacting a compound having a dibenzo[g,p]chrysene skeleton without substituents at the 2, 7, 10, and 15 positions with an acyl halide compound. This reaction is a Friedel-Crafts reaction, preferably carried out in the presence of a Lewis acid (see T. Iwasawa, et al., Tetrahedron Lett. 2020, 61, 152033). Even if an excess of the acyl halide compound is reacted in this reaction, only the 2 and 7 positions are acylated, and the 10 and 15 positions in particular are not acylated. Introducing electron-donating groups at the 2 and 7 positions reduces the electron density at the 10 and 15 positions, making them less susceptible to acylation.

[0027] Examples of the acyl halide compound include acetyl chloride, propanoyl chloride, butanoyl chloride, dichloromethyl formate, etc. Examples of the Lewis acid include aluminum trichloride, alkyl aluminum dichloride, aluminum tribromide, boron tribromide, boron trifluoride, tin tetrachloride, etc.

[0028] [Esterification step (b)] The diketone compound synthesized in the acylation step (a) is oxidized. This reaction is a Bayer-Villiger oxidation reaction. Examples of oxidizing agents include metachloroperbenzoic acid (mCBA), perbenzoic acid, tert-butyl peroxide, and sodium hypochlorite. The reaction temperature is preferably 0 to 100°C, and the reaction time is preferably 1 to 24 hours.

[0029] [Hydrolysis step (c)] The ester compound synthesized in the esterification step (b) is hydrolyzed. The reaction is preferably carried out in the presence of a base or an acid, more preferably in the presence of a base. Examples of the base include potassium t-butoxide, sodium t-butoxide, potassium carbonate, potassium hydroxide, and sodium hydroxide. The reaction temperature is preferably 25 to 100°C, and the reaction time is preferably 1 to 24 hours.

[0030] The compounds having a dibenzo[g,p]chrysene skeleton of the present invention are applicable to the fields of polymer materials, highly heat-resistant resins, optical functional materials, organic electronics materials, chemical sensor materials, highly functional carbon materials, molecular nanocarbon materials, and graphene nanoribbon materials. Specific examples include low-transmission-loss substrate materials, raw materials for low-dielectric and photo-adhesive polyimide resins, lithography materials, resist materials, organic electroluminescence (EL) materials, resin materials such as adhesives, super engineering plastic materials, organic semiconductor materials, organic battery materials, and flexible printed circuit boards. In particular, they are applicable as hole-transport materials for thin-film transistors, light-emitting elements for organic light-emitting diodes, and precursor compounds thereof. Furthermore, due to their high refractive index, they are applicable as high-refractive-index materials for plastic lenses and other optical materials. [Example]

[0031] Examples of the present invention will be described below, but the present invention is not limited to the following examples.

[0032] In the examples, reactions were carried out under an argon or nitrogen atmosphere, and unless otherwise specified, experiments were carried out under water-free conditions. Purchased anhydrous solvents and reagents were used without further purification to improve purity. Thin-layer chromatography was performed using Merck silica 60F. 254 Silica gel 60 was used for column chromatography. N (Kanto Chemical Co., Ltd.) was used. For high-resolution mass measurement (HRMS), either time-of-flight mass spectrometry (MALDI-TOF or LCMS-IT-TOF) or direct mass spectrometry (DART-MS) was used.

[0033] 1 H-NMR, 13 The C-NMR spectra were measured at 400 MHz and 100 MHz using a 5 mm QNP probe. The chemical shift values ​​are shown in δ (ppm), and the reference values ​​in each solvent are 1 H-NMR: CHCl3 (7.26), CH2Cl2 (5.32), DMSO (2.50); 13 C-NMR: CDCl3 (77.0), DMSO (39.5). Splitting patterns are indicated as s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad line.

[0034] Example 1 Acylation step (a) (synthesis of dibutanoyl dibenzo[g,p]chrysene)

[0035] [ka]

[0036] Under an argon atmosphere, butyryl chloride (6.3 mL, 60 mmol) was added to a cloudy solution of aluminum trichloride (8.0 g, 60 mmol) in anhydrous methylene chloride. After stirring at room temperature for 15 minutes, dibenzo[g,p]chrysene (5.0 g, 15 mmol) was added. The reaction solution was stirred for 2 hours, and then 3 M hydrochloric acid was added at 0°C to quench the reaction. The organic layer was separated, and the aqueous layer was extracted with methylene chloride. The combined organic layer was washed with saturated brine, dried over sodium sulfate, and vacuum dried to obtain a crude product. Purification using a silica gel filtration column yielded 6.4 g of the desired product as a pale yellow solid (90%).

[0037] [ka]

[0038] Esterification step (b) To a solution of the resulting dibutanoyl derivative of dibenzo[g,p]chrysene (1.0 g, 2.1 mmol) in 1,2-dichloroethane under atmospheric pressure, m-chloroperbenzoic acid (2.6 g, 11 mmol) was added and the temperature was raised to 60°C. After stirring for 6 hours, the mixture was allowed to cool to room temperature and saturated aqueous sodium bicarbonate was added at room temperature to quench the reaction. After diluting with ethyl acetate and transferring to a separatory funnel, the organic layer was washed with saturated aqueous sodium bicarbonate and saturated brine, dried over sodium sulfate, and concentrated to remove the solvent, yielding a crude product. Purification using a silica gel filtration column yielded 420 mg (38% yield) of the ester compound as a pale orange viscous substance.

[0039] Identification of ester compounds Rf value 0.62(toluene / CH2Cl2,1:9); 1HNMR(400MHz,CDCl3)8.69(dd,J=7.8,2.8Hz,2H),8.66(d,J=9.1Hz,2H),8.60(dd,J=7.0,2.2Hz,2H),8.38(d,J=2.4Hz,2H),7.68(ddd,J=7.5,7.0,2. 2Hz,2H),7.65(ddd,J=7.0,7.0,2.8Hz,2H),7.38(dd,J=9.1,2.4Hz,2H),2. 68(t,J=7.4Hz,4H),1.89(qt,J=7.4,7.4Hz,4H),1.13(t,J=7.4Hz,6H)ppm; 13 CNMR(100MHz,CDCl3)172.7,149.6,132.4,130.6,130.5,129.7,129.1,127 .4,127.3,127.2,127.1,126.9,124.1,121.1,116.1,36.7,18.9,14.1ppm; MS(DART-TOF) m / z: 501[MH] + ; IR(neat)2963,2873,1750(C=O),1434,1238,1134,749cm -1 ; HRMS (DART-TOF) calculation for C 34 H 29 O4:501.2066[MH] + ,found;501.2047.

[0040] Hydrolysis step (c) Under an argon atmosphere, potassium tert-butoxide (1.2 g, 10 mmol) and water (0.05 mL, 2.6 mmol) were added to a solution of the resulting ester compound (580 mg, 1.2 mmol) in anhydrous tetrahydrofuran. The reaction solution was heated to 70°C, stirred for 30 minutes, and then allowed to cool to room temperature. 3 M hydrochloric acid was added to terminate the reaction. The mixture was diluted with ethyl acetate and transferred to a separatory funnel, after which the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over sodium sulfate, and concentrated to remove the solvent, yielding a crude product. Purification was performed using a silica gel filtration column, yielding 410 mg (93% yield) of dibenzo[g,p]chrysene-2,7-diol as a light brown solid.

[0041] Identification of diols Rf value 0.36(toluene / EtOAc,9:1); Mp252-253℃; 1 HNMR(400MHz,CD3CN)8.65(dd,J=7.5,1.6Hz,2H),8.63(dd,J=7.6,1.6Hz,2H),8.50(d,J=9.0Hz,2H),8.09(d,J=2.6Hz,2 H),7.66(ddd,J=7.5,7.1,1.6Hz,2H),7.64(ddd,J=7.6,7.1,1.6Hz,2H),7.44(s,2H,-OH)7.20(dd,J=9.0,2.6Hz,2H)ppm; 13 CNMR(100MHz,CD3CN)156.8,133.5,131.7,130.5,130.2,129.2,128.7,127.7,126.9,124.7,124.2,123.6,117.0,108.9ppm; MS(DART-TOF) m / z: 361[MH] + ; IR(neat)3431,3162,3058,1607,1431,1167,815,750,728cm -1 ; HRMS (DART-TOF) calculation for C 26 H 17 O 2 :361.1229[MH] + ,found;361.1206. [Industrial Applicability]

[0042] The compounds having a dibenzo[g,p]chrysene skeleton of the present invention are applicable to the fields of polymer materials, highly heat-resistant resins, optical functional materials, organic electronics materials, chemical sensor materials, highly functional carbon materials, molecular nanocarbon materials, and graphene nanoribbon materials. Specific examples include low-transmission-loss substrate materials, raw materials for low-dielectric and optically adhesive polyimide resins, lithography materials, resist materials, organic electroluminescence (EL) materials, resin materials such as adhesives, super engineering plastic materials, organic semiconductor materials, organic battery materials, and flexible printed circuit boards. In particular, the compounds are applicable as hole-transport materials for thin-film transistors, light-emitting elements for organic light-emitting diodes, and precursor compounds thereof. Furthermore, due to their high refractive index, they are applicable as high-refractive-index materials for plastic lenses and other optical materials. Furthermore, the method for producing the compounds having a dibenzo[g,p]chrysene skeleton of the present invention is applicable as a method for producing compounds having a dibenzo[g,p]chrysene skeleton that are useful as hole-transport materials for thin-film transistors and light-emitting elements for organic light-emitting diodes.

[0043] The most important element of the present invention is the discovery that dibenzo[g,p]chrysene having alkanoyl groups at the 2- and 7-positions can be converted to dibenzo[g,p]chrysene-2,7-diol. The main effects of this discovery are as follows: (1) We discovered that dibenzo[g,p]chrysene bearing alkanoyl groups at the 2- and 7-positions can be converted to the corresponding diester compounds by Bayer-Villiger oxidation. (2) We discovered hydrolysis conditions that convert the diester compound obtained in (1) into dibenzo[g,p]chrysene-2,7-diol. (3) Dibenzo[g,p]chrysene-2,7-diol can be obtained safely and with high quality in large quantities at low cost from unsubstituted dibenzo[g,p]chrysene in three steps.

Claims

1. A compound having a dibenzo[g,p]chrysene skeleton which has oxygen atom-containing functional groups directly bonded to an aromatic ring via oxygen atoms at the 2- and 7-positions and which does not have substituents at the 10- and 15-positions.

2. The chemical formula: 【Chemistry 1】 ,or, 【Chemistry 2】 The compound having a dibenzo[g,p]chrysene skeleton according to claim 1, which is a compound represented by the formula:

3. (a) an acylation step of reacting a compound having a dibenzo[g,p]chrysene skeleton that does not have substituents at the 2-, 7-, 10-, and 15-positions with an acyl halide compound to obtain a diketone compound; (b) an esterification step of oxidizing the obtained diketone compound with an oxidizing agent to obtain a diester compound; and (c) a hydrolysis step of hydrolyzing the obtained diester compound A method for producing a compound having a dibenzo[g,p]chrysene skeleton according to claim 1 or 2, comprising:

4. 4. The method for producing a compound having a dibenzo[g,p]chrysene skeleton according to claim 3, wherein the acyl halide compound is butanoic acid chloride and the oxidizing agent is m-chloroperbenzoic acid.

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