JP2022165751A - DIBENZO[g,p]CHRYSENE DERIVATIVE - Google Patents

Abstract

To provide a dibenzo[g,p]chrysene derivative that has four or more substituents that facilitate solubility in organic solvent and four or more oxygen atom-containing functional groups that facilitate reaction.SOLUTION: The invention relates to a dibenzo[g,p]chrysene derivative that has 4 or more substituents selected from the group consisting of an alkyl group having a branched structure, an alkenyl group, and an alkynyl group, and 4 or more oxygen atom-containing functional groups.SELECTED DRAWING: None

Description

The present invention relates to dibenzo[g,p]chrysene derivatives.

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 much interest from the viewpoint of physical properties. 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 element 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 have the problem that they are difficult to dissolve in organic solvents.

Non-Patent Document 1 discloses a compound having hydroxyl groups at the 2nd and 10th positions of dibenzo[g,p]chrysene and n-hexyl groups at the 6th and 14th positions, and having improved solubility in organic solvents. However, neither an alkyl group having a branched structure nor a compound having 8 or more substituents is disclosed. In addition, Non-Patent Document 2 discloses compounds having bromo groups at the 7- and 10-positions of dibenzo[g,p]chrysene and t-butyl groups at the 2- and 15-positions, respectively. Compounds in which the number of substituents of is 8 or more are not disclosed.

Patent Document 1 discloses a dibenzo[g,p]chrysene derivative having a plurality of substituents, but discloses only derivatives having up to three iodo groups, and has eight or more substituents. A method for preparing the derivative is also not disclosed. Patent Document 2 discloses a dibenzo[g,p]chrysene derivative having a plurality of substituents, and discloses a derivative having four iodo groups. Neither is disclosed, nor is its method of manufacture disclosed.

International Publication No. 2015/170734 JP 2013-227307 A

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

An object of the present invention is to provide a dibenzo[g,p]chrysene derivative having 4 or more substituents that facilitate solubility in an organic solvent and 4 or more oxygen atom-containing functional groups that facilitate reaction.

That is, the present invention provides dibenzo[g , p]chrysene derivatives.

Furthermore, it is preferable to have four halogeno groups.

The oxygen atom-containing functional group is preferably a hydroxyl group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group.

、または、

であることが好ましい。 The derivative has the following formula

,or,

is preferably

Further, the present invention provides a dibenzo[g,p]chrysene derivative having 4 or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups, and an alkyl halide, alkenyl halide, or alkynyl halide having a branched structure, and a Lewis acid. It relates to a method for producing the dibenzo[g,p]chrysene derivative, comprising the step of reacting in the presence of.

Since the dibenzo[g,p]chrysene derivative of the present invention has an alkyl group or the like having a bulky branched structure of 4 or more, it has very high solubility in organic solvents and contains oxygen atoms such as 4 or more hydroxyl groups. Since it has a functional group, it can be incorporated into polymeric materials and developed as polymeric materials. Therefore, it becomes an important technical element when considering development as a product.

The dibenzo[g,p]chrysene derivative of the present invention has 4 or more substituents selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group having a branched structure, and 4 oxygen atom-containing functional groups. It is characterized by having the above.

で表される化合物である。各炭素の置換位置を化学式中に示す。 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 chemical formula.

The number of substituents selected from the group consisting of alkyl groups, alkenyl groups, and alkynyl groups having a branched structure is 4 or more, preferably 8 or less.

The substitution position of the substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group is not particularly limited, but positions 3, 6, 11, 14 or positions 2, 7, 10, 15, respectively is preferably substituted with

The number of carbon atoms in the alkyl group having a branched structure is preferably 3-12, more preferably 3-8. For example, iso-propyl, iso-butyl, t-butyl, 2,2-dimethylpropyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl, iso-decyl, iso-undecyl, iso-dodecyl, etc. mentioned. Among them, iso-propyl, iso-butyl and t-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.

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

The number of oxygen atom-containing substituents is 4 or more, preferably 8 or less.

Although the substitution position of the oxygen atom-containing substituent is not particularly limited, it is preferably substituted at positions 3, 6, 11 and 14 or positions 2, 7, 10 and 15, respectively.

Examples of oxygen-containing substituents include hydroxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, and polyoxyalkylene groups. Among them, a hydroxyl group and an alkoxy group are preferable in terms of ease of synthesis and high cost performance. The number of carbon atoms in the alkoxy group is preferably 1-12, more preferably 1-8. For example, methyl ether group, ethyl ether group, normal propyl ether group, iso-propyl ether group, normal butyl ether group, t-butyl ether group, 2,2-dimethylpropyl ether group, pentyl ether group, hexyl ether group, heptyl ether group group, octyl ether group, nonyl ether group, decyl ether group, undecyl ether group, dodecyl ether group and the like. Among them, a methyl ether group, an ethyl ether group, a normal propyl ether group, an iso-propyl ether group, a normal butyl ether group and a t-butyl ether group are preferable. 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.

Polyoxyalkylene 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, etc., methoxy group, ethoxy group, 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.

The dibenzo[g,p]chrysene of the present invention preferably has a halogeno group. The number of halogeno groups is 4 or less, preferably 2 or more.

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

Although the substitution position of the halogeno group is not particularly limited, substitution at any one of the 1, 4, 5, 8, 9, 12, 13 and 16 positions is preferred.

、または、

で表される化合物が好ましい。 Among the dibenzo[g,p]chrysene derivatives, the following formula

,or,

A compound represented by is preferred.

Further, the method for producing a dibenzo[g,p]chrysene derivative of the present invention includes a dibenzo[g,p]chrysene derivative having four or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups, and a branched structure. It is characterized by having a step of reacting an alkyl halide, alkenyl halide, or alkynyl halide in the presence of a Lewis acid.

An alkoxy group, an alkenyloxy group, and an alkynyloxy group are the same substituents as described above. Alkyl halides, alkenyl halides, or alkynyl halides having a branched structure are halides of the aforementioned alkyl, alkenyl, and alkynyl groups having a branched structure. The number of substituents in the dibenzo[g,p]chrysene derivative as a starting material is 4 or more, but preferably 8 or less.

Examples of Lewis acids include aluminum reagents, boron reagents, and the like. Among them, aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, and boron tribromide are preferable. The reaction temperature is not particularly limited, and minus 78 to 25°C is preferred.

By carrying out the Friedel-Crafts reaction, alkyl groups having a branched structure can be selectively introduced at positions 2, 3, 6, 7, 10, 11, 14 and 15.

By using the method for producing a dibenzo[g,p]chrysene derivative of the present invention, four or more substituents such as alkyl groups having a branched structure such as compounds 1, 5, 9, and 13, and an oxygen atom-containing functional group A dibenzo[g,p]chrysene derivative having four or more alkoxy groups or the like as groups can be synthesized.

In the compound obtained by the above method, the alkoxy group, alkenyloxy group, and alkynyloxy group are removed using a Lewis acid such as boron tribromide or aluminum trichloride, or a basic reagent such as an alkanethiolate. It can be converted to a hydroxyl group by alkylation. By this method, dibenzo[g,p] having four or more substituents such as alkyl groups having a branched structure such as compounds 2, 6, 10, and 14 and four or more hydroxyl groups as oxygen atom-containing functional groups Chrysene derivatives can be synthesized.

The compounds obtained by the methods described above can be halogenated with a halogenating agent such as bromine, iodine, chlorine, iodine monochloride, bromine monochloride. By this method, 4 or more substituents such as alkyl groups having a branched structure such as compounds 3, 7, 11, 15, etc., 4 or more hydroxyl groups as oxygen atom-containing functional groups, and 4 or more halogeno groups. can be synthesized with dibenzo[g,p]chrysene derivatives.

In the compound obtained by the method described above, the hydroxyl group can be converted to an alkoxy group by alkylating with an alkyl halide such as methyl iodide or ethyl iodide. By this method, 4 or more substituents such as alkyl groups having a branched structure such as compounds 4, 8, 12 and 16, 4 or more alkoxy groups as oxygen atom-containing functional groups, and 4 or more halogeno groups can be synthesized with dibenzo[g,p]chrysene derivatives.

The dibenzo[g,p]chrysene derivative and spiroketone derivative of the present invention are applied to the fields of polymer materials, optical functional materials, and electronic materials. Specific examples include lithography materials, organic EL materials, resin materials such as adhesives, super engineering plastic materials, 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.

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 Compound 1)
Under an argon atmosphere, aluminum chloride (6.40 g, 48 mmol) and 2-chloropropane (19.4 g, 48 mmol) were added to a solution of 3,6,11,14-tetramethoxyDBC (4.49 g, 10 mmol) in anhydrous methylene chloride (50 mL) at room temperature. 6 mL, 160 mmol) was added. After stirring at room temperature for 89 hours, the reaction was stopped using 1M hydrochloric acid aqueous solution (200 mL) at 0°C. The aqueous layer was extracted with methylene chloride (50 mL x 3), the combined organic layer was washed with saturated brine (50 mL), dried over Glauber's salt, and dried under vacuum to obtain 7.51 g of crude product. . Filtration column purification using silica gel (developing solvent: hexane/methylene chloride = 4/1) was performed to obtain 5.07 g (82%) of compound 1 as a yellow solid.

Data for compound 1:
¹ H NMR (400 MHz, _CDCl3 ) 8.42 (s, 4H), 8.19 (s, 4H), 3.96 (s, 12H), 3.53 (sept, J=6.8Hz, 4H), 1.45 (d, J = 6.8 Hz, 24 H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 155.7, 137.4, 128.2, 127.7, 125.0, 121.0, 108.5, 55.9, 28.0, 23.2 ppm;
MS (DART-TOF) m/z: 617 [MH] ⁺ ;
IR (neat): 2956, 2865, 1619, 1491, 1459, 1412, 1244, 1045, 877 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₂ H ₄₉ O ₄ : 617.3631 [MH] ⁺ , Found: 617.3626;
Anal. _Calcd for _C42H48O4 : C, _82.05 ; H, 7.54. Found: C, 82.03; H, 7.56.

Example 2 (synthesis of compound 2)
Under an argon atmosphere, 1 M boron tribromide (66 mL, 66 mmol, methylene chloride solution) was added dropwise at 0° C. to a solution of compound 1 (6.5 g, 11 mmol) in anhydrous methylene chloride (55 mL) over 5 minutes. After stirring for 2 hours at 0° C., the reaction was quenched with water (125 mL). The aqueous layer was extracted with ethyl acetate (50 mL×3), and the combined organic layer was washed with saturated brine (50 mL), dried over Glauber's salt, and dried under vacuum to obtain 5.63 g of crude product. Filtration column purification using silica gel (developing solvent: toluene/ethyl acetate=9/1) was performed to obtain 4.37 g (74%) of compound 2 as a green solid.

Data for compound 2:
¹ H NMR (400 MHz, _CDCl3 ) 8.37 (s, 4H), 8.02 (s, 4H), 5.01 (s, 4H), 3.43 (sept, J = 6.8 Hz, 4H), 1.48 (d, J = 6.8 Hz, 24H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 151.7, 135.2, 128.2, 126.8, 125.5, 121.3, 113.1, 28.3, 23.0 ppm;
MS (DART-TOF) m/z: 561 [MH] ⁺ ;
IR (neat): 3386, 2956, 2865, 1623, 1499, 1423, 1236, 1152, 989, 877 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₃₈ H ₄₁ O ₄ : 561.3005 [MH] ⁺ , Found: 561.2988.

Example 3 (synthesis of compound 3)
Under an argon atmosphere, a solution of compound 2 (5.9 g, 10.5 mmol) in anhydrous methylene chloride (105 mL) was added with bromine (50.5 mL, 50.5 mmol, 1 M methylene chloride solution) at -20°C over 5 minutes. Dripped. After the temperature was naturally raised to room temperature, the mixture was stirred for 2 hours, and 1M sodium thiosulfate aqueous solution (130 mL) and 1M hydrochloric acid aqueous solution (130 mL) were added at 0°C to terminate the reaction. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (50 mL×3). The combined organic layer was washed with saturated brine (50 mL), dried over Glauber's salt, and dried under vacuum to give 11.2 g of crude oil. The product was obtained. A filtration column purification operation using silica gel (developing solvent was only toluene) was performed to obtain 7.39 g (80%) of compound 3 as a yellow solid.

Data for compound 3:
¹ H NMR (400 MHz, _CDCl3 ) 8.39 (s, 4H), 6.17 (s, 4H), 3.55 (qq, J = 6.9, 6.9 Hz, 4H), 1.53 (d , J=6.9 Hz, 12 H), 1.42 (d, J=6.9 Hz, 12 H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 149.1, 135.8, 133.4, 127.9, 124.5, 120.9, 110.7, 29.5, 23.0, 22.8 ppm;
MS (DARTTOF) m/z: 877 [MH] ⁺ ;
IR (neat): 3438, 2959, 2865, 1144, 752, 582 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₃₈ H ₃₇ Br ₄ O ₄ : 876.9384 [MH] ⁺ , Found: 876.9352.

Example 4 (Synthesis of Compound 4)
Under an argon atmosphere, compound 3 (11.0 g, 12.6 mmol) was suspended in acetone (200 mL), and methyl iodide (31.4 mL, 504 mmol) and diazabicycloundecene (37.5 mL, 252 mmol) were added. rice field. After stirring at room temperature for 14 hours, the reaction was stopped using 3M hydrochloric acid aqueous solution (300 mL). The organic layer was separated, the aqueous layer was extracted with toluene (70 mL×3), the combined organic layer was washed with saturated brine (50 mL), dried over Glauber's salt, and dried under vacuum to give 10.8 g of crude product. got stuff Column purification operation using silica gel (developing solvent: hexane/ethyl acetate=19/1) was performed to obtain 8.63 g (74%) of Compound 4 as a whitish yellow solid.

Data for compound 4:
¹ H NMR (400 MHz, _CDCl3 ) 8.43 (s, 4H), 4.00 (s, 12H), 3.55 (qq, J = 6.9, 6.9 Hz, 4H), 1.55 (d , J=6.9 Hz, 12 H), 1.39 (d, J=6.9 Hz, 12 H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 154.7, 141.9, 134.4, 130.1, 127.1, 121.3, 118.3, 61.8, 28.6, 24.24, 24. 16 ppm;
MS (DART-TOF) m/z: 933 [MH] ⁺ ;
IR (neat): 2955, 2928, 1456, 1389, 1330, 1254, 1040, 784 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₂ H ₄₅ Br ₄ O ₄ : 933.0010 [MH] ⁺ , Found: 932.9991;
Anal. _Calcd for _C42H44Br4O4 : C, _54.10 ; H, _4.76 . Found: C, 54.39; H, 4.98.

Example 5 (Synthesis of Compound 5)
Under an argon atmosphere, 3,6,11,14-tetramethoxydibenzo[g,p]chrysene (3.59 g, 8.0 mmol) and tert-butyl chloride (40 mL, 360 mmol) were added to a 200 mL one-necked flask. After stirring for 10 minutes at room temperature, ethylaluminum dichloride (2 mL, 2.0 mmol, 1 M hexane solution) was added over 1 minute. After heating to 50°C and stirring for 12 hours, the reaction was stopped at 0°C with water (70 mL). The aqueous layer was extracted with toluene (30 mL×3), and the combined organic layer was washed with saturated brine (100 mL), dried over Glauber's salt, and dried under vacuum to obtain 5.80 g of a crude product. Filtration column purification using silica gel (developing solvent: hexane/toluene = 9/1) was performed to obtain 4.95 g (92%) of compound 5 as a yellowish white solid.

Data for compound 5:
¹ H NMR (400 MHz, _CDCl3 ) 8.53 (s, 4H), 8.21 (s, 4H), 3.98 (s, 12H), 1.58 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.2, 138.5, 128.4, 127.4, 124.8, 121.6, 109.5, 55.6, 35.7, 30.2 ppm;
MS (DART-TOF) m/z: 673 [MH] ⁺ ;
IR (neat) 2949, 1610, 1491, 1451, 1404, 1228, 1085, 882, 838 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₆ H ₅₇ O ₄ : 673.4257 [MH] ⁺ , Found; 673.4261;
Anal. Calcd for _C46H56O4 ; C, _82.10 ; H, _8.39 . Found: C, 82.10; H, 8.43.

Example 6 (synthesis of compound 6)
Dimethylformamide (180 mL) and 1-decanethiol (31 mL, 150 mmol) were added to a 1000 mL single diameter flask under an argon atmosphere. Potassium tert-butoxide (12.6 g, 112 mmol) was added at 0° C., and after stirring for 15 minutes, the temperature was allowed to rise to room temperature, and compound 5 (6.30 g, 9.36 mmol) was added. After heating to 145° C. and stirring for 17 hours, the reaction was quenched with 1M hydrochloric acid aqueous solution (120 mL). The aqueous layer was extracted with ethyl acetate (50 mL×3), and the combined organic layer was washed with saturated brine (100 mL), dried over Glauber's salt, and dried under vacuum to obtain 30.1 g of crude product. Filtration column purification using silica gel (developing solvent: toluene/methylene chloride=4/1) was performed to obtain 4.91 g (85%) of compound 6 as a greenish yellow solid.

Data for compound 6:
¹ H NMR (400 MHz, _CDCl3 ) 8.50 (s, 4H), 7.96 (s, 4H), 5.09 (s, 4H), 1.61 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 152.7, 136.6, 128.1, 126.1, 125.0, 121.7, 114.0, 35.3, 29.8 ppm;
MS (DART-TOF) m/z: 616 [M] ⁺ ;
IR (neat) 3598, 3538, 3379, 2952, 2909, 2865, 1619, 1415, 1165, 882 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₂ H ₄₈ O ₄ : 616.3553 [M] ⁺ , Found; 616.3533.

Example 7 (Synthesis of Compound 7)
Under an argon atmosphere, to a solution of compound 6 (6.17 g, 10 mmol) in anhydrous methylene chloride (104 mL), bromine (48 mL, 48 mmol, 1M methylene chloride solution) was added dropwise at -78°C over 15 minutes, and the mixture was allowed to stand for 30 minutes. Stirred. After heating to 0° C. and stirring for 1 hour, 3M sodium thiosulfate aqueous solution (100 mL) and 1M hydrochloric acid aqueous solution (130 mL) were added to stop the reaction. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (50 mL×3). The combined organic layer was washed with saturated brine (100 mL), dried over Glauber's salt, and dried under vacuum to give 8.32 g of crude oil. The product was obtained. Filtration column purification using silica gel (developing solvent: hexane/toluene = 4/1) was performed to obtain 4.31 g (46%) of compound 7 as a yellow solid.

Data for compound 7:
1H NMR (400 MHz, CDCl3) 8.52 (s, 4H), 6.38 (s, 4H), 1.61 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 149.6, 137.0, 133.1, 127.9, 123.8, 121.2, 112.2, 36.1, 29.7 ppm;
MS (DART-TOF) m/z: 932 [M] ⁺ ;
IR (neat) 3458, 2952, 2908, 2865, 1405, 1385, 1175, 1025, 875, 728 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₂ H ₄₄ Br ₄ O ₄ : 931.9932 [M] ⁺ , Found; 931.9931.

Example 8 (Synthesis of Compound 8)
Under an argon atmosphere, compound 7 (11.1 g, 12 mmol) was suspended in acetone (150 mL), and iodomethane (30 mL, 480 mmol) and diazabicycloundecene (36 mL, 240 mmol) were added over 12 minutes. After stirring at room temperature for 1 hour, the reaction was stopped with 1M hydrochloric acid aqueous solution (100 mL). The aqueous layer was extracted with methylene chloride (100 mL×3), and the combined organic layers were washed with saturated brine (100 mL), dried over Glauber's salt, and dried under vacuum to obtain 12.5 g of crude product. Filtration column purification using silica gel (developing solvent: hexane/toluene = 2/1) was performed to obtain 10.3 g (87%) of compound 8 as a white-yellow solid.

Data for compound 8:
¹ H NMR (400 MHz, _CDCl3 ) 8.53 (s, 4H), 4.15 (s, 12H), 1.59 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.1, 142.9, 134.1, 130.5, 126.4, 122.1, 118.6, 61.8, 36.1, 31.0 ppm;
MS (DART-TOF) m/z: 989 [MH] ⁺ ;
IR (neat) 2955, 2920, 2853, 1373, 1358, 1230, 1207, 1045, 827 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₆ H ₅₃ Br ₄ O ₄ : 989.0636 [MH] ⁺ , Found; 989.0609;
Anal. _Calcd for _C46H52Br4O4 ; C, _55.89 ; H, _5.30 . Found: C, 55.88; H, 5.42.

Example 9 (Synthesis of compound 9)
Synthesized according to the synthesis of compound 1.

Data for compound 9:
¹ H NMR (400 MHz, _CDCl3 ) 8.50 (s, 4H), 7.89 (s, 4H), 4.13 (s, 12H), 3.54 (sept, J=6.8Hz, 4H), 1.33 (d, J = 6.8Hz, 24H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 155.9, 137.1, 129.5, 126.7, 125.1, 124.1, 103.2, 55.9, 27.3, 23.4 ppm;
MS (DART-TOFMS) m/z: 617 [MH] ⁺ ;
IR (neat): 2946, 2862, 1611, 1458, 1411, 1236, 1164, 1065, 829, 753 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₉ O ₄ : 617.3631 [MH] ⁺ , Found: 617.3614;
Anal. _Calcd for _C42H48O4 , C, _81.78 ; H, 7.84. Found: C, 82.08; H, 7.88.

Example 10 (Synthesis of compound 10)
Synthesized according to the synthesis of compound 2.

Data for Compound 10:
¹ H NMR (400 MHz, DMSO-d ₆ ) 9.96 (s, 4H), 8.30 (s, 4H), 7.84 (s, 4H), 3.44 (sept, J = 6.9 Hz, 4H ), 1.28 (d, J=6.9 Hz, 24 H) ppm;
¹³ C NMR (100 MHz, DMSO _- d6) 153.3, 134.9, 128.6, 125.4, 123.5, 122.1, 106.9, 26.5, 22.9 ppm;
MS (DART-TOFMS) m/z: 561 [MH] ⁺ ;
IR (neat): 3518 (OH), 3367 (OH), 2955, 1610, 1420, 1155, 1053, 843 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₃₈ H ₄₁ O ₄ : 561.3005 [MH] ⁺ , Found: 561.2993.

Example 11 (Synthesis of Compound 11)
Synthesized according to the synthesis of compound 3.

Data for compound 11:
¹ H NMR (400 MHz, _CDCl3 ) 8.29 (s, 4H), 6.20 (s, 4H), 3.52 (qq, J = 6.9, 6.9 Hz, 4H), 1.47 (d , J=6.9 Hz, 12 H), 1.24 (d, J=6.9 Hz, 12 H) ppm;
¹³ C NMR (100 MHz, DMSO _- d6) 150.5, 137.8, 128.8, 125.3, 124.6, 123.0, 112.2, 27.5, 22.8, 22.6 ppm;
MS (DART-TOFMS) m/z: 873 [MH] ⁺ ;
IR (neat): 3482 (OH), 2956, 1372, 1204, 1169, 615 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₃₈ H ₃₇ Br ₄ O ₄ : 872.9425 [MH] ⁺ , Found: 872.9378.

Example 12 (Synthesis of compound 12)
Synthesized according to the synthesis of compound 4.

Data for Compound 12:
¹ H NMR (400 MHz, _CDCl3 ) 8.27 (s, 4H), 4.12 (s, 12H), 3.53 (qq, J = 6.8, 6.9Hz, 4H), 1.48 (d , J=6.9 Hz, 12 H), 1.21 (d, J=6.8 Hz, 12 H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 155.0, 143.2, 130.8, 128.7, 128.0, 124.7, 119.1, 62.6, 28.3, 24.1 ppm;
MS (DART-TOFMS) m/z: 929 [MH] ⁺ ;
IR (neat): 2955, 2924, 1389, 1314, 1061, 1006, 803, 634 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₆ Br ₄ O ₄ : 929.0051 [MH] ⁺ , Found: 929.0047;
Anal. _Calcd for _C42H45Br4O4 , C, _54.10 ; H, _4.76 . Found: C, 54.20; H, 4.87.

Example 13 (Synthesis of compound 13)
Synthesized according to the synthesis of compound 5.

Data for compound 13:
¹ H NMR (400 MHz, _CDCl3 ) 8.52 (s, 4H), 7.90 (s, 4H), 4.13 (s, 12H), 1.49 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.5, 138.0, 129.3, 127.3, 125.5, 123.7, 104.2, 55.4, 35.7, 30.4 ppm;
MS (DART-TOF) m/z: 673 [MH] ⁺ ;
IR (neat): 2949, 1447, 1412, 1212, 1073, 1013, 890, 830, 786, 750 cm ^-1 ;
HRMS (DART _- TOF) calcd for _C46H57O4 [MH] ⁺ : _673.4257 , Found: 673.4243;
Anal. Calcd for _C46H56O4 ; C, _82.10 ; H, _8.39 . Found: C, 82.00; H, 8.64.

Example 14 (Synthesis of Compound 14)
Synthesized according to the synthesis of compound 6.

Data for Compound 14:
¹ H NMR (400 MHz, _CD3CN ) 8.44 (s, 4H), 7.88 (s, 4H), 7.45 (s, 4H), 1.51 (s, 36H) ppm;
¹³ C NMR (100 MHz, CD ₃ CN) 155.1, 137.1, 129.7, 127.8, 125.7, 123.9, 109.6, 35.8, 30.1 ppm;
MS (DART-TOFMS) m/z: 617 [MH] ⁺ ;
IR (neat): 3526 (OH), 2952, 1615, 1419, 1356, 1161, 1057, 583 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₉ O ₄ : 617.3631 [MH] ⁺ , Found: 617.3616.

Example 15 (Synthesis of Compound 15)
Synthesized according to the synthesis of compound 7.

Data for compound 15:
¹ H NMR (400 MHz, _CDCl3 ) 8.35 (s, 4H), 6.41 (s, 4H), 1.52 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 150.0, 138.4, 128.9, 127.2, 125.6, 125.3, 113.0, 36.4, 30.0 ppm;
MS (DART-TOFMS) m/z: 933 [MH] ⁺ ;
IR (neat): 3459, 2952, 1408, 1328, 1189, 922, 882, 754 cm ^-1 ;
HRMS (DART _- TOFMS) _calcd for _C42H45Br4
O ₄ : 933.0010 [MH] ⁺ , Found: 932.9922.

Example 16 (Synthesis of Compound 16)
Synthesized according to the synthesis of compound 8.

Data for compound 16:
¹ H NMR (400 MHz, _CDCl3 ) 8.32 (s, 4H), 4.25 (s, 12H), 1.51 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.9, 144.6, 131.9, 128.8, 128.1, 125.8, 120.1, 63.1, 36.7, 31.6 ppm;
MS (DART-TOFMS) m/z: 989 [MH] ⁺ ;
IR (neat): 2949, 1379, 1225, 1065, 943, 754 cm ^-1 ;
HRMS (DART-TOFMS) calcd for C ₄₆ H ₅₃ Br ₄ O ₄ : 989.0636 [MH] ⁺ , Found: 989.0625.
Anal. _Calcd for _C46H52Br4O4 ; C, _55.89 ; H, _5.30 . Found: C, 55.73; H, 5.22.

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.

The most important element of the present invention is that it has made it possible for the first time to regiospecifically introduce four bulky alkyl groups into the dibenzo[g,p]chrysene skeleton. The main effects are as follows.
(1) Since a dibenzo[g,p]chrysene derivative that is extremely soluble in an organic solvent can be prepared simply and concisely, various dibenzo[g,p]chrysene derivatives can be synthesized by liquid phase synthesis.
(2) Since easily soluble dibenzo[g,p]chrysene derivatives in which four bromine atoms are regioselectively introduced can be prepared simply and simply, various and diverse functional groups can be created using these bromine atoms as a foothold. can be introduced. Furthermore, by conducting precise substitution reactions by cross-coupling reaction and lithium-halogen exchange reaction, it becomes possible to create new compounds, and it is an opportunity to create new functional materials based on dibenzo[g,p]chrysene. Become. Thus, it is considered to be one of the useful inventions for related industries, and is expected to contribute to the industry.

Claims (5)

A dibenzo[g,p]chrysene derivative having 4 or more substituents selected from the group consisting of an alkyl group, an alkenyl group and an alkynyl group having a branched structure, and 4 or more oxygen atom-containing functional groups. 2. The dibenzo[g,p]chrysene derivative according to claim 1, further comprising four halogeno groups. 3. The dibenzo[g,p]chrysene derivative according to claim 1 or 2, wherein the oxygen atom-containing functional group is a hydroxyl group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group. the following formula

,or,

The dibenzo[g,p]chrysene derivative according to any one of claims 1 to 3, wherein reacting a dibenzo[g,p]chrysene derivative having 4 or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups with an alkyl halide, alkenyl halide, or alkynyl halide having a branched structure in the presence of a Lewis acid; The method for producing a dibenzo[g,p]chrysene derivative according to any one of claims 1 to 4, comprising steps.