JP2023070620A - DIBENZO [g,p] CHRYSENE DERIVATIVE, AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

To provide a dibenzo [g,p] chrysene derivative having horizontally asymmetrical substituent to a central naphthalene ring, and a method for producing the derivative, especially a dibenzo [g,p] chrysene derivative having a same first substituent at position 3 and position 14, and having a same second substituent different from the first substituent at position 6 and position 11, and a method for producing the derivative.SOLUTION: There is provided, a dibenzo [g,p] chrysene derivative having a same first substituent at position 3 and position 14, and having a same second substituent different from the first substituent at position 6 and position 11. A method for producing the dibenzo [g,p] chrysene derivative includes: (a) a process of dimerizing fluorenone derivative having the same first substituent at positions 2, 7, and fluorenone derivative having the same second substituent different from the first substituent at positions 2, 7, and producing a spiro ketone derivative; (b) a process of reducing a carbonyl group of the obtained spiro ketone derivative, and manufacturing a spiro alcohol derivative having a hydroxyl group; and (c) a process of dehydrating the obtained spiro alcohol derivative, and obtaining a dibenzo [g,p] chrysene derivative.SELECTED DRAWING: None

Description

The present invention relates to a dibenzo[g,p]chrysene derivative and a method for producing the same.

Dibenzo[g,p]chrysene synthesized from spiroketone derivatives is a promising organic compound as a highly functional material. The most distinctive feature of the dibenzo[g,p]chrysene structure is its highly non-planar pi-conjugated structure, which has attracted the interest of many researchers. Here, non-planarity means that the π-conjugated aromatic group is helically twisted, and the helical structure is expected as a hole transport material for thin film transistors and as a light emitting device for organic light emitting diodes. It has high potential value in optical quantum physical properties (quantum yield, excitation lifetime), electronic properties, and heat resistance, and attempts are being made to incorporate it into polymer materials. In addition, dibenzo[g,p]chrysene has a high refractive index and is expected to be used as an optical material for plastic lenses and the like.

However, dibenzo[g,p]chrysene does not have reactive substituents, and it is necessary to introduce reactive substituents in order to use it as a functional material. For example, a heteroatom such as halogen, nitrogen, oxygen, or sulfur is introduced, and after converting the heteroatom into another substituent, a polymerizable substituent such as a three-membered ring ether, a methacrylate group, or a terminal alkene is introduced at the terminal. Then, it is necessary to prepare a functional material by polymerizing it or reacting it with the side chain or end of the polymer. However, polycyclic aromatic hydrocarbons also have the problem that they are difficult to dissolve in organic solvents, making liquid-phase synthesis difficult and attaching reactive substituents to them is not easy.

Non-Patent Document 1 discloses a compound having hydroxyl groups at the 10th and 15th positions of dibenzo[g,p]chrysene and n-butyl groups at the 2nd and 7th positions and having improved solubility in organic solvents. It is Non-Patent Document 2 discloses a compound having bromo groups at the 7- and 10-positions and tert-butyl groups at the 2- and 15-positions of dibenzo[g,p]chrysene. However, none of the non-patent documents disclose compounds having substituents at the 3-, 6-, 11- and 14-positions.

Non-Patent Document 3 discloses a dibenzo[g,p]chrysene derivative having two methoxy groups at the 3- and 11-positions, and a dibenzo[g,p]chrysene derivative having four methoxy groups at the 3-, 6-, 11- and 14-positions. g,p]chrysene derivatives are disclosed. However, although the former derivative has methoxy groups as different substituents at symmetrical positions with respect to the central naphthalene ring, it has only two methoxy groups and does not have sufficient solubility in organic solvents. On the other hand, the latter derivative has four methoxy groups, so it is highly soluble in organic solvents, but has the same methoxy groups as substituents at symmetrical positions with respect to the central naphthalene ring. Therefore, Non-Patent Document 3 has the same first substituents at positions 3 and 14, has the same second substituents different from the first substituents at positions 6 and 11, and Dibenzo[g,p]chrysene derivatives having different substituents at symmetrical positions with respect to the naphthalene ring are not disclosed.

By the way, polyimide resin has very high heat resistance and high strength. An aromatic polyimide is synthesized by polymerizing a tetracarboxylic dianhydride and an aromatic diamine to form a polyamic acid, followed by an imidization reaction by cyclization. The simplest chemical method to improve the performance of polyimide resins is to improve the aromatic groups of aromatic diamines. Merely introducing an aliphatic substituent into the aromatic ring in an attempt to improve transparency and moldability results in a decrease in heat resistance. In other words, it is important to consider materials that improve moldability and transparency while maintaining heat resistance and high strength performance. For this purpose, it is required to create and create monomers that are highly soluble in organic solvents, structurally rigid, and highly productive.

Tetrahedron Lett. , 2020, 61, 152406. Thin Solid Films, 2017, 636, 8-14. J. Org. Chem. , 2007, 72, 9203.

The present invention relates to a dibenzo[g,p]chrysene derivative having a left-right asymmetric substituent with respect to the central naphthalene ring and a method for producing the same, particularly having the same first substituent at the 3-position and the 14-position, and a dibenzo[g,p]chrysene derivative having the same second substituent different from the first substituent at the 11-position, and a method for producing the same.

The present inventors have investigated a method for synthesizing a spiroketone derivative, which is a precursor for synthesizing a dibenzo[g,p]chrysene derivative. , the cross-dimerization reaction proceeds efficiently between specific fluorenone compounds, and it is possible to synthesize dibenzo[g,p]chrysene derivatives having left-right asymmetric substituents with respect to the central naphthalene ring, thereby completing the present invention. .

That is, the present invention provides dibenzo[g,p]chrysene having identical first substituents at positions 3 and 14 and identical second substituents different from the first substituents at positions 6 and 11. Regarding derivatives.

A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. A substituent selected from is preferred.

、または、

で表されることが好ましい。 the following formula

,or,

is preferably represented by

The present invention also provides (a) a fluorenone derivative having the same first substituents at the 2 and 7-positions, and a fluorenone derivative having the same second substituents at the 2- and 7-positions, which are different from the first substituents. dimerization to produce a spiroketone derivative;
(b) reducing the carbonyl group of the obtained spiroketone derivative to prepare a spiroalcohol derivative having a hydroxyl group;
(c) dehydrating the obtained spiroalcohol derivative to obtain a dibenzo[g,p]chrysene derivative;

The present invention also relates to a spiroketone derivative having identical first substituents at positions 2 and 7 and identical second substituents different from the first substituents at positions 2' and 7'.

A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. A substituent selected from is preferred.

または、

で表されることが好ましい。 the following formula

or,

is preferably represented by

Furthermore, the present invention dimerizes a fluorenone derivative having the same first substituents at the 2 and 7-positions and a fluorenone derivative having the same second substituents at the 2 and 7-positions that are different from the first substituents. The present invention relates to a method for producing the spiroketone derivative, comprising steps.

The dibenzo[g,p]chrysene derivative of the present invention has the same first substituents at positions 3 and 14, and the same second substituents different from the first substituents at positions 6 and 11. and have asymmetrical substituents with respect to the central naphthalene ring. Therefore, dibenzo[g,p]chrysene derivatives having various kinds of substituents, which have been impossible so far, can be created and created.

The dibenzo[g,p]chrysene derivative of the present invention has the same first substituents at positions 3 and 14, and the same second substituents different from the first substituents at positions 6 and 11. It is characterized by Two different fluorenone compounds are cross-dimerized to induce a spiroketone derivative, and the spiroketone derivative is used as a precursor to synthesize a dibenzo[g,p]chrysene derivative. is a dibenzo[g,p]chrysene derivative having different substituents at symmetrical positions with respect to the naphthalene ring. Having the same first substituents at positions 3 and 14 and having the same second substituents different from the first substituents at positions 6 and 11 is a very unique chemical structure.

で表される化合物である。各炭素の置換位置を図中に示す。 Dibenzo[g,p]chrysene has the following chemical formula

It is a compound represented by The substitution position of each carbon is shown in the figure.

A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. A substituent selected from is preferred. Having these substituents improves the solubility in organic solvents. As the organic solvent, solvents such as toluene, methylene chloride, methyl ethyl ketone, acetone, tetrahydrofuran, N,N-dimethylformamide, and dimethyl sulfoxide are preferably used in terms of solubility in the temperature range of -78°C to 150°C.

Among alkyl groups, allyl groups, aryl groups, alkenyl groups, and alkynyl groups, alkyl groups are preferred in terms of solubility in a wide variety of organic solvents.

Alkyl groups, alkenyl groups, and alkynyl groups preferably have 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. For example, iso-propyl, iso-butyl, tert-butyl, 2,2-dimethylpropyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, iso-undecyl, iso-dodecyl, etc. Those having a branched structure are preferred. Among them, iso-propyl, iso-butyl and tert-butyl are preferred. An alkenyl group is a group having a double bond inside or at the end of the alkyl group, and an alkynyl group is a group having a triple bond inside or at the end of the alkyl group. The aryl group preferably has 6 to 14 carbon atoms. Examples include phenyl group, naphthyl group and anthryl group.

The halogeno group includes a fluoro group, a chloro group, a bromo group and an iodo group, with the bromo group being preferred.

Alkyl ether groups include linear or branched alkyl ether groups which may have a substituent. The number of carbon atoms in the alkyl ether group is preferably 1-12, more preferably 1-8. For example, methyl ether group, ethyl ether group, normal propyl ether group, isopropyl 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 and the like, methyl ether group, ethyl ether group , normal propyl ether group, n-butyl ether group, 2-methylpropyl ether group, n-pentyl ether group, 2,2-dimethylpropyl ether group and n-hexyl ether group are preferred. The alkenyl ether group is a group having a double bond inside or at the end of the alkyl ether group, and the alkynyl ether group is a group having a triple bond inside or at the end of the alkyl ether group.

The polyoxyalkylene group is a substituent obtained by removing hydrogen from the terminal of an alkylenediol homopolymer or copolymer. By introducing such a substituent, it becomes easier to dissolve in water or a water-soluble organic solvent. Polyoxyalkylenes include polyoxyethylene, polyoxypropylene, polyoxybutylene and the like. The degree of polymerization is preferably 4 to 450 in the case of polyethylene glycol, and 450 to 10,000 in the case of polyethylene oxide.

An amide group is a functional group represented by -NHCOR. Examples of R include an alkyl group, an aryl group, an alkoxy group, and the like. Amino groups include not only primary amines (--NH ₂ ), but also secondary amines (--NHR ¹ ) and tertiary amines (--NR ¹ R ² ). Examples of the R ¹ group of the secondary amine and the R ¹ and R ² groups of the tertiary amine include alkyl groups and aryl groups. The alkyl group in the amide group, secondary amine, and tertiary amine preferably has 1 to 12 carbon atoms, and the aryl group preferably has 6 to 14 carbon atoms. More specifically, alkyl groups include iso-propyl, iso-butyl, tert-butyl, 2,2-dimethylpropyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, Examples include iso-undecyl and iso-dodecyl, and examples of aryl groups include phenyl, naphthyl, and anthryl groups.

If the 3-position and the 14-position have the same first substituent, and the 6-position and the 11-position have the same second substituent different from the first substituent, a substituent is added to the other substitution position. You may have Other substituents, like the first and second substituents, include alkyl groups, allyl groups, aryl groups, alkenyl groups, alkynyl groups, halogeno groups, hydroxyl groups, alkyl ether groups, polyoxyalkylene groups, amide groups, and an amino group.

または、

、または、

で表されることが好ましい。 Among the dibenzo[g,p]chrysene derivatives, the following formula

or,

,or,

is preferably represented by

The compounds represented by formulas 10 and 11 have relatively large substituents in the fjord region of dibenzo[g,p]chrysene, and can impart optical activity to the non-planar π-conjugated system. can. In particular, the compound represented by Formula 11 has a sulfonyl group, which is a strong electron-withdrawing group, and a methoxy group and a tert-butyl group, which are electron-donating groups. Therefore, it can be used as a push-pull organic material. can also be expected to have characteristic physicochemical properties.

The method for producing the dibenzo[g,p]chrysene derivative of the present invention comprises
(a) a fluorenone derivative having the same first substituents at the 2 and 7-positions and a fluorenone derivative having the same second substituents different from the first substituents at the 2 and 7-positions are dimerized to obtain a spiroketone derivative; a step of making
(b) reducing the carbonyl group of the obtained spiroketone derivative to prepare a spiroalcohol derivative having a hydroxyl group;
(c) dehydrating the resulting spiro alcohol derivative to obtain a dibenzo[g,p]chrysene derivative.

If a fluorenone derivative having the same first substituents at the 2 and 7-positions and a fluorenone derivative having the same second substituents different from the first substituents at the 2- and 7-positions, two derivatives of the same kind The rate of quantification decreases, and cross-dimerization reactions between different fluorenones proceed preferentially.

A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. A substituent selected from is preferred. Details of these substituents are as described above.

The method for dimerizing the fluorenone derivative is not particularly limited, and a preferred method is a method carried out in the presence of a Lewis base reagent having a high affinity for oxygen, such as trialkyl phosphite. An activating reagent such as trialkyl phosphite is preferably at least 2 equivalents. The reaction temperature is not particularly limited, and is preferably 90 to 200°C.

A method for reducing the spiroketone derivative is not particularly limited, and examples thereof include a catalytic reduction method using a reducing agent such as sodium borohydride and lithium aluminum hydride, and hydrogen (gas).

The dehydration method of the spiroketone derivative having a hydroxyl group is not particularly limited. acid, p-toluenesulfonic acid, benzenesulfonic acid, acetic acid, trifluoromethanesulfonic acid and the like.

When the resulting dibenzo[g,p]chrysene derivative has a halogeno group, the halogeno group can be converted to an alkoxy group with sodium alkoxide and copper iodide, copper bromide, copper chloride, or the like.

A compound represented by Formula 1 is synthesized using 2,7-dibromofluorenone and 2,7-di-tert-butylfluorenone as starting materials by the method for producing dibenzo[g,p]chrysene derivatives of the present invention. be able to. The compound represented by Formula 2 can be synthesized by etherifying the compound represented by Formula 1 using monovalent copper such as copper iodide, copper bromide, and copper chloride. The compound represented by Formula 3 is synthesized by subjecting the compound represented by Formula 2 to dealkylation such as demethylation using a Lewis acidic reagent such as boron bromide or a basic reagent such as thiolate. can do.

The compound represented by formula 4 can be obtained by treating the compound represented by formula 2 or formula 3 with tert-butyl chloride or the like in the presence of a Lewis acid such as aluminum trichloride, ethyl aluminum dichloride, iron trichloride, or zerovalent iron. It can be synthesized by a Friedel-Crafts reaction in which it is reacted with an alkyl halide. A compound of Formula 5 is a thiolate compound formed by treating a compound of Formula 4 with a basic reagent to treat an alkyl thiol having an alkyl chain of C ₁₀ H ₂₁ SH to C ₂ H ₅ SH. It can be synthesized by reacting and dealkylating such as demethylation. The compound represented by the formula 6 can be synthesized by reacting the compound represented by the formula 5 with a halogen compound such as bromine, chlorine, iodine, iodine monochloride, bromine monochloride, and halogenating the compound. . The compound represented by Formula 7 is synthesized by reacting the compound represented by Formula 6 with an alkylating agent such as methyl iodide, methyl bromide, allyl iodide, and allyl bromide to etherify. be able to.

The compound represented by formula 8 is obtained by combining the compound represented by formula 1 with monovalent copper such as copper iodide, copper bromide, copper chloride and ethylenediamine, dimethylethylenediamine, 1,2-cyclohexyldiamine, 1,2- It can be synthesized by reacting with a carbamic acid ester (eg, tert-butoxycarbonylamine (BocNH ₂ )) or an amide compound to amidate in the presence of a diamine reagent such as cyclohexyldimethylamine. The compound represented by Formula 9 can be synthesized by hydrolyzing the compound represented by Formula 8 in the presence of an acid such as trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, sulfuric acid, or hydrochloric acid. .

The compound represented by Formula 10 is obtained by reacting the compound represented by Formula 7 with an organic lithium compound such as methyllithium, normal-butyllithium, normal-hexyllithium, and phenyllithium to lithiate the compound, followed by dimethyldisulfide or dialkylsulfide. or diaryl sulfide. The compound represented by Formula 11 can be synthesized by oxidizing the compound represented by Formula 10 with an oxidizing agent such as hydrogen peroxide, meta-chloroperbenzoic acid, tert-butyl peroxide and the like. In these methods, the compounds obtained are racemic because they have bulky substituents at the 4-position and 13-position. Isomers can be separated and isolated.

The spiroketone derivative of the present invention is characterized by having the same first substituents at positions 2 and 7 and having the same second substituents different from the first substituents at positions 2′ and 7′. .

A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. A substituent selected from is preferred. Details of these substituents are as described above.

If it has the same first substituent at the 2-position and the 7-position and has the same second substituent different from the first substituent at the 2'-position and the 7'-position, it is substituted at another substitution position You may have a group.

または、

が好ましい。 Among the spiroketone derivatives, the following formula

or,

is preferred.

The method for producing the spiroketone derivative of the present invention comprises
comprising a step of dimerizing a fluorenone derivative having the same first substituents at the 2 and 7-positions and a fluorenone derivative having the same second substituents different from the first substituents at the 2 and 7-positions; characterized by

The step of dimerization is as described above in step (a).

According to the method for producing the spiroketone derivative of the present invention, the compound represented by Formula 12 can be synthesized using 2,7-dibromofluorenone and 2,7-di-tert-butylfluorenone as starting materials. Further, the compound represented by Formula 13 can be synthesized by reducing the compound represented by Formula 12 with a reducing agent such as sodium borohydride or lithium aluminum hydride.

The dibenzo[g,p]chrysene derivative and spiroketone derivative of the present invention are applied to the fields of polymer materials, highly heat-resistant resins, optical functional materials, organic electronic materials, and chemical sensor materials. Specifically, low transmission loss substrate materials, raw materials for low dielectric/photoadhesive polyimide resins, lithography materials, resist materials, organic EL materials, resin materials such as adhesives, super engineering plastic materials, and organic semiconductors. materials, organic solar cell materials, flexible printed circuit boards, and the like. In particular, it can be applied as a hole transport material for thin film transistors, light emitting elements for organic light emitting diodes, and precursor compounds thereof. In addition, it has a high refractive index and can be applied as an optical material such as a plastic lens. In particular, the compound represented by formula (9) is applicable to polymers such as polyimide, polyamide, polyetherimide, and polyurea having high heat resistance, high glass transition temperature, and high thermal conductivity.

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

In the examples, water-free reactions were carried out in an argon or nitrogen atmosphere, and experiments were carried out under water-free conditions unless otherwise specified. Purchased anhydrous solvents and reagents were used without further purification to improve their purity. Merck silica 60F ₂₅₄ was used for thin-layer chromatography, and silica gel 60 _N (manufactured by Kanto Kagaku Co., Ltd.) was used for column chromatography. Either time-of-flight mass spectrometry (MALDI-TOF or LCMS-IT-TOF) or direct mass spectrometry (DART-MS) was used as high resolution mass spectrometry (HRMS).

¹ H-NMR and ¹³ C-NMR spectra were measured at 400 MHz and 100 MHz, respectively, using a 5 mm QNP probe. Chemical shift values are given in δ (ppm), and reference values in respective solvents are ¹ H-NMR: CHCl ₃ (7.26), CH ₂ Cl ₂ (5.32), DMSO (2.50). ); ¹³ C-NMR: CDCl ₃ (77.0), DMSO (39.5). Splitting patterns are indicated by s: single line, d: double line, t: triple line, q: quartet, m: multiple line, br: broad line.

Example 1
Synthesis of 3,14-dibromo-6,11-di-tert-butylspiroketone (compound 1) In a 20 mL Schlenk tube under an argon atmosphere, 2,7-dibromofluorenone (510 mg, 1.5 mmol) and 2,7 -Di-tert-butylfluorenone (440 mg, 1.5 mmol) and triisopropyl phosphite (1.0 mL, 4.5 mmol) were added, immersed in an oil bath at room temperature, and the oil bath temperature was raised to 110°C. . After stirring for 2 hours, the temperature was naturally lowered to 60°C. After adding distilled water (1.0 mL, 55 mmol), the temperature was raised to 80° C. again. After stirring for 2 hours, the temperature was naturally lowered to room temperature. The aqueous layer was extracted with toluene, and the combined organic layer was washed with saturated saline, dried over Glauber's salt, concentrated to remove the solvent, and dried in a vacuum to obtain a viscous substance. Filtration column purification using silica gel (only methylene chloride as a developing solvent) was performed to obtain 790 mg of solid. Column purification using silica gel was performed to obtain 600 mg (65%) of solid. The chemical structure was determined by X-ray crystallography.

Analytical Data for Compound 1:
Rf value 0.45 (Hexane/EtOAc = 9/1);
M. p. 259-260°C;
¹ H NMR (400 MHz, _CDCl3 ) 8.07 (d, J = 2.2 Hz, 1 H), 8.02 (d, J = 8.6 Hz, 1 H), 7.90 (d, J = 8.5 Hz, 1H), 7.89 (dd, J = 8.6, 2.2 Hz, 1H), 7.67 (d, J = 8.0 Hz, 2H), 7.50 (dd, J = 8.5, 2 0 Hz, 1 H), 7.43 (dd, J=8.0, 1.6 Hz, 2 H), 6.99 (d, J=1.6 Hz, 2 H), 6.78 (d, J=2. 0 Hz, 1H), 1.20 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 195.8 (C=O), 151.4, 145.8, 142.2, 139.2, 137.9, 136.6, 131.8, 131.6 (two peaks are overlapped), 131.4, 129.3, 126.2, 125.9, 125.2, 124.0, 123.1, 121.8, 120.4, 69.1, 35.2, 31 .7 ppm;
MS (DART-TOFMS) m/z: 615 [MH] ⁺ ;
IR (neat): 2956, 1686 (C=O), 1459, 1399, 1249, 1225, 810, 742 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₃₄ H ₃₁ Br ₂ O: 615.0721 [MH] ⁺ , found: 615.0707 [MH] ⁺ ;
Anal. Calcd for _{C34H30Br2O :} C, 66.46; _H , 4.92. Found: C, 66.31; H, 4.87.

Example 2
Synthesis of 3,14-dibromo-6,11-di-tert-butylspirofluorenephenanthrenol (Compound 2) 1 (2.8 g, 4.6 mmol) and toluene (14 mL) were placed in a 50 mL one-necked flask under atmospheric pressure. , methanol (2.8 mL) was added, and the temperature was raised to 45°C. After stirring for 15 minutes, sodium borohydride (70 mg, 1.8 mmol) was added over 30 minutes and then stirred for 30 minutes. After adding acetone and stirring, the temperature was naturally lowered to room temperature. The organic layer was washed with water, washed with saturated brine, dried over Glauber's salt, concentrated to remove the solvent, and dried under vacuum to obtain a crude product of Compound 2. Column purification using silica gel was performed to give 2.6 g (91%) of white-orange solid.

Analytical Data for Compound 2:
_Rf value 0.56 (Hexane/ _CH2Cl2 = 1/1);
M. p. 136-139°C;
¹ H NMR (400 MHz, _CDCl3 ) 7.77 (d, J = 8.0 Hz, 1 H), 7.74 (d, J = 8.0 Hz, 1 H), 7.68 (d, J = 8.0 Hz, 1H), 7.66-7.63 (m, 2H), 7.62 (d, J = 8.0Hz, 1H), 7.48 (dd, J = 8.0, 2.1Hz, 1H), 7.47 (dd, J=8.0, 1.8Hz, 1H), 7.34 (dd, J=8.0, 1.8Hz, 1H), 7.23 (brs, 1H), 6.85 (d, J = 2.0 Hz, 1 H), 6.69 (brs, 1 H), 5.26 (d, J = 6.2 Hz, 1 H), 1.58 (d, J = 6.2 Hz, 1 H) , 1.30 (s, 9H), 1.08 (s, 9H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 151.5, 150.5, 146.4, 144.3, 141.7, 139.9, 139.7, 138.5, 132.63, 132.57, 131. 9, 131.6, 131.0, 130.1, 126.1, 126.0, 125.9, 125.4, 123.0, 122.9, 122.8, 121.8, 119.9, 119.8, 74.6, 61.2, 35.4, 35.0, 31.8, 31.5 ppm;
MS (DART-TOFMS) m/z: 617 [MH] ⁺ ;
IR (neat): 3528 (OH), 2956, 1593, 1462, 1362, 1254, 1085, 1004, 809, 747, 731 cm ^-1 ,
HRMS (DART-TOFMS) calcd for C ₃₄ H ₃₃ Br ₂ O: 616.0799 [MH] ⁺ , found: 616.0810 [MH] ⁺ .

Example 3
Synthesis of 3,14-dibromo-6,11-di-tert-butyldibenzo[g,p]chrysene (compound 3) 2 (2.6 g, 4.2 mmol) and toluene (2.6 g, 4.2 mmol) were placed in a 200 mL one-necked flask under atmospheric pressure. 50 mL) was added, and the mixture was stirred under reflux conditions for 15 minutes. After that, methanesulfonic acid (0.010 mL, 0.15 mmol) was added, and after stirring for 1 hour, the temperature was naturally lowered to room temperature. The reaction solution was washed with saturated saline, dried over Glauber's salt, concentrated to remove the solvent, and dried in a vacuum to obtain a crude product of Compound 3. Filtration column purification using silica gel was performed to obtain 2.4 g (97%) of compound 3 as a white-yellow solid.

Analytical data for compound 3:
Rf value 0.67 (Hexane/ _CH2Cl2 = _2/1 );
M. p. 303-305°C;
¹ H NMR (400 MHz, _CDCl3 ) 8.89 (d, J = 1.8 Hz, 2H), 8.63 (d, J = 1.9 Hz, 2H), 8.61 (d, J = 8.9 Hz, 2H), 8.51 (d, J = 8.8 Hz, 2H), 7.77 (dd, J = 8.9, 1.9 Hz, 2H), 7.76 (dd, J = 8.8, 1 .8 Hz, 2 H), 1.48 (s, 18 H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 149.7, 131.8, 131.2, 129.8, 129.13, 129.09, 128.4, 127.9, 125.44, 125.39, 125. 3, 123.6, 121.2, 35.4, 31.7 ppm;
MS (DART-TOFMS) m/z: 598 [M] ⁺ ;
IR (neat): 2963, 1588, 1469, 1358, 1089, 910, 883, 808, 792 ^{cm -1} ;
HRMS (DART-TOFMS) calcd for C ₃₄ H ₃₀ Br ₂ : 598.0694 [M] ⁺ , found: 598.0679 [M] ⁺ ;
Anal. Calcd for _{C34H30Br2 :} C, _68.24 ; H, 5.05. Found: C, 68.15; H, 5.00.

Example 4
Synthesis of 3,14-dimethoxy-6,11-di-tert-butyldibenzo[g,p]chrysene (Compound 4) Compound 3 (4.8 g, 8.0 mmol) was added to dimethylformamide (80 mL) under an argon atmosphere. Suspended, copper iodide (9.1 g, 48 mmol) and sodium methoxide (80 mL, 400 mmol, 28% methanol solution) were added. The reaction solution was stirred at 120° C. for 2 hours, naturally cooled to room temperature, and filtered through a glass filter packed with celite and silica gel. It was transferred to a 500 mL separatory funnel, washed with saturated saline, dried over Glauber's salt, and dried in a vacuum to obtain a crude product of compound 4. Filtration column purification using silica gel was performed to obtain 3.3 g (82%) of compound 4 as a white-yellow solid.

Analytical Data for Compound 4:
Rf value 0.40 (Hexane/ _CH2Cl2 = _2/1 );
M. p. 239-240°C;
¹ H NMR (400 MHz, _CDCl3 ) 8.77 (d, J = 1.8 Hz, 2H), 8.60 (d, J = 8.6 Hz, 2H), 8.52 (d, J = 9.0 Hz, 2H), 8.14 (d, J = 2.5 Hz, 2H), 7.74 (dd, J = 8.6, 1.8 Hz, 2H), 7.29 (dd, J = 9.0, 2 .5Hz, 2H), 3.93 (s, 6H), 1.46 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.9, 149.2, 130.1, 129.3, 128.84, 128.83, 125.5, 125.02, 124.99, 124.8, 123. 6, 116.9, 110.3, 55.7, 35.4, 31.9 ppm;
MS (DART-TOFMS) m/z: 501 [MH] ⁺ ;
IR (neat): 2952, 1610, 1483, 1459, 1272, 1228, 1049, 806, 786 ^{cm -1} ;
HRMS (DART-TOFMS) calcd for C ₃₆ H ₃₇ O ₂ : 501.2794 [MH] ⁺ , found: 501.2781 [MH] ⁺ ;
Anal. _Calcd for _C36H36O2 : C, _86.36 ; H, 7.25. Found: C, 86.36; H, 7.24.

Example 5
Synthesis of 3,14-dihydroxy-6,11-di-tert-butyldibenzo[g,p]chrysene (compound 5). , 1 M boron tribromide (30 mL, 30 mmol, methylene chloride solution) was added dropwise over 5 minutes at 0°C. After stirring at 0° C. for 15 minutes, the temperature was naturally raised to room temperature, and the mixture was stirred for 1.5 hours. The reaction was quenched with water. The aqueous layer was extracted with ethyl acetate, and the combined organic layer was washed with saturated brine, dried over Glauber's salt, and dried under vacuum to obtain a crude product. Filtration column purification using silica gel was performed to obtain 4.4 g (94%) of compound 5 as a pale yellow solid.

Analytical data for compound 5:
Rf value 0.33 (Hexane/EtOAc = 2/1);
M. p. 301-318°C;
¹ H NMR (400 MHz, _CDCl3 ) 8.71 (d, J = 2.0 Hz, 2H), 8.59 (d, J = 8.6 Hz, 2H), 8.49 (d, J = 8.8 Hz, 2H), 8.09 (d, J = 2.6 Hz, 2H), 7.73 (dd, J = 8.6, 2.0 Hz, 2H), 7.20 (dd, J = 8.8, 2 .6 Hz, 2H), 4.87 (s, 2H), 1.46 (s, 18H) ppm;
¹³ C NMR (100 MHz, DMSO- _d6 ) 155.5, 148.5, 129.0, 128.2, 127.7, 127.4, 124.82, 124.78, 123.8, 123.7, 123.3, 116.8, 112.1, 34.7, 31.1 ppm;
MS (DART-TOFMS) m/z: 473 [MH] ⁺ ;
IR (neat): 3339 (OH), 2955, 1612, 1578, 1482, 1215, 1176, 958, 792, 479 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₃₄ H ₃₃ O ₂ : 473.2481 [MH] ⁺ , found: 473.2468 [MH] ⁺ .

Example 6
Synthesis of 3,14-dimethoxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (compound 6) Under an argon atmosphere, compound 4 (3.6 g, 7.2 mmol) was treated with tert chloride. -butyl (35 mL, 320 mmol), and aluminum trichloride (240 mg, 1.8 mmol) was added at room temperature. After stirring for 10 minutes, the temperature was raised to 50° C., and the mixture was further stirred for 30 minutes. The reaction was stopped with 1M hydrochloric acid at 0°C. The aqueous layer was subjected to an extraction operation with toluene, and the combined organic layer was washed with saturated brine, dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Filtration column purification using silica gel was performed to obtain 3.7 g (84%) of compound 6 as a white-yellow solid.

Analytical Data for Compound 6:
Rf value 0.49 (Hexane/CH2Cl2, 4:1);
M. p. 208°C (dec.);
¹ H NMR (400 MHz, _CDCl3 ) 8.77 (d, J = 1.9 Hz, 2H), 8.60 (d, J = 8.6 Hz, 2H), 8.52 (s, 2H), 8.09 (s, 2H), 7.71 (dd, J = 8.6, 1.9Hz, 2H), 3.95 (s, 6H), 1.58 (s, 18H), 1.46 (s, 18H) ) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.3, 149.1, 138.7, 129.6, 128.7, 128.3, 128.1, 125.0, 124.8, 124.4, 123. 6, 121.6, 110.0, 55.4, 35.7, 35.4, 32.0, 30.2 ppm;
MS (DART-TOFMS) m/z: 613 [MH] ⁺ ;
IR (neat) 2947, 1616, 1486, 1463, 1399, 1361, 1222, 1178, 1055, 816 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₄ H ₅₃ O ₂ : 613.4046 [MH] ⁺ , found; 613.4046 [MH] ⁺ .

Example 7
Synthesis of 3,14-dihydroxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (compound 7). Decanethiol (15 mL, 72 mmol) was added. Potassium tert-butoxide (6.1 g, 54 mmol) was added at 0° C., and after stirring for 15 minutes, the temperature was allowed to rise to room temperature, and 7 (3.7 g, 6.0 mmol) was added. After stirring for 21 hours under reflux conditions, the reaction was stopped with 1M hydrochloric acid. The aqueous layer was extracted with ethyl acetate, and the combined organic layer was washed with saturated brine, dried over Glauber's salt, and dried under vacuum to obtain a crude product. Filtration column purification using silica gel was performed to obtain 2.7 g (80%) of compound 7 as a greenish-yellow solid.

Analytical data for compound 7:
Rf value 0.53 (Hexane/EtOAc = 4/1);
M. p. 163°C (dec.);
¹ H NMR (400 MHz, _CDCl3 ) 8.69 (d, J = 2.0 Hz, 2H), 8.58 (d, J = 8.6 Hz, 2H), 8.51 (s, 2H), 7.92 (s, 2H), 7.70 (dd, J = 8.6, 2.0Hz, 2H), 4.91 (s, 2H), 1.62 (s, 18H), 1.46 (s, 18H) ) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 153.0, 149.0, 136.9, 129.3, 128.7, 128.4, 127.6, 125.5, 124.9, 124.5, 123. 5, 122.1, 114.6, 35.5, 35.3, 31.9, 30.1 ppm;
MS (DART-TOFMS) m/z: 585 [MH] ⁺ ;
IR (neat) 3606 (OH), 3551 (OH), 2953, 1620, 1418, 1404, 1389, 1361, 1164, 813 ^{cm -1} ;
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₉ O ₂ : 585.3733 [MH] ⁺ , found; 585.3729 [MH] ⁺ .

Example 8
Synthesis of 4,13-dibromo-3,14-dihydroxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (compound 8) Under an argon atmosphere, compound 7 (1.8 g, 3 .1 mmol) in anhydrous methylene chloride (31 mL), bromine (13 mL, 13 mmol, 1 M methylene chloride solution) was added dropwise over 15 minutes at −78° C. and stirred for 15 minutes. A 3M sodium thiosulfate aqueous solution (9 mL) was added, and after heating to 0°C, 1M hydrochloric acid was added to stop the reaction. The organic layer was separated, the aqueous layer was extracted with ethyl acetate, and the combined organic layer was washed with saturated brine, dried over Glauber's salt, and dried under vacuum to obtain a crude product. Column purification using silica gel was performed to obtain 1.5 g (67%) of compound 8 as a yellow solid.

Analytical data for compound 8:
Rf value 0.40 (Hexane/Toluene = 9/1);
M. p. 166-176°C;
¹ H NMR (400 MHz, _CDCl3 ) 8.70 (s, 2H), 8.45 (d, J = 8.5 Hz, 2H), 7.82 (d, J = 2.0 Hz, 2H), 7.66 (dd, J = 8.5, 2.0 Hz 2H), 6.60 (s, 2H), 1.64 (s, 18H), 1.40 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 151.5, 147.3, 137.2, 131.3, 129.6, 127.5, 127.2, 126.3, 126.0, 124.5, 122. 9, 121.8, 110.4, 36.4, 35.2, 31.7, 29.9 ppm;
MS (DART-TOFMS) m/z: 743 [MH] ⁺ ;
IR (neat) 3463 (OH), 2953, 1596, 1464, 1400, 1386, 1362, 1185, 813, 740, 626, 421 ^cm-1 ;
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₇ Br ₂ O ₂ : 743.1922 [MH] ⁺ , found; 743.1928 [MH] ⁺ .

Example 9
Synthesis of 4,13-dibromo-3,14-dimethoxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (compound 9) Under an argon atmosphere, compound 8 (1.8 g, 2 .4 mmol) was suspended in acetone (20 mL) and iodomethane (3.7 mL, 62 mmol) and diazabicycloundecene (4.6 mL, 31 mmol) were added over 5 minutes. After stirring for 1 hour at room temperature, the reaction was quenched with 1M hydrochloric acid. The aqueous layer was subjected to an extraction operation with toluene, and the combined organic layer was washed with saturated brine, dried over Glauber's salt, and dried in a vacuum to obtain 1.8 g of a crude product. Column purification using silica gel was performed to obtain 1.3 g (70%) of compound 9 as a white-yellow solid.

Analytical data for compound 9:
_Rf value 0.42 (Hexane/ _CH2Cl2 = 4:1);
M. p. 280°C (dec.);
¹ H NMR (400 MHz, _CDCl3 ) 8.72 (s, 2H), 8.47 (d, J = 8.5 Hz, 2H), 7.93 (d, J = 1.9 Hz), 7.68 (dd , J=8.5, 1.9 Hz, 2H), 4.21 (s, 6H), 1.62 (s, 18H), 1.41 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 159.6, 147.4, 142.9, 131.6, 130.0, 128.9, 128.4, 127.2, 127.1, 124.5, 122. 9, 122.4, 117.0, 62.6, 36.3, 35.2, 31.7, 31.1 ppm;
MS (DART-TOFMS) m/z: 771 [MH] ⁺ ;
IR (neat) 2955, 1610, 1463, 1360, 1258, 1228, 1059, 991, 812, 795, 740 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₄ H ₅₁ Br ₂ O ₂ : 771.2235 [MH] ⁺ , found; 771.2245 [MH] ⁺ ;
Anal. _Calcd for _{C44H50Br2O2 :} C, 68.57; H, 6.54 _. Found: C, 68.56; H, 6.53.

Example 10
Synthesis of di-tert-butyl (6,11-di-tert-butyldibenzo[g,p]chrysene-3,14-diyl)dicarbamate (Compound 10) Under an argon atmosphere, Compound 3 (2.5 g, 4. 2 mmol), copper iodide (1.6 g, 8.4 mmol), tert-butyl carbamate (2.4 g, 20 mmol), and potassium carbonate (2.3 g, 17 mmol) in anhydrous toluene (63 mL). '-dimethylethylenediamine (1.8 mL, 17 mmol) was added. After stirring at 110° C. for 48 hours, the mixture was filtered through celite at room temperature. The resulting organic layer was washed with saturated brine, dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Filtration column purification using silica gel was performed to obtain 1.9 g (65%) of compound 10 as a pale yellow solid.

Analytical data for compound 10:
¹ H NMR (400 MHz, _CDCl3 ) 8.91 (s, 2H), 8.75 (d, J = 1.8 Hz, 2H), 8.58 (d, J = 8.6 Hz, 2H), 8.51 (d, J = 8.7 Hz, 2H), 7.73 (dd, J = 8.6, 1.8 Hz, 2H), 7.49 (dd, J = 8.7, 2.0 Hz, 2H), 6.61 (s, 2H), 1.53 (s, 18H), 1.48 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 152.6, 148.9, 136.4, 129.8, 128.8, 128.6, 128.5, 126.5, 124.9, 124.7, 123. 9, 123.0, 117.9, 117.5, 80.5, 35.1, 31.4, 28.3 ppm;
MS (DART-TOF) m/z: 669 [MH] ^- ;
IR (neat): 3414, 2956, 1722, 1510, 1363, 1217, 1148, 1053, 877 ^{cm -1} ;
HRMS (DART-TOF) calcd for C ₄₄ H ₄₉ N ₂ O ₄ : 669.3692 [MH] ⁻ , found: 669.3705 [MH] ⁻ ;
Anal. Calcd _{for C44H50N2O4} ; C, 78.77; _H , 7.55; N, _4.22 . Found: C, 78.49; H, 7.51; N, 4.18.

Example 11
Synthesis of 6,11-di-tert-butyldibenzo[g,p]chrysene-3,14-diamine (Compound 11) Compound 10 (1.9 g, 2.9 mmol) in anhydrous methylene chloride (48 mL) under an argon atmosphere. Trifluoroacetic acid (11 mL, 144 mmol) was added dropwise to the solution at 0°C. After stirring for 2 hours at room temperature, the reaction was stopped using saturated aqueous sodium bicarbonate. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride, dried over mirabilite, and dried in a vacuum to obtain a brown-yellow crude product. Filtration column purification using silica gel was performed to obtain 1.3 g (98%) of compound 11 as a yellow solid.

Analytical data for compound 11:
¹ H NMR (400 MHz, _CDCl3 ) 8.76 (d, J = 1.7 Hz, 2H), 8.57 (d, J = 8.5 Hz, 2H), 8.38 (d, J = 8.6 Hz, 2H), 7.93 (d, J = 2.2 Hz, 2H), 7.71 (dd, J = 8.5, 1.7 Hz, 2H), 7.05 (dd, J = 8.6, 2 .2Hz, 2H), 3.79 (brs, 4H), 1.46 (s, 18H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 148.4, 143.8, 129.6, 129.1, 128.4, 128.2, 124.9, 124.1 (two peaks are overlapped), 124.06, 123.0, 116.1, 113.0, 35.0, 31.5 ppm;
MS (DART-TOF) m/z: 471 [MH] ⁺ ;
IR (neat): 3446, 3355, 3208, 2952, 1610, 1483, 1189, 1137, 806 ^{cm -1} ;
HRMS (DART-TOF) calcd for C ₃₄ H ₃₅ N ₂ : 471.2795 [MH] ⁺ , found: 471.2788 [MH] ⁺ ;
Anal. Calcd _{for C34H34N2} ; C, 86.77; H, 7.28; N, _5.95 . Found: C, 86.76; H, 7.06; N, 5.90.

Example 12
Synthesis of 4,13-methylthio-3,14-dimethoxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (Compound (±)-12) The starting dibromide (1.5 g, 1.9 mmol) and anhydrous toluene were added to the flask. Methyllithium (6.3 mL, 7.6 mmol, 1.2 M diethyl ether solution) was added dropwise at −45° C. over 5 minutes, and after stirring for 30 minutes, dimethyl disulfide (1.4 mL, 15 mmol) was added. After stirring the reaction solution for 1 hour, the temperature was raised to room temperature, stirring was continued for an additional 1 hour, and water was added to terminate the reaction. The aqueous layer was subjected to an extraction operation with toluene, washed with saturated brine, dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Column purification using silica gel was performed to obtain 1.2 g (89%) of the desired compound (±)-12.

Analytical Data for Compound (±)-1:
M. p. 308-318°C.
¹ H NMR (400 MHz, _CDCl3 ) 8.61 (s, 2H), 8.54 (d, J = 8.6 Hz, 2H), 7.94 (d, J = 2.0 Hz, 2H), 7.69 (dd, J = 8.6 Hz, 2.0 Hz, 2H), 4.31 (s, 6H), 1.81 (s, 6H), 1.60 (s, 18H), 1.42 (s, 18H) ppm.
¹³ C NMR (100 MHz, _CDCl3 ) 160.9, 148.1, 142.4, 132.3, 131.1, 130.3, 127.0, 126.6, 124.4 (two peaks are overlapped), 124.3, 123.2, 121.2, 60.4, 36.2, 35.3, 31.7, 30.9, 20.3 ppm.
MS (DART-TOF) m/z: 705 [MH] ⁺ .
IR (neat): 2954, 1357, 1227, 1061, 994, 812, 758, 629 cm ^-1 .
HRMS (DART-TOF) calcd. for _C46H57O2S2 : _705.3794 [MH] _< ^+> , found: _705.3787 .

Example 13
Synthesis of 4,13-methylsulfonyl-3,14-dimethoxy-2,6,11,15-tetra-tert-butyldibenzo[g,p]chrysene (Compound (±)-13) 1.5 g, 2.2 mmol), dichloromethane and acetic acid were added. After a hydrogen peroxide solution (30%, 22 mL) was added dropwise, the temperature was raised to 60° C. and the reaction solution was stirred for 24 hours. Further, aqueous hydrogen peroxide (30%, 5.0 mL) was added, and after stirring for 6 hours, a saturated aqueous sodium hydrogencarbonate solution was added at 0°C to terminate the reaction. The aqueous layer was subjected to an extraction operation with toluene, washed with saturated brine, dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Silica gel column purification was performed to obtain 1.3 g (79%) of compound (±)-2.

Analytical Data for Compound (±)-2:
M. p. 300°C (dec.).
¹ H NMR (400 MHz, _CDCl3 ) 8.89 (s, 2H), 8.48 (d, J = 8.6 Hz, 2H), 8.43 (d, J = 1.7 Hz, 2H), 7.69 (dd, J = 8.6 Hz, 1.9 Hz, 2H), 4.49 (s, 6H), 2.78 (s, 6H), 1.64 (s, 18H), 1.42 (s, 18H) ppm.
¹³ C NMR (100 MHz, _CDCl3 ) 161.7, 148.1, 142.4, 134.3, 134.0, 129.7, 127.0, 126.9 (two peaks are overlapped), 126.2, 125.8, 123.0, 122.0, 67.9, 46.2, 35.9, 35.1, 31.2, 30.7 ppm.
MS (DART-TOF) m/z: 786 [M ⁺ NH4] ⁺ .
IR (neat): 2952, 1427, 1361, 1304, 1228, 1138, 1127, 752 ^{cm -1} .
HRMS (DART-TOF) calcd. _{For C46H60NO6S2} : 786.3857 [M ⁺ NH4] ⁺ , found _{: 786.3851} .
Anal. Calcd. For _C46H56O6S2 ; C, _71.84 ; H _, 7.34 _. Found: C, 71.59; H, 7.22.

The method for producing a dibenzo[g,p]chrysene derivative of the present invention can be applied as a method for producing a dibenzo[g,p]chrysene derivative that is useful as a hole transport material for thin film transistors or as a light-emitting element for organic light-emitting diodes. In addition, the dibenzo[g,p]chrysene derivative of the present invention can be applied to a hole transport material for a thin film transistor and a light emitting element for an organic light emitting diode. In addition, the dibenzo[g,p]chrysene derivative of the present invention can be applied to the development of materials having chiroptical properties.

The most important elements of the present invention are fluorenone with two tert-butyl groups (2,7-di-tert-butyl-9-fluorenone) and fluorenone with two bromine groups (2,7-di-bromo- 9-fluorenone), and synthesized a derivative of dibenzo[g,p]chrysene using that method to synthesize a precursor of diindenochrysene-type Buckybowls. That is.

The main effects are as follows.
(1) Since it can be synthesized in a shorter process than before, it leads to a reduction in cost and time. This eliminates the need to attach a tert-butyl group or a bromine group after synthesizing dibenzo[g,p]chrysene, which has the effect of increasing productivity.
(2) A dibenzo[g,p]chrysene derivative that has a bromine atom and is soluble in an organic solvent can be synthesized very simply and simply. It is possible to introduce a wide variety of functional groups using the bromine atom as a foothold, and it will be an opportunity to create new functional materials based on the dibenzo[g,p]chrysene skeleton.
(3) A dibenzo[g,p]chrysene derivative that has a hydroxyl group and is soluble in an organic solvent can be synthesized very simply and simply. Contribution to synthesis and invention of various other nonplanar pi-conjugated compounds are expected.
(4) Since the primary amino group of the diamine compound (11) has high reactivity, it is worth creating polymers such as polyimide, polyamide, polyetherimide, and polyurea with high heat resistance, high glass transition temperature, and high thermal conductivity. have.

Claims (8)

A dibenzo[g,p]chrysene derivative having identical first substituents at positions 3 and 14 and identical second substituents different from the first substituents at positions 6 and 11. A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. 2. The dibenzo[g,p]chrysene derivative according to claim 1, which is a substituent selected from the following formula

,or,

3. The dibenzo[g,p]chrysene derivative according to claim 2, represented by: (a) a fluorenone derivative having the same first substituents at the 2 and 7-positions and a fluorenone derivative having the same second substituents different from the first substituents at the 2 and 7-positions are dimerized to obtain a spiroketone derivative; a step of making
(b) reducing the carbonyl group of the obtained spiroketone derivative to prepare a spiroalcohol derivative having a hydroxyl group;
4. The method for producing a dibenzo[g,p]chrysene derivative according to any one of claims 1 to 3, comprising the step of (c) dehydrating the obtained spiroalcohol derivative to obtain a dibenzo[g,p]chrysene derivative. . A spiroketone derivative having identical first substituents at positions 2 and 7 and identical second substituents different from the first substituents at positions 2' and 7'. A group in which the first substituent and the second substituent are an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, a halogeno group, a hydroxyl group, an alkyl ether group, a polyoxyalkylene group, an amide group, and an amino group. The spiroketone derivative according to claim 5, which is a substituent selected from the following formula

or,

The spiroketone derivative according to claim 6, represented by 5. A step of dimerizing a fluorenone derivative having identical first substituents at positions 2 and 7 and a fluorenone derivative having identical second substituents different from the first substituents at positions 2 and 7. 8. A method for producing a spiroketone derivative according to any one of items 1 to 7.