JP2022034432A - EASILY-SOLUBLE DIBENZO [g, p] CHRYSENE DERIVATIVE AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

To provide a dibenzo [g, p] chrysene derivative that is easily dissolved in organic solvent and has selectively halogeno groups at symmetrical two positions: the positions 2 and 7 or the positions 10 and 15.SOLUTION: The present invention discloses a dibenzo [g, p] chrysene derivative represented by the following chemical formula (where R1 is an alkyl group, alkenyl group, alkynyl group, alkanoyl group, alkenoyl group, or alkynoyl group, and R2 is a halogeno group).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 is a promising material as a functional material. The greatest feature of the dibenzo [g, p] chrysene structure is its highly non-planar pi-conjugated structure, which has attracted a lot of interest. Here, the non-planarity means that the aromatic ring is twisted in a spiral shape, and the spiral structure is expected as a hole transporting substance of a thin film or a light emitting element of an organic light emitting diode. In particular, it has high potential value in photon physical characteristics (quantum yield / excitation lifetime), electronic properties, and heat resistance, and attempts are being made to incorporate it into polymer materials.

However, dibenzo [g, p] chrysene does not have a reactive substituent, and it is necessary to introduce a reactive substituent in order to use it as a functional material. For example, a heteroatom such as halogen, nitrogen, oxygen, or sulfur is introduced, the heteroatom is converted to another substituent, and then 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 produce a functional material by polymerizing or reacting with a side chain or a terminal of the polymer. In particular, selective introduction of a halogeno group, especially a bromo group, into two symmetrical positions at the 2- and 7-positions or the 10- and 15-positions of dibenzo [g, p] chrysene converts them into various substituents. Since it is easy to use, it can be expected to be a useful compound as an intermediate for functional materials. However, polycyclic aromatic hydrocarbons have a problem that they are difficult to dissolve in organic solvents.

Non-Patent Document 1 discloses a compound having hydroxyl groups at the 2- and 10-positions of dibenzo [g, p] chrysene and n-hexyl groups at the 6- and 14-positions and having improved solubility in an organic solvent. However, even the compounds having substituents at the 7-position and the 15-position do not disclose the compounds having two bromo groups. Further, Non-Patent Document 2 discloses a compound having a bromo group at the 7-position and a 10-position of dibenzo [g, p] chrysene and a t-butyl group at the 2-position and the 15-position, respectively. Compounds having bromo groups at the 7-position and the 7-position, or both the 10-position and the 15-position are not disclosed. Further, in the methods described in these non-patent documents, a dibenzo [g, p] chrysene derivative having a halogeno group selectively at two symmetrical positions at the 2-position and the 7-position or the 10-position and the 15-position is used. It cannot be synthesized.

Angew. Chem. Int. Ed. 2019, 58, 7385-7389 Thin Solid Films, 2017, 636, 8-14

The present invention provides a dibenzo [g, p] chrysene derivative that is easily soluble in an organic solvent and selectively has a halogeno group at two symmetrical positions at the 2-position and the 7-position, or the 10-position and the 15-position. With the goal.

The present inventor has found a method for synthesizing 2,7-dihalogeno-10,15-dialkyldibenzochrysene, confirmed that the compound is easily soluble in an organic solvent, and completed the present invention.

（式中、Ｒ^１はアルキル基、アルケニル基、アルキニル基、アルカノイル基、アルケノイル基、アルキノイル基であり、Ｒ^２はハロゲノ基である。）
で表されるジベンゾ［ｇ，ｐ］クリセン誘導体に関する。 That is, the present invention
The following chemical formula

(In the formula, R ¹ is an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, and R ² is a halogeno group.)
It relates to a dibenzo [g, p] chrysene derivative represented by.

In the above formula, it is preferable that R ¹ is an alkyl group and R ² is a bromo group.

Further, the present invention
(1) A step of reacting dibenzo [g, p] chrysene with an alkanoyl halide in the presence of Lewis acid to synthesize 10,15-dialkanoyl dibenzochrysene.
(2) A step of reducing 10,15-dialkanoyldibenzochrysene to synthesize 10,15-dialkyldibenzochrysene, and
(3) The present invention relates to a method for producing 2,7-dihalogeno-10,15-dialkyldibenzochrysene, which comprises a step of halogenating 10,15-dialkyldibenzochrysene.

It is preferable that the dibenzo [g, p] chrysene used in the step (1) does not have a substituent on the aromatic ring.

、または、

で表されるジベンゾ［ｇ，ｐ］クリセン誘導体に関する。 Further, the present invention
The following chemical formula:

,or,

It relates to a dibenzo [g, p] chrysene derivative represented by.

Since the dibenzo [g, p] chrysen derivative of the present invention has high solubility in an organic solvent and has a halogeno group at a specific position, it is possible to introduce various functional groups, cross-coupling reaction and lithium-. By performing a precise substitution reaction by a halogen exchange reaction, it becomes possible to produce a new compound. For example, a 6-substituted dibenzo [g, p] chrysen derivative in which two alkyl groups, two triflate groups, and two chloro groups are introduced at their respective positions can be synthesized from the derivative, and the triflate group and chloro can be synthesized. The group can be converted into various functional groups, and various new compounds can be produced by performing a precise substitution reaction by a cross-coupling reaction or a lithium-halogen exchange reaction. As described above, the dibenzo [g, p] chrysene derivative of the present invention and the method for producing the same are triggers for producing a new functional material based on dibenzo [g, p] chrysene.

(A) In the ORTEP diagram of compound 12, it is a diagram showing a twist angle determined by four carbon atoms (C017, C02Q, C03W, C03D). (B) It is a top view of the ORTEP diagram of compound 12. (C) A side view from the butyl group side fjord region described at a twist angle of 47.13 ° ( _three CF groups are omitted). (D) A side view from the bay area region (Tf and C ₃ H ₇ sites of butyl groups omitted).

（式中、Ｒ^１はアルキル基、アルケニル基、アルキニル基、アルカノイル基、アルケノイル基、アルキノイル基であり、Ｒ^２はハロゲノ基である。）
で表される。 The first dibenzo [g, p] chrysene derivative of the present invention is
The following chemical formula

(In the formula, R ¹ is an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, and R ² is a halogeno group.)
It is represented by.

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。 Here, 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.

Examples of the alkyl group in R ¹ include a linear or branched alkyl group which may have a substituent. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. For example, methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n. -Undecyl, n-dodecyl and the like can be mentioned, with n-propyl, n-butyl, iso-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl and n-octyl being 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.

Examples of the alkanoyl group in R ¹ include a linear or branched alkanoyl group which may have a substituent. The alkanoyl group preferably has 1 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. For example, metanoyl, etanoyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, Examples thereof include n-undecanoyl and n-dodecanoyl, with propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl and n-octanoyl being preferred. An alkenoyl group is a group having a double bond inside or at the end of the alkanoyl group, and an alkinoyl group is a group having a triple bond inside or at the end of the alkanoyl group.

Examples of the halogeno group in ^R2 include a fluoro group, a chloro group, a bromo group and an iodine group, and a bromo group is preferable.

Among the above derivatives, a compound in which R ¹ is an alkyl group and R ² is a bromo group is preferable.

The method for producing 2,7-dihalogeno-10,15-dialkyldibenzochrysene of the present invention is as follows.
(1) A step of reacting dibenzo [g, p] chrysene with an alkanoyl halide in the presence of Lewis acid to synthesize 10,15-dialkanoyl dibenzochrysene.
(2) A step of reducing 10,15-dialkanoyldibenzochrysene to synthesize 10,15-dialkyldibenzochrysene, and
(3) Includes a step of halogenating 10,15-dialkyldibenzochrysene.

Process (1)
As the dibenzo [g, p] chrysen used in the step (1), a compound having no substituent on the aromatic ring or a compound having a substituent can be used, but the steric hindrance is said to be the smallest. In that respect, compounds having no substituent on the aromatic ring are preferred. The substituent is not particularly limited, and examples thereof include an alkoxy group, an alkylamino group, an alkylsulfide group, and a hydroxyl group. Of these, an alkoxy group is preferable, and among the alkoxy groups, a methoxy group and an ethoxy group are preferable. The substitution position of the substituent is not particularly limited, and examples thereof include substitution positions other than the 2, 7, 10, and 15 positions into which the alkyl group, alkanoyl group, and halogeno group are introduced.

As the alkanoyl halide, alkanoyl chloride corresponding to the above-mentioned alkanoyl group can be used, and examples thereof include propanoyl chloride and butyryl chloride. The amount of the alkanoyl halide used is preferably 2 to 4 equivalents with respect to dibenzo [g, p] chrysene, and more preferably 4 equivalents. If it is less than 2 equivalents, it becomes a mixture of a compound containing one alkanoyl group and a compound containing two alkanoyl groups. Excess alkanoyl chloride tends to be wasted.

Examples of Lewis acid include aluminum chloride. The amount of Lewis acid used is preferably 2 to 4 equivalents with respect to dibenzo [g, p] chrysene, more preferably 4 equivalents. If it is less than 2 equivalents, it becomes a mixture of a compound containing one alkanoyl group and a compound containing two alkanoyl groups. Excess alkanoyl chloride tends to be wasted.

By carrying out the acylation reaction under the above conditions, the alkanoyl group can be regioselectively introduced into the 10-position and the 15-position (or the 2-position and the 7-position).

Process (2)
The method for reducing 10,15-dialkanoyldibenzochrysene is not particularly limited, and examples thereof include a reduction reaction using a metal hydride such as sodium borohydride and lithium aluminum hydride. The reaction conditions can also be appropriately selected. For example, when sodium borohydride is used, it may be reduced by a known method in combination with aluminum chloride.

Process (3)
The method for halogenating 10,15-dialkyldibenzochrysene is not particularly limited, and for example, a method for contacting 10,15-dialkyldibenzochrysene with bromine to bromine, a method for contacting with chlorine for chlorination, iodine and the like. Examples thereof include a method of contacting and iodination. The reaction conditions can also be appropriately selected.

（式中、Ｒ^１ははアルキル基、アルケニル基、アルキニル基、アルカノイル基、アルケノイル基、アルキノイル基であり、Ｒ^２はハロゲノ基である。）
で表される２，７－ジハロゲノ－１０，１５－ジアルキルジベンゾクリセンを得る。 According to step (3), the formula

(In the formula, R ¹ is an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, and R ² is a halogeno group.)
The 2,7-dihalogeno-10,15-dialkyldibenzochrysene represented by is obtained.

2,7-Dihalogeno-10,15-dialkyldibenzochrysene is suitable as a raw material for producing a dibenzo [g, p] chrysene derivative because it has excellent solubility in an organic solvent. It is possible to convert two bromo groups into the same substituent to form a symmetric derivative, or to convert into different substituents into an asymmetric derivative.

、または、

で表されることを特徴とする。 The second dibenzo [g, p] chrysene derivative of the present invention has the following chemical formula:

,or,

It is characterized by being represented by.

Compound 2 can be obtained by using butyryl chloride as the alkanoyl halide in the step (1) of the method for producing 2,7-dihalogeno-10,15-dialkyldibenzochrysene of the present invention. Compound 3 can be obtained by reducing compound 2 in step (2) of the above-mentioned production method. Compound 1 can be obtained by brominating compound 3 in the step (3) of the above-mentioned production method. Compound 4 can be obtained, for example, by cross-coupling compound 1 with acetylene using a palladium catalyst. Compound 5 can be obtained, for example, by cross-coupling compound 1 with pyrrolidine using a palladium catalyst. Compound 6 can be obtained by lithiolating the bromo group of compound 1, for example with n-butyllithium, and then reacting with, for example, dimethylformamide. Compound 7 can be obtained by lithiolating the bromo group of compound 1, then reacting with, for example, carbon dioxide as an electrophile to form a dicarboxylic acid, and then reacting with, for example, iodomethane. Compound 8 is obtained by lithiolating the bromo group of compound 1, for example, reacting with dimethylsilane chloride to form a bisdimethylsilane form, then reacting with, for example, methanol to form a dimethoxysilyl form, and further using hydrogen peroxide, for example, for framing. -It can be obtained by oxidizing Tamao.

Compound 9b is a so-called "push-pull type" structure having an electron-donating group and an electron-withdrawing group, and can be a dye material responsive to the flow of electrons. Compound 9a, which is a raw material for compound 9b, can be obtained by lithiolating one of the bromo groups of compound 1, then reacting with, for example, carbon dioxide as an electrophile, and then reacting with, for example, iodomethane. In order to lithium only one of the bromo groups, the amount of n-butyllithium added and the reaction temperature may be appropriately adjusted. Compound 9b can be obtained, for example, by cross-coupling compound 9a with pyrrolidine using a palladium catalyst.

Compound 10a can be obtained by lithiolating one of the bromo groups of compound 1 and then reacting with, for example, trimethylsilyl chloride. Compound 10b can be obtained by lithiolating the bromo group of compound 10a and then reacting with, for example, dimethyl disulfide as an electrophile. Compound 10c can be obtained by reacting compound 10b with, for example, iodine monochloride. Compound 10d can be obtained by subjecting compound 10c to the Rosenmund-von Braun reaction using copper cyanide.

Compound 11 can be obtained by reacting compound 8 with, for example, iodine monochloride. Compound 12 can be obtained by triflate the hydroxyl group of compound 11 with, for example, trifluoromethanesulfonic anhydride (Tf ₂ O). Since compound 12 has a trifluoromethylsulfonyl group and a chloro group, it is expected that each of the trifluoromethylsulfonyl group and the chloro group can be selectively converted into various substituents by palladium-catalyzed cross-coupling or the like. can.

The dibenzo [g, p] chrysene derivative of the present invention is applied to the fields of polymer materials, photofunctional materials, and electronic materials. Specific examples thereof include materials for lithography, materials for organic EL, materials for resins such as adhesives, materials for super engineering plastics, and the like. In particular, it can be applied as a hole transporting substance for a thin film, a light emitting device for an organic light emitting diode, or a compound as a precursor thereof. Further, according to the method for producing a dibenzo [g, p] chrysene derivative of the present invention, the compound of the present invention can be selectively and easily produced with almost no by-production of isomers.

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

In the examples, the water-reactive reaction was carried out in an argon or nitrogen atmosphere, and the experiment was carried out under water-reactive conditions unless otherwise specified. The purchased anhydrous solvent / reagent was purified again and used without improving its purity. Merck silica 60F ₂₅₄ was used for thin layer chromatography, and silica gel 60 _N (manufactured by Kanto Chemical Co., Inc.) 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).

The ¹ H-NMR and ¹³ C-NMR spectra were measured at 400 MHz and 100 MHz, respectively, using a 5 mm QNP probe. The chemical shift values are indicated by δ (ppm), and the reference values in each solvent 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). The pattern of division is shown by s: single line, d: double line, t: triple line, q: quadruple line, m: multiple line, br: wide line.

Synthesis Example 1 (Synthesis of dibenzo [g, p] chrysene)

9-Fluorenone (80 g, 444 mmol) and triethyl phosphite (153 mL, 888 mmol) were added to a 1 L flask, and the mixture was stirred at 175 ° C. After 24 hours, the reaction solution was allowed to cool to 60 ° C., water (160 mL, 8.88 mmol) was added over 10 minutes, the temperature was raised to 80 ° C., and the remaining triethyl phosphate was hydrolyzed. After stirring for another 12 hours, the reaction solution was collected by filtration and washed with methanol (500 mL). The obtained solid was refluxed in methanol (252 mL, 6.21 mol) for 1 hour, and the filtration operation was performed again using methanol (400 mL). The obtained sample was dried on a rotary evaporator (70 ° C., 30 minutes) to obtain 49.7 g (yield 65%) of the spiroketone compound as a yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.20 (dd, J = 7.8, 1.2Hz, 1H), 8.10 (dd, J = 7.8, 1.2Hz, 1H), 7. 99 (dd, J = 7.8, 1.2Hz, 1H), 7.81-7.77 (m, 3H), 7.45 (ddd, J = 7.8, 7.8, 1.2Hz, 1H), 7.41-7.35 (m, 3H), 7.18 (ddd, J = 7.6,7.6,1.2Hz, 1H), 7.18 (ddd, J = 7.8) , 7.8, 1.2Hz, 1H), 7.08 (ddd, J = 7.8, 7.8, 1.2Hz, 1H), 7.04 (ddd, J = 7.8, 7.8) , 1.2Hz, 2H), 6.61 (dd, J = 7.8, 1.2Hz, 1H) ppm
¹³ C-NMR (100 MHz, CDCl ₃ ) 197.6, 147.4 (two peaks are overlapped), 142.0, 138.4, 135.2, 130.9, 130.4, 129.6, 128. 9,128.7 (two peaks are overlapped), 128.6, 128.4, 128.3 (two peaks are overlapped), 125.1 (two peaks are overwrapped), 124.5, 123.6, 120. 9 (two peaks are overlapped), 69.0 ppm
MS (DART-TOF) m / z: 345 [MH] ⁺
IR (neat): 3068, 1686 (C = O), 1603, 1478, 1447, 1256, 1132, 746, 718 cm ^-1
HRMS (DART-TOF) calcd for C ₂₆ H ₁₇ O: 345.1279, Found; 345.1276

The obtained spiroketone compound was subjected to the next reaction without further purification. Spiroketone (30 g, 87.1 mmol), toluene (132 mL) and methanol (24 mL) were added to a 500 mL flask, and the temperature was raised to 45 ° C. Sodium borohydride (1.32 g, 34.8 mmol) was slowly added to the flask over 30 minutes (189 mg each was added in 7 portions every 5 minutes), and the mixture was stirred for 1 hour. The reaction was stopped with acetone (0.64 mL, 8.4 mmol) and stirred for another 30 minutes. After washing the organic layer with water (100 mL × 3), the organic layer was transferred to a 500 mL flask and heated to 120 ° C. to remove azeotropic water. Methanesulfonic acid (0.06 mL, 0.87 mmol) is added thereto, and after stirring for 1 hour, the second azeotropic removal of water is performed using toluene as a reaction solvent, and the reaction solution is cooled to room temperature. Crystals were precipitated. The crystal was dibenzo [g, p] chrysene, and 23.5 g (yield 82%) of yellow crystals was obtained. The physical data of this compound was in perfect agreement with the product of Tokyo Chemical Industry Co., Ltd.

^{1 1} H-NMR (400 MHz, CDCl ₃ ) 8.72 (dd, J = 8.0, 1.3 Hz, 4H), 8.71 (dd, J = 8.0, 1.3 Hz, 4H), 7. 69 (ddd, J = 8.0, 8.0, 1.3Hz, 4H), 7.64 (ddd, J = 8.0, 8.0, 1.3Hz, 4H) ppm
¹³ C-NMR (100 MHz, CDCl ₃ ) 130.8, 129.2, 128.9, 127.4, 126.5 (two peaks are overlapped), 123.6 ppm

Example 1 (Synthesis of 2,7-dihalogeno-10,15-dibutyldibenzo [g, p] chrysene)

Process (1)
10,15-Dibutanoyldibenzo [g, p] chrysene (Compound 2)
Aluminum chloride (8.53 g, 64 mmol), methylene chloride (40 mL) and normal butyryl chloride (6.69 mL, 64 mmol) were added to a 200 mL two-necked flask under an argon atmosphere. After stirring the solution for 15 minutes, dibenzo [g, p] chrysene (5.25 g, 16 mmol) synthesized in Synthesis Example 1 was added. After stirring at room temperature for 1 hour, 1M hydrochloric acid (120 mL) was slowly added at 0 ° C. (10 minutes) to stop the reaction. An extraction operation (40 mL x 3) was performed on the aqueous layer with methylene chloride, and the combined organic layers were washed with water (100 mL x 2) and saturated saline (100 mL x 1), respectively, and then dried with sardine and vacuum dried. , 8.11 g of crude product was obtained. Filtration column purification using silica gel (developing solvent: toluene / methylene chloride = 2/1) was carried out to obtain 7.16 g of a yellow solid. A reprecipitation operation (methylene chloride / methanol = 1/8, v / v) was performed to obtain 6.52 g (87%) of a yellow solid, and then a recrystallization operation (10.7 mL / g) was performed with propionitrile. Then, 5.74 g (yield 77%) of Compound 2 was obtained as white-yellow crystals.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.33 (d, J = 1.6Hz, 2H), 8.80 (d, J = 8.6Hz, 2H), 8.69 (d, J = 7. 4Hz, 2H), 8.67 (d, J = 7.4Hz, 2H), 8.18 (dd, J = 8.6, 1.6Hz, 2H), 7.77 (dd, J = 7.5Hz) , 2H), 7.69 (dd, J = 7.5Hz, 2H), 3.19 (t, J = 7.4Hz, 4H), 1.91 (q, J = 7.4Hz, 4H), 1 .11 (t, J = 7.4Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 200.4, 134.9, 132.2, 131.6, 131.5, 131.3, 129.5, 129.4, 129.0, 127.9, 127. 53, 127.52, 125.8, 124.3, 124.1, 41.1, 18.3, 14.3 ppm
MS (DART-TOF) m / z: 469 [MH] ⁺
IR (neat): 2965, 2928, 1873, 1678, 1595, 1189, 735 cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₂₉ O ₂ : 469.2168 [MH] ⁺ , Found: 469.2168

Process (2)
10,15-Dibutyldibenzo [g, p] chrysene (Compound 3)
In a 300 mL flask under an argon atmosphere, compound 2 (3.75 g, 8 mmol) obtained in step (1), THF (80 mL), aluminum chloride (5.76 g, 43.2 mmol) and sodium borohydride (2. 91 g, 76.8 mmol) were added in order. After reacting under reflux conditions for 12 hours, the mixture was cooled to room temperature. After further cooling, 1M hydrochloric acid (100 mL) was added dropwise at 0 ° C. over 10 minutes to stop the reaction. An extraction operation (30 mL × 3) was performed on the aqueous layer with toluene, and the combined organic layer was washed with water (100 mL × 1) and saturated saline (100 mL × 1), respectively, and dried with sardine and vacuum. 4.55 g of crude product was obtained. Filtration column purification using silica gel (developing solvent: hexane / methylene chloride = 19/1) was carried out to obtain 2.74 g (yield 78%) of compound 3 as a white solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.71 (d, J = 8.4Hz, 2H), 8.69 (d, J = 8.4Hz, 2H), 8.61 (d, J = 8. 4Hz, 2H), 8.49 (s, 2H), 7.68-7.59 (m, 4H), 7.47 (dd, J = 8.4, 1.4Hz, 2H), 2.91 ( t, J = 7.4Hz, 4H), 1.80 (tt, J = 7.4,7.4Hz, 4H), 1.48 (tq, J = 7.4,7.4Hz, 4H), 1 .00 (t, J = 7.4Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 144.4, 131.2, 130.9, 129.7, 129.1, 129.0, 128.0, 127.6, 127.5, 126.5, 126. 4,123.8, 123.1, 36.3, 34.1, 22.8, 14.4 ppm
MS (DART-TOF) m / z: 441 [MH] ⁺
IR (neat): 3064,2952,2925,2854,1613,1434,828,764cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₃₃ : 441.2577 [MH] ⁺ , Found: 441.2600

Process (3)
2,7-Dibromo-10,15-dibutyldibenzo [g, p] chrysene (Compound 1)
Compound 3 (2.2 g, 5.0 mmol) obtained in step (2) and methylene chloride (20 mL) were added to a 100 mL flask under an argon atmosphere. After stirring at −20 ° C. for 15 minutes, bromine (0.51 mL, 10.0 mmol, 4.2 M methylene chloride solution) was added dropwise over 5 minutes. After returning to room temperature and stirring for 30 minutes, 1 M sodium thiosulfate (20 mL) was added dropwise at 0 ° C. to stop the reaction. An extraction operation (20 mL × 3) was performed on the aqueous layer with methylene chloride, and the combined organic layer was washed with saturated brine (20 mL × 1), dried with sardine and vacuum dried, and 2.94 g of crude product was obtained. Got Filtration column purification using silica gel (developing solvent: hexane / toluene = 9/1) was carried out to obtain 2.84 g of a yellow solid. A reprecipitation operation (methylene chloride / methanol = 1/8, v / v) was performed to obtain 2.62 g of a yellowish white solid, and then a recrystallization operation (28.3 mL / g) was performed with propionitrile. .34 g (78% yield) of compound 1 was obtained as white crystals.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.79 (d, J = 1.8Hz, 2H), 8.56 (d, J = 8.5Hz, 2H), 8.38 (d, J = 8. 5,2H), 8.37 (s, 2H), 7.66 (dd, J = 8.5,1.8Hz, 2H), 7.48 (dd, J = 8.5,1.8Hz, 1H) ), 2.90 (t, J = 7.4Hz, 4H), 1.79 (tt, J = 7.4,7.4,4H), 1.48 (tq, J = 7.4,7. 4Hz, 4H), 1.00 (t, J = 7.4Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 141.6, 131.8, 129.7, 129.4, 129.0, 128.6, 127.8, 127.7, 127.2, 127.1, 126. 2,124.7,122.7,120.3, 36.1,33.8,22.8,14.2ppm
MS (DART-TOF) m / z: 599 [MH] ⁺
IR (neat): 2952, 2920, 2853, 1413, 1085, 918, 863, 812, 562 cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₃₁ Br ₂ : 599.0772 [MH] ⁺ , Found: 599.0788
Anal. Calcd for C ₃₄ H ₃₀ Br ₂ : C, 68.24; H, 5.05. Found: C, 67.88; H, 5.10

<Measurement of solubility>
The amount of methylene chloride required to dissolve 1 mmol of unsubstituted dibenzo [g, p] chrysene without an alkyl group was 100 ml. In contrast, 3 milliliters of methylene chloride was required to dissolve 1 mmol of 10,15-dibutyldibenzo [g, p] chrysene with two alkyl groups. An improvement in solubility of approximately 33 times was observed.

Example 2
2,7-Dietinyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 4)

Compound 1 (240 mg, 0.4 mmol) was dissolved in toluene (3.0 mL) and triethylamine (3.0 mL) to bis (triphenylphosphine) palladium (II) dichloride (28 mg, 0.04 mmol), copper iodide (28 mg, 0.04 mmol). 15.2 mg, 0.08 mmol), triphenylphosphine (21 mg, 0.08 mmol) and trimethylsilylacetylene (0.33 mL, 2.4 mmol) were added. After stirring at 70 ° C. for 14 hours, the mixture was filtered through cerite and floridyl (developing solvent: toluene 20 mL), and the filtrate was removed and concentrated. The obtained reaction product was diluted with toluene (20 mL), washed with water (20 mL × 3) and saturated brine (20 mL × 3) using a 100 mL separatory funnel, dried with sardine and vacuum dried. 320 mg of crude brown product was obtained.

THF (4 mL), methanol (4 mL) and potassium carbonate (514 mg, 3.72 mmol) were added to this crude product, and the mixture was stirred at room temperature for 1 hour, and then the disappearance of the starting material was confirmed by thin layer chromatography. The obtained reaction product was diluted with toluene and filtered through cerite. The reaction was stopped with a saturated aqueous solution of ammonium chloride (40 mL), washed with water (40 mL × 3) and saturated saline (40 mL × 3) using a 200 mL separatory funnel, dried with sardine and vacuum dried, and a brown solid. 216 mg of crude product was obtained. Column purification using silica gel (developing solvent: hexane / toluene = 9/1) was carried out to obtain 143 mg (yield 73%) of compound 4 as an orange solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.82 (d, J = 1.6Hz, 2H), 8.55 (d, J = 8.4Hz, 2H), 8.50 (d, J = 8. 5Hz, 2H), 8.43 (d, J = 1.4Hz, 2H), 7.67 (dd, J = 8.5, 1.6Hz, 2H), 7.47 (dd, J = 8.4) , 1.4Hz, 2H), 3.26 (s, 2H), 2.90 (t, J = 7.5Hz, 4H), 1.79 (tq, J = 7.5, 7.5Hz, 4H) , 1.49 (tq, J = 7.5Hz, 4H), 1.01 (t, J = 7.5Hz, 2H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 142.2, 130.54, 130.52, 129.7, 129.6, 129.4, 129.2, 128.7, 128.1, 128.0, 127. 5,125.6, 123.2, 119.8, 84.6, 78.2, 36.3, 34.1, 22.9, 14.4 ppm
MS (DART-TOF) m / z: 489
IR (neat): 3284,2952,2924,2848,2097,1610,1456,1424,820,590cm ^-1
HRMS (DART-TOF) calcd for C ₃₈ H ₃₃ : 489.2582 [MH] ⁺ , Found; 489.2583
Anal. Calcd for C ₃₈ H ₃₂ : C, 93.40; H, 6.60. Found: C, 93.39; H, 6.71

Example 3
2,7-di (1-pyrrolidinyl) -10,15-dibutyldibenzo [g, p] chrysene (Compound 5)

Tris (dibenzylideneacetone) dipalladium (0) (73 mg, 0.08 mmol), 2,2-bis (diphenylphosphino) -1,1-binaphthyl (149 mg, 0.24 mmol) and sodium tert-butoxide in Schlenk tubes. After adding (231 mg, 2.4 mmol), it was filled with argon gas. Toluene (16 mL) was added and the mixture was stirred for 15 minutes. Then, compound 1 (479 mg, 0.8 mmol) was added, the mixture was further stirred for 1 minute, and pyrrolidine (0.26 mL, 3.2 mmol) was added. The temperature was slowly raised to 90 ° C., and after stirring for 14 hours, the temperature was lowered to stop the reaction, and the mixture was filtered using cerite and floridil. The obtained crude product was purified by a filtration column using silica gel (developing solvent: hexane / methylene chloride = 4/1) to obtain 382 mg (yield 83%) of compound 5 as an orange-yellow solid. ..

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.39 (d, J = 1.6Hz, 1H), 8.68 (d, J = 8.6Hz, 1H), 8.58 (dd, J = 8. 4,8.4Hz, 2H), 8.55 (d, J = 1.1Hz, 1H), 8.45 (d, J = 9.0Hz, 1H), 8.37 (d, J = 1.1Hz) , 1H), 8.17 (dd, J = 8.6, 1.6Hz, 1H), 7.62 (d, J = 2.3Hz, 1H), 7.45 (dd, J = 8.4) 1.1Hz, 2H), 6.99 (dd, J = 9.0, 2.3Hz, 1H), 4.06 (s, 3H), 3.57 (t, J = 6.5Hz, 4H), 2.93-2.89 (m, 4H), 2.14 (t, J = 6.5Hz, 4H), 1.83-1.74 (m, 4H), 1.02-0.98 (m) , 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 167.8, 146.7, 141.5, 140.9, 132.8, 132.6, 131.4, 130.4, 130.2, 130.1, 129. 32, 123.28, 128.8, 128.2, 128.0, 127.8, 127.4, 127.0, 126.9, 126.3, 126.2, 126.0, 123.4 123.2, 120.1, 113.5, 103.7, 52.5, 48.1, 36.4, 36.3, 34.3, 34.2, 25.8, 22.91,22. 90, 14.37, 14.36 ppm
MS (DARTTOF) m / z: 579 [MH] ⁺
IR (neat): 2949, 2925, 2853, 1718, 1606, 1367, 1236, 1113, 806, 763 cm ^-1
HRMS (DART-TOF) calcd for C ₄₂ H ₄₇ N ₂ : 579.3739 [MH] ⁺ , Found: 579.3721
Anal. Calcd for C ₄₂ H ₄₆ N ₂ : C, 87.15; H, 8.01; N, 4.84. Found: C, 87.13; H, 8.16; N, 4.79

Example 4
2,7-Diformyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 6)

Under an argon atmosphere, normal butyllithium (0.6 mL, 0.96 mmol, 1.59 M hexane solution) was added dropwise to an anhydrous tetrahydrofuran (2 mL) solution of compound 1 (240 mg, 0.4 mmol) at −78 ° C. over 3 minutes. did. After stirring at −78 ° C. for 30 minutes, N, N-dimethylformamide (0.6 mL, 8 mmol) was added. The temperature was raised to 0 ° C., stirring was performed for 10 minutes, and then the reaction was stopped with 1M hydrochloric acid. The aqueous layer was subjected to an extraction operation (20 mL × 3) with toluene, washed with saturated brine, dried with sardine and vacuum dried to obtain a crude product of a pale yellow solid. A column purification operation using silica gel (developing solvent: hexane / methylene chloride = 1/4) was carried out to obtain 168 mg (yield 84%) of compound 6 as a pale yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 10.18 (s, 2H), 8.97 (d, J = 1.5Hz, 2H), 8.36 (d, J = 1.5Hz, 2H), 8 .32 (d, J = 8.5Hz, 2H), 8.28 (d, J = 8.5Hz, 2H), 7.84 (dd, J = 8.5, 1.5Hz, 2H), 7. 35 (dd, J = 8.5, 1.5Hz, 2H), 2.84 (t, J = 7.4Hz, 4H), 1.76 (t, J = 7.4, 7.4Hz, 4H) , 1.48 (tq, J = 7.4, 7.4Hz, 4H), 1.02 (t, J = 7.4Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 192.2, 143.2, 133.8, 133.2, 132.5, 131.2, 130.5, 129.4, 129.1, 128.4, 127. 2,126.8, 125.9, 124.9, 123.1, 36.3, 34.0, 22.9, 14.3 ppm
MS (DART-TOFMS) m / z: 497 [MH] ⁺
IR (neat): 2952, 2924, 2853, 2718, 1689, 1595, 1191, 823 cm ^-1
HRMS (DART-TOFMS) calcd for C ₃₆ H ₃₃ O ₂ : 497.2475 [MH] ⁺ , Found: 497.2468

Example 5
2,7-di (methoxycarbonyl) -10,15-dibutyldibenzo [g, p] chrysene (Compound 7)

Under an argon atmosphere, normal butyllithium (0.30 mL, 1.59 M hexane solution) was added dropwise to a solution of compound 1 (120 mg, 0.2 mmol) in anhydrous tetrahydrofuran (4 mL) at −78 ° C. over 3 minutes. After stirring for 30 minutes, carbon dioxide was blown in for 5 minutes while keeping the open system (to ensure safety). After raising the temperature to room temperature, stirring for 1 hour, the reaction was stopped with 1 M hydrochloric acid (10 mL). The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (10 mL × 3) with toluene. The collected organic layer was washed with saturated brine and dried over Glauber's salt and vacuum dried to obtain a crude product.

Next, lithium carbonate (126 mg, 1.7 mmol) was added to a solution of the obtained crude product (91 mg, 0.17 mmol) in DMF (2.2 mL) under an argon atmosphere at room temperature. After stirring for 5 minutes, methyl iodide (0.11 mL, 1.7 mmol) was added dropwise over 1 minute. After stirring at room temperature for 20 hours, the reaction was stopped with 1 M hydrochloric acid (10 mL). The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (10 mL × 3) with toluene. The collected organic layer was washed with saturated brine, dried over glass and vacuum dried to obtain 85 mg of a crude product. A column purification operation using silica gel (developing solvent: hexane / methylene chloride = 1/1) was carried out to obtain 74 mg (yield 78%) of compound 7 as a yellowish white solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.41 (d, J = 1.5Hz, 2H), 8.65 (d, J = 8.6Hz, 2H), 8.60 (d, J = 8. 5Hz, 2H), 8.58 (d, J = 1.3Hz, 2H), 8.22 (dd, J = 8.6, 1.5Hz, 2H), 7.52 (dd, J = 8.5) , 1.3Hz, 2H), 4.07 (s, 6H), 2.94 (t, J = 7.3Hz, 4H), 1.80 (tt, J = 7.3, 7.3Hz, 4H) , 1.49 (tq, J = 7.3, 7.3Hz, 4H), 1.01 (t, J = 7.3Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 167.5, 142.6, 132.3, 131.3, 131.2, 130.2, 129.3, 128.6, 128.1, 127.5, 127. 2,126.7, 125.9, 125.0, 123.2, 52.6, 36.3, 34.1, 22.9, 14.3 ppm
MS (DART-TOF) m / z: 557
IR (neat): 2949,2952,2853,1718,1606,1427,1272,1249,1105,763cm ^-1
HRMS (DART-TOF) calcdforC ₃₈ H ₃₇ O ₄ : 557.2692 [MH] ⁺ , Found; 557.2681
Anal. Celsius for C ₃₈ H ₃₆ O ₄ : C, 81.99; H, 6.52. Found: C, 82.30; H, 6.70

Example 6
2,7-Dihydroxy-10,15-dibutyldibenzo [g, p] chrysene (Compound 8)

Under an argon atmosphere, normal butyllithium (4.8 mL, 1.59 M hexane solution) was added dropwise to an anhydrous tetrahydrofuran (64 mL) solution of compound 1 (1.91 g, 3.2 mmol) over 4 minutes at −78 ° C. After stirring for 30 minutes, dimethylsilane chloride (1.32 mL, 19.2 mmol) was added over 20 seconds. After stirring at room temperature for 1 hour, the reaction was stopped with a saturated aqueous solution of ammonium chloride (48 mL). The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (20 mL × 3) with toluene. The collected organic layer was washed with saturated brine (30 mL), dried with sardine and vacuum dried to obtain a crude product. A column purification operation using silica gel (developing solvent: hexane only) was carried out to obtain 1.5 g (yield 78%) of the bisdimethylsilane compound as a white solid.

Under an argon atmosphere, a bisdimethylsilane compound (4.30 g, 7.72 mmol) was dissolved in toluene (72 mL) and methanol (72 mL), and 10 wt% palladium / carbon (821 mg, 0.77 mmol) was added at room temperature. After stirring for 5 minutes, cerite filtration (solvent: toluene) was performed to remove the medium and concentrate. Tetrahydrofuran (72 mL), methanol (72 mL), potassium hydrogen carbonate (1.55 g, 15.4 mmol) and potassium fluoride (897 mg, 15.4 mmol) were added to the residual dimethoxysilane compound. 30% hydrogen peroxide solution (10.5 mL, 92.7 mmol) was added dropwise at room temperature over 5 minutes, the mixture was stirred at room temperature for 4 hours, the reaction was stopped with 1 M hydrochloric acid (200 mL), and toluene was added to the aqueous layer. The extraction operation (50 mL × 3) was performed in. The collected organic layer was washed with saturated brine, dried over glass and vacuum dried to obtain 4.87 g of a crude brown solid product. Filtration column purification using silica gel (developing solvent: toluene / ethyl acetate = 4/1) was carried out to obtain 2.6 g (yield 72%) of compound 8 as a green solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.59 (d, J = 8.4Hz, 2H), 8.50 (d, J = 8.9Hz, 2H), 8.34 (d, J = 1. 4Hz, 2H), 8.07 (d, J = 2.6Hz, 2H), 7.45 (dd, J = 8.4, 1.4Hz, 2H), 7.14 (dd, J = 8.9) , 2.6Hz, 2H), 5.04 (S, 2H), 2.88 (t, J = 7.6Hz, 4H), 1.78 (tt, J = 7.6,7.6Hz, 4H) , 1.46 (tq, J = 7.6, 7.6Hz, 4H), 0.99 (t, J = 7.6Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 154.1, 140.9, 132.7, 131.0, 130.1, 128.9, 128.0, 127.8, 126.7, 124.9, 124. 2,123.2,115.8,108.6,36.2,34.1,22.8,14.3ppm
MS (DART-TOF) m / z: 473
IR (neat): 3296, 2920, 2853, 1614, 1437, 1260, 1172, 812 cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₃₃ O ₂ : 473.2481 [MH] ⁺ , Found; 473.2476
Anal. Calcd for C ₃₄ H ₃₂ O ₂ : C, 86.40; H, 6.82. Found: C, 86.41; H, 6.64

Example 7

a) 2-Bromo-7-methoxycarbonyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 9a)
Under an argon atmosphere, normal butyllithium (0.35 mL, 0.55 mmol, 1.59 M hexane solution) was applied to an anhydrous tetrahydrofuran (2.5 mL) solution of compound 1 (299 mg, 0.5 mmol) at −78 ° C. for 3 minutes. And dropped. After stirring for 30 minutes, carbon dioxide was blown in for 5 minutes while maintaining the open system. After raising the temperature to room temperature, the mixture was stirred for 1 hour, and the reaction was stopped using 1M hydrochloric acid (10 mL) at 0 ° C. The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (10 mL × 3) with toluene. The collected organic layer was washed with saturated brine (10 mL), dried with sardine and vacuum dried to obtain a crude product. Lithium carbonate (185 mg, 2.5 mmol) was added to a solution of this crude product (278 mg, 0.49 mmol) in DMF (3.5 mL) under an argon atmosphere at room temperature. After stirring for 5 minutes, methyl iodide (0.15 mL, 2.5 mmol) was added dropwise over 1 minute. After stirring at room temperature for 13 hours, 1M hydrochloric acid (10 mL) was added to stop the reaction. The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (10 mL × 3) with toluene. The collected organic layer was washed with saturated brine (20 mL), dried with sardine and vacuum dried to obtain 265 mg of a crude product. A filtration column purification operation using silica gel (developing solvent: hexane / methylene chloride = 2/1) was carried out to obtain 185 mg (yield 64%) of compound 9a as a white-yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.40 (d, J = 1.6Hz, 1H), 8.80 (d, J = 1.9Hz, 1H), 8.60 (d, J = 8. 5Hz, 2H), 8.59 (s, 1H), 8.46 (d, J = 8.8Hz, 1H), 8.39 (s, 1H), 8.21 (dd, J = 1.6, 8.6Hz, 1H), 7.71 (dd, J = 1.9, 8.8Hz, 1H), 7.50 (d, J = 8.5Hz, 2H), 4.06 (s, 3H), 2.93 (m, 4H), 1.84 (tq, J = 7.8, 7.8Hz, 4H), 1.55 (tq, J = 7.8, 7.8Hz, 4H), 1.01 (M, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 149.5, 129.4, 129.3, 121.4, 121.2, 120.3, 119.6 (threpeaks overlapped), 119.3, 119.2, 118 9.9, 118.7, 118.3, 118.1, 118.0, 117.8, 117.44, 117.40 (two peaks overlapped), 116.8, 116.7, 116.3, 115. 6,114.11,114.0, 112.1, 57.6, 44.5, 42.8, 42.7, 33.83, 33.79, 27.0 ppm
MS (DART-TOF) m / z: 577 [MH] ⁺
IR (neat): 2948, 2924, 2848, 1717, 1606, 1244, 1243, 816,764 cm ^-1
HRMS (DART-TOF) calcd for C ₃₆ H ₃₃ Br ₂ O: 577.1742 [MH] ⁺ , Found: 577.1746

b) 2- (1-pyrrolidinyl) -7-methoxycarbonyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 9b)
Tris (dibenzylideneacetone) dipalladium (0) (18 mg, 0.02 mmol), 2,2-bis (diphenylphosphino) -1,1-binaphthyl (37 mg, 0.06 mmol) and sodium in a dried Schlenk tube. tert-butoxide (38 mg, 0.4 mmol) was added and the vessel was filled with argon. Toluene (3 mL) was added, the mixture was stirred for 15 minutes, compound 9a (116 mg, 0.2 mmol) was added, the mixture was further stirred for 1 minute, and pyrrolidine (0.05 mL, 0.6 mmol) was added. The mixture was stirred at 80 ° C. for 2 hours and filtered through cerite and floridil. The obtained crude product was purified by filtration column using silica gel (developing solvent: hexane / methylene chloride = 2/1) to obtain 72 mg (yield 63%) of compound 9b as a yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.39 (d, J = 1.6Hz, 1H), 8.68 (d, J = 8.6Hz, 1H), 8.58 (dd, J = 8. 4,8.4Hz, 2H), 8.55 (d, J = 1.1Hz, 1H), 8.45 (d, J = 9.0Hz, 1H), 8.37 (d, J = 1.1Hz) , 1H), 8.17 (dd, J = 8.6, 1.6Hz, 1H), 7.62 (d, J = 2.3Hz, 1H), 7.45 (dd, J = 8.4) 1.1Hz, 2H), 6.99 (dd, J = 9.0, 2.3Hz, 1H), 4.06 (s, 3H), 3.57 (t, J = 6.5Hz, 4H), 2.93-2.89 (m, 4H), 2.14 (t, J = 6.5Hz, 4H), 1.83-1.74 (m, 4H), 1.02-0.98 (m) , 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 167.8, 146.7, 141.5, 140.9, 132.8, 132.6, 131.4, 130.4, 130.2, 130.1, 129. 32, 123.28, 128.8, 128.2, 128.0, 127.8, 127.4, 127.0, 126.9, 126.3, 126.2, 126.0, 123.4 123.2, 120.1, 113.5, 103.7, 52.5, 48.1, 36.4, 36.3, 34.3, 34.2, 25.8, 22.91,22. 90, 14.37, 14.36 ppm
MS (DART-TOF) m / z: 568 [MH] ⁺
IR (neat): 2949, 2925, 2853, 1718, 1606, 1367, 1236, 1113, 806, 763 cm ^-1
HRMS (DART-TOF) calcd for C ₄₀ H ₄₂ NO ₂ : 568.3216 [MH] ⁺ , Found: 568.3224

Example 8

a) 2-Bromo-7-trimethylsilyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 10a)
Under an argon atmosphere, normal butyllithium (0.83 mL, 1.32 mmol, 1.59 M hexane solution) was added dropwise to an anhydrous tetrahydrofuran (8 mL) solution of compound 1 (718 mg, 1.2 mmol) over 5 minutes at −78 ° C. did. After stirring at −78 ° C. for 30 minutes, trimethylsilyl chloride (0.46 mL, 3.6 mmol) was added over 5 minutes. After stirring at −78 ° C. for 2 hours, methanol was added at 0 ° C. to stop the reaction, and the medium was removed and concentrated. The obtained residue diluted with a toluene solvent was transferred to a 50 mL separatory funnel, washed with water (10 mL) and saturated brine (10 mL), dried with sardine and vacuum dried, and coarsely formed as a greenish-yellow solid. 683 mg of product was obtained. A column purification operation using silica gel (developing solvent: hexane / toluene = 19/1) was carried out to obtain 529 mg (yield 75%) of compound 10a as a white solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.84 (s, 1H), 8.80 (d, J = 1.9Hz, 1H), 8.57 (d, J = 8.5, 2H), 8 .54-8.50 (m, 3H), 8.38 (s, 1H), 7.74 (dd, J = 8.5, 1.9Hz, 1H), 7.67 (dd, J = 8. 5,1.9Hz, 1H), 7.49-7.46 (m, 2H), 2.92 (tt, J = 7.8, 7.8Hz, 4H), 1.82-1.77 (m) , 4H), 1.53-1.44 (m, 4H), 1.01 (t, J = 7.8Hz, 6H), 0.46 (s, 9H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 142.2, 142.1, 138.9, 132.8, 131.7, 131.5, 130.9, 130.24, 130.23, 129.9, 129. 8, 129.5, 129.4, 129.3, 128.7, 128.6, 128.5, 128.13, 128.08, 127.9, 127.8, 126.8, 126.3, 123.41, 123.35, 120.9, 36.61, 36.55, 34.44, 34.41,23.1 (two peaks are overlapped), 14.6 (two peaks are overlapped), -0 .34ppm
MS (DART-TOFMS) m / z: 590
IR (neat): 2955, 2924, 2848, 1243, 835, 816,752 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₃₇ H ₄₀ BrSi: 590.2004 [MH] ⁺ , Found: 590.2010
Anal. Calcd for C ₃₇ H ₃₉ BrSi: C, 75.11; H, 6.64. Found: C, 75.11; H, 6.53

b) 2-Methylthio-7-trimethylsilyl-10,15-dibutyldibenzo [g, p] chrysene (Compound 10b)
Under an argon atmosphere, normal butyllithium (0.69 mL, 1.1 mmol, 1.59 M hexane solution) was added dropwise to an anhydrous tetrahydrofuran (5 mL) solution of compound 10a (592 mg, 1.0 mmol) at −78 ° C. over 3 minutes. did. After stirring at −78 ° C. for 30 minutes, dimethyl disulfide (0.46 mL, 3.6 mmol) was added over 1 minute. After stirring at room temperature for 2 hours, methanol was added to stop the reaction. An extraction operation (20 mL × 3) was performed on the aqueous layer with toluene, washed with saturated brine, dried with sardine and vacuum dried to obtain a crude product. A column purification operation using silica gel (developing solvent: hexane / toluene = 19/1) was carried out to obtain 360 mg (yield 64%) of compound 10b as a yellowish white solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 8.86 (s, 1H), 8.62-8.58 (m, 4H), 8.55 (d, J = 2.0Hz, 1H), 8.51 (D, J = 1.6Hz, 1H), 8.43 (d, J = 1.6Hz, 1H), 7.75 (dd, J = 8.1, 1.1Hz, 1H), 7.52 ( dd, J = 8.6, 2.0Hz, 1H), 7.47 (dd, J = 8.5, 1.6Hz, 2H), 2.93 (tt, J = 7.4, 7.4Hz, 4H), 2.72 (s, 3H), 1.82-1.80 (m, 4H), 1.54-1.47 (m, 4H), 1.05-1.01 (m, 6H) , 0.48 (s, 9H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 141.7, 141.6, 138.4, 136.6, 131.4, 131.3, 131.2, 130.5, 130.0, 129.9,
129.6, 129.3, 129.2, 129.0, 128.1, 128.0, 127.94, 127.90, 127.8, 127.6, 127.4, 126.5, 125. 6, 123.2, 123.1, 121.5, 36.38, 36.36, 34.24, 34.21, 22.89, 22.88, 16.7 (two peaks are overlapped), 14. 4, -0.55ppm
MS (DART-TOF) m / z: 559
IR (neat): 2952,2921,2853,142,124,814cm ^-1
HRMS (DART-TOF) calcd for C ₃₈ H ₄₂ SSi: 559.2855, Found; 559.2827 [MH] ⁺

c) 2-Methylthio-7-iodo-10,15-dibutyldibenzo [g, p] chrysene (Compound 10c)
Iodine monochloride (0.28 mL, 1 M methylene chloride solution) was added dropwise to an anhydrous methylene chloride (2.3 mL) solution of compound 10b (150 mg, 0.27 mmol) under an argon atmosphere over 3 minutes at 0 ° C. After stirring at 0 ° C. for 30 minutes and further at room temperature for 1 hour, a saturated aqueous sodium thiosulfate solution (10 mL) was added to stop the reaction at 0 ° C. An extraction operation (10 mL × 3) was performed on the aqueous layer with toluene, the collected organic layer was washed with saturated brine, dried with sardine and vacuum dried, and 155 mg (yield 94%) of compound 10c was pale yellow. Obtained as a solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.00 (d, J = 1.8Hz, 1H), 8.58 (dd, J = 8.8, 1.8Hz, 2H), 8.52 (d, J = 1.8Hz, 1H), 8.46 (d, J = 8.8Hz, 1H), 8.41 (d, J = 1.5Hz, 1H), 8.37 (d, J = 1.5Hz) , 1H), 8.30 (d, J = 8.8Hz, 1H), 7.85 (dd, J = 8.8, 1.8Hz, 1H), 7.52-7.46 (m, 3H) , 2.90 (tt, J = 7.4, 7.4Hz, 4H), 2.70 (s, 3H), 1.79 (tt, J = 7.4, 7.4Hz, 4H), 1. 48 (tq, J = 7.4, 7.4 Hz, 4H), 1.02-0.98 (m, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 141.9, 141.8, 136.8, 135.1, 132.9, 132.7, 131.3, 130.5, 130.48, 129.6, 129. 2,129.1, 129.0, 128.6, 128.2, 128.0, 127.9, 127.75, 127.72, 126.8, 125.8, 125.4, 123.2 123.1, 121.4, 92.3, 36.34, 36.33, 34.20, 34.17, 22.92, 22.90, 16.50, 16.49, 14.4 ppm
MS (DART-TOF) m / z: 613
IR (neat): 2952, 2920, 2848, 1416, 812, 582 cm ^-1
HRMS (DART-TOF) calcd for C ₃₅ H ₃₄ IS: 613.1426 [MH] ⁺ , Found; 613.1412

d) 2-Methylthio-7-cyano-10,15-dibutyldibenzo [g, p] chrysene (Compound 10d)
Copper cyanide (30 mg, 0.33 mmol) was added to a solution of compound 10c (132 mg, 0.22 mmol) in anhydrous N, N-dimethylformamide (2 mL) at room temperature under an argon atmosphere. After raising the temperature to 135 ° C. and stirring for 8 hours, a saturated aqueous solution of ammonium chloride (10 mL) was added to stop the reaction, an extraction operation (15 mL × 3) was performed on the aqueous layer with toluene, and the collected organic layer was saturated with saline. Washed with water. After drying with Glauber's salt and vacuum drying, 91 mg (yield 81%) of compound 10d was obtained as a white-yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.00 (d, J = 1.7Hz, 1H), 8.65 (d, J = 8.6Hz, 1H), 8.58 (dd, J = 8. 6,8.6Hz, 2H), 8.52 (d, J = 1.7Hz, 1H), 8.43-8.41 (m, 3H), 7.77 (dd, J = 8.6, 1) .7Hz, 1H), 7.55-7.48 (m, 3H), 2.92 (tt, J = 7.3, 7.3Hz, 4H), 2.71 (s, 3H), 1.79 (Tt, J = 7.3, 7.3Hz, 4H), 1.48 (tq, J = 7.3, 7.3Hz, 4H), 1.03-0.99 (m, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 142.7, 142.3, 137.4, 131.8, 131.3, 130.8, 130.4, 129.61, 129.57, 129.4, 129. 3,129.1, 128.83, 128.81, 128.7, 128.1, 128.0, 127.7, 127.3, 126.4, 125.4, 125.2, 123.2, 123.0, 121.1, 119.9, 109.1, 36.3, 36.2, 34.1, 34.0, 22.88, 22.87, 16.3 (two peaks are overlapped), 14.4ppm
MS (DART-TOF) m / z: 512 [MH] ⁺
IR (neat): 2952,2921,2853,2224,1591,1419,810cm ^-1
HRMS (DART-TOF) calcd for C ₃₆ H ₃₄ NS: 512.2406 [MH] ⁺ , Found; 512.2406
Anal. Calcd for C ₃₆ H ₃₃ NS: C, 84.50; H, 6.50; N, 2.74. Found: C, 84.16; H, 6.42; N, 2.68

Example 9

a) 1,8-Dichloro-2,7-dihydroxy-10,15-dibutyldibenzo [g, p] chrysene (Compound 11)
Iodine monochloride (3.6 mL, 3.6 mmol, 1 M methylene chloride solution) was added dropwise to an anhydrous methylene chloride (10 mL) solution of compound 8 (473 mg, 1.0 mmol) under an argon atmosphere at 0 ° C. over 10 minutes. .. The reaction solution was stirred at 0 ° C. for 15 minutes, heated to room temperature, and further stirred for 2 hours. Halogen seeds were decomposed with 1 M sodium thiosulfate (20 mL), and the reaction was stopped with 1 M hydrochloric acid (30 mL). An extraction operation (15 mL × 3) was performed on the aqueous layer with methylene chloride, and the collected organic layer was washed with saturated brine, dried with sardine and vacuum dried to obtain crude crystals. A filtration column purification operation using silica gel (developing solvent: chloroform / ethyl acetate = 19/1) was carried out to obtain 508 mg (yield 94%) of compound 11 as a green-yellow solid.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.00 (d, J = 1.3Hz, 2H), 8.49 (d, J = 8.4Hz, 2H), 8.32 (d, J = 8. 9Hz, 2H), 7.47 (dd, J = 8.4,1.3Hz, 2H), 7.32 (d, J = 8.9Hz, 2H), 6.22 (s, 2H), 2. 86 (t, J = 7.6Hz, 4H), 1.76 (tt, J = 7.6,7.6ppm, 4H), 1.46 (tq, J = 7.6,7.6Hz, 4H) , 0.98 (t, J = 7.6,6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 151.1, 139.1, 129.1, 129.0, 128.9, 128.8, 128.5, 128.0, 127.8, 126.9, 126. 5,125.6, 116.8, 115.8, 36.2, 34.0, 22.7, 14.4 ppm
MS (DART-TOF) m / z: 539 [MH] ^-
IR (neat): 3506, 3331, 2952, 2920, 2853, 1595, 1179, 816 cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₂₉ Cl ₂ O ₂ : 539.1545 [MH] ^- , Found: 539.1553

b) 1,8-Dichloro-2,7-bis (trifluoromethylsulfonyloxy) -10,15-dibutyldibenzo [g, p] chrysene (Compound 12)
Under an argon atmosphere, triethylamine (0.5 mL, 3.6 mmol) was added dropwise to a solution of compound 11 (541 mg, 1.0 mmol) in anhydrous methylene chloride (15 mL) at 0 ° C. The reaction solution was stirred at 0 ° C. for 15 minutes, and then trifluoromethanesulfonic anhydride (0.3 mL, 1.8 mmol) was added dropwise over 2 minutes. The mixture was stirred at 0 ° C. for 30 minutes, and the reaction was stopped with water (15 mL). An extraction operation (20 mL × 3) was performed on the aqueous layer with methylene chloride, and the collected organic layer was washed with saturated brine, dried with sardine and vacuum dried to obtain crude crystals. A column purification operation using silica gel (developing solvent: hexane / chloroform = 1/4) was carried out to obtain 608 mg (yield 75%) of compound 12 as a white solid.

A single crystal of compound 12 was prepared using an acetone solvent, and an X-ray crystal structure analysis was performed. FIGS. 1 (a) to 1 (d) show ORTEP diagrams (hydrogen atoms are not drawn for ease of viewing) in which the molecular structure is displayed at a probability level of 50%. Since the twist angle of compound 12 is 47.13 ° and it is very large, it can be said that it is a π-conjugated compound having high non-planarity.

^{1 1} H-NMR (400MHz, CDCl ₃ ) 9.08 (d, J = 1.4Hz, 2H), 8.59 (d, J = 8.4Hz, 2H), 8.40 (d, J = 9. 1Hz, 2H), 7.58 (d, J = 9.1Hz, 2H), 7.56 (dd, J = 8.4, 1.4Hz, 2H), 2.88 (t, J = 7.6Hz) , 4H), 1.77 (tt, J = 7.6,7.6Hz, 4H), 1.46 (tq, J = 7.6,7.6Hz, 4H), 0.99 (t, J = 7.6Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 145.1, 141.2, 131.6, 130.8, 130.3, 130.0, 129.1, 128.53, 128.49, 128.4, 128. 1,125.8, 124.4, 121.0, 119.1, 36.3, 34.0, 22.7, 14.3 ppm
MS (DART-TOF) m / z: 806 [MH] ⁺
IR (neat): 2965, 2928, 2857, 1415, 1200, 1133, 1057, 854, 603,503 cm ^-1
HRMS (DART-TOF) calcd for C ₃₆ H ₂₉ F ₆ Cl ₂ O ₆ S ₂ : 805.0687 [MH] ⁺ , Found: 805.0676
Anal. Calcd for C ₃₆ H ₂₈ F ₆ Cl ₂ O ₆ S ₂ : C, 53.67; H, 3.50. Found: C, 53.67; H, 3.39

The method for producing a dibenzo [g, p] chrysen derivative of the present invention can be applied as a method for producing a dibenzo [g, p] chrysen derivative useful as a hole transporting substance for a thin film or a light emitting device for an organic light emitting diode. Further, the dibenzo [g, p] chrysen derivative of the present invention can be applied to a hole transporting substance of a thin film and a light emitting device of an organic light emitting diode.

Claims (5)

The following chemical formula

(In the formula, R ¹ is an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, and R ² is a halogeno group.)
A dibenzo [g, p] chrysene derivative represented by. The dibenzo [g, p] chrysene derivative according to claim 1, wherein R ¹ is an alkyl group and R ² is a bromo group. (1) A step of reacting dibenzo [g, p] chrysene with an alkanoyl halide in the presence of Lewis acid to synthesize 10,15-dialkanoyl dibenzochrysene.
(2) A step of reducing 10,15-dialkanoyldibenzochrysene to synthesize 10,15-dialkyldibenzochrysene, and
(3) A method for producing 2,7-dihalogeno-10,15-dialkyldibenzochrysene, which comprises a step of halogenating 10,15-dialkyldibenzochrysene. The method for producing 2,7-dihalogeno-10,15-dialkyldibenzochrysene according to claim 3, wherein the dibenzo [g, p] chrysene used in the step (1) does not have a substituent on the aromatic ring. The following chemical formula:

,or,

A dibenzo [g, p] chrysene derivative represented by.

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