JP2022170638A - Multisubstituted diindeno (1,2,3,4-defg: 1',2',3',4'-mnop) chrysene derivative - Google Patents

Abstract

To provide a diindeno (1,2,3,4-defg: 1',2',3',4'-mnop) chrysene derivative that has four or more substituents facilitating dissolution into organic solvent and four or more oxygen atom-containing functional groups facilitating introduction of a wide range of functional groups.SOLUTION: This invention relates to a diindeno (1,2,3,4-defg: 1',2',3',4'-mnop) chrysene derivative that has four or more substituents selected from the group consisting of an alkyl group, an alkenyl group, and alkynyl group having a branched-chain structure and four or more oxygen atom-containing functional groups.SELECTED DRAWING: None

Description

The present invention relates to diindeno(1,2,3,4-defg:1',2',3',4'-mnop)chrysene derivatives.

Diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene (DIC) constitutes part of Buckminsterfullerene C60. It has a bowl-shaped curved structure and a typical non-planar π-conjugated structure. They are classified as polycyclic aromatic hydrocarbons ( _PAHs ) and are relatively small organic molecules of the composition formula _C26H12 . Since it is a partial structure of C60, it is expected as an organic electronic material/organic semiconductor material similar to C60. More specifically, it is expected to function as an n-type semiconductor based on its high electron acceptor property, and is considered promising as a small molecule type organic electronic material that uses electrons as carriers. 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 organic electronic devices such as polymer materials and organic solar cells.

So far, only three cases of synthesis have been reported. Non-Patent Document 1 discloses a preparation method by FVP (flash vacuum pyrolysis) treatment of dibromobifluorenylidene at 1000°C. Non-Patent Document 2 discloses a preparation method by intramolecular cross-coupling of anthracene trichloride. Non-Patent Document 3 discloses a preparation method by an intramolecular cyclization reaction of fluorinated dibenzo[g,p]chrysene using aluminum oxide at 180°C.

However, not only the target diindenochrysene but also the synthetic intermediates were poorly soluble in organic solvents, the yield in each step was low, and the absolute amount of the target product obtained was small. Moreover, the target product, diindenochrysene, is hardly functionalized, and no method for functionalization has been proposed. Therefore, it was practically difficult to develop it as a material. Furthermore, the efficiency of intramolecular cyclization was poor and not suitable for practical production.

H. E. Bronstein, N.; Choi, L.; T. Scott, J.; Am. Chem. Soc. 2002, 124, 8870-8875. H. -I. Chang, H. -T. Huang, C.; -H. Huang, M.; -Y. Kuo, Y.; -T. Wu, Chem. Commun. 2010, 46, 7241-7243. V. Akhmetov, M.; Feofanov, S.; Troyanov, K.; Amsharov, Chem. Eur. J. 2019, 25, 7607-7612.

The present invention provides a diindeno (1,2,3,4-defg:1 An object of the present invention is to provide a ',2',3',4'-mnop) chrysene derivative.

That is, the present invention provides a diindeno (1 ,2,3,4-defg: 1′,2′,3′,4′-mnop) relates to chrysene derivatives.

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 diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop) chrysene derivative is
the following formula

,

,

,

,

,

,or,

is preferably

In addition, the present invention has 4 or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups, 4 or more oxygen atom-containing functional groups, and 4 or less halogeno groups at positions 4, 5, 12, and 13. said diindeno (1,2,3,4-defg : 1′,2′,3′,4′-mnop) relates to a method for producing chrysene derivatives.

Since the diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivative of the present invention has an alkyl group or the like having a bulky branched structure of 4 or more, It has extremely high solubility in organic solvents and has 4 or more oxygen atom-containing functional groups such as hydroxyl groups. Become. Since all target substances and synthetic intermediates can be performed under liquid-phase synthesis conditions, scale-up is possible, yields are high, and high-productivity production of target substances and the like is possible. Therefore, it becomes an important technical element when considering development as a product.

The diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivative of the present invention is a group consisting of an alkyl group having a branched structure, an alkenyl group, and an alkynyl group. It is characterized by having 4 or more substituents selected from and 4 or more oxygen atom-containing functional groups. Here, the derivative means not only a compound having a diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene skeleton as it is, but also Also included are compounds obtained by addition reactions to 6:6-carbon-carbon double bonds.

で表される化合物である。バックミンスターフラーレンＣ６０の一部分を構成し、お椀型湾曲構造の非平面性π共役系構造を有している。ＤＩＣについて、各炭素の置換位置を記した模式図を示す。 Diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene has the following structural formula

It is a compound represented by It constitutes a part of Buckminsterfullerene C60 and has a nonplanar π-conjugated structure with a bowl-shaped curved structure. A schematic diagram showing the substitution position of each carbon is shown for DIC.

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. is preferred.

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 functional groups is 4 or more, preferably 8 or less.

The substitution position of the oxygen atom-containing functional group is not particularly limited, but it is preferable that they are substituted at positions 3, 4, 9 and 10 on the periphery of DIC, respectively.

Oxygen atom-containing functional groups include hydroxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, polyoxyalkylene groups and the like. Among them, an alkoxy group and a hydroxyl 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. Two alkoxy groups may be linked to form a ring. Moreover, the alkoxy group may have a hydroxyl 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.

Examples of substituents in which two alkoxy groups are linked to form a ring include methylenedioxy, ethylenedioxy, propylenedioxy and the like. The alkoxy group having a hydroxyl group includes a hydroxymethyl ether group, a hydroxyethyl ether group, a hydroxypropyl ether group, a hydroxybutyl ether group, a hydroxypentyl ether group, a hydroxyhexyl ether group, a hydroxyheptyl ether group, a hydroxyoctyl ether group, and a hydroxynonyl ether group. group, hydroxydecyl ether group, and the like.

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.

（化合物１）、

（化合物２）、

（化合物３）、

（化合物４）、

（化合物５）、

（化合物６）、または、

（化合物７）
で表される化合物が好ましい。 Among the diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivatives, the following formula

(compound 1),

(compound 2),

(compound 3),

(compound 4),

(compound 5),

(Compound 6), or

(Compound 7)
A compound represented by is preferred.

Further, the method for producing the diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivative of the present invention comprises an alkoxy group, an alkenyloxy group, or an alkynyloxy group. A dibenzo[g,p]chrysene derivative having 4 or more groups, 4 or more oxygen atom-containing functional groups, and 4 or less halogeno groups at the 4,5,12,13 positions is dehalogenated or dehydrogenated. It is characterized by including a step of intramolecular cyclization in which two five-membered rings are constructed intramolecularly.

Dehalogenation involves adding the starting halogenated compound to a palladium complex such as bis(tri-tert-butylphosphine)palladium, tetrakistriphenylphosphinepalladium, trisdibenzylideneacetone bispalladium, bisdibenzylideneacetone palladium, and the like. can be synthesized by the addition of external ligands such as tritertiarybutylphosphine, tricyclohexylphosphine and triphenylphosphine.

Dehydrogenation is carried out by converting a starting material in which a halogenated compound having four halogeno groups, in which some of the halogeno groups are substituted with hydrogen, to 2,3-dichloro-5,6-dicyano-para-benzoquinone, hypervalent It can be synthesized by dehydrogenation with iodine, boron tribromide, sulfur, selenium, or the like.

A starting material having 4 or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups, 4 or more oxygen atom-containing functional groups, and 4 or less halogeno groups at positions 4, 5, 12, and 13 The dibenzo[g,p]chrysene derivative is
(a) 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 in the presence of a Lewis acid; and
(b) It can be synthesized through a step of halogenating the obtained compound.

Before the step of halogenation, (c) an alkoxy group, alkenyloxy group, or alkynyloxy group is treated with a Lewis acid such as boron tribromide or aluminum trichloride, or a basic reagent such as an alkanethiolate, It can also be halogenated after being converted to a hydroxyl group by dealkylation.

Examples of the Lewis acid used in step (a) (Friedel-Crafts reaction) include aluminum reagents and boron reagents. Among them, aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, boron triiodide, boron tribromide, boron trichloride, and boron trifluoride are preferable. The reaction temperature is not particularly limited, and minus 78 to 25°C is preferred.

The Friedel-Crafts reaction selectively introduces an alkyl group having a branched structure into positions 2, 3, 6, 7, 10, 11, 14 and 15 of the dibenzo[g,p]chrysene derivative. be able to.

Reagents used in step (c) (dealkylation reaction) include Lewis acids such as boron tribromide and aluminum trichloride, and basic nucleophiles such as alkanethiolates. By this method, a dibenzo[g,p]chrysene derivative having 4 or more substituents such as alkyl groups having a branched structure and 4 or more hydroxyl groups as oxygen atom-containing functional groups can be synthesized.

Reagents used in step (b) (halogenation reaction) include bromine, iodine, chlorine, iodine monochloride, iodine monobromide, bromine monochloride, N-bromosuccinimide, N-iodosuccinimide, dimethyldibromohydantoin, and the like. Halogenating agents can be mentioned. By this method, a dibenzo[g,p]chrysene derivative having 4 or more substituents such as an alkyl group having a branched structure, 4 or more hydroxyl groups as oxygen atom-containing functional groups, and 4 or less halogeno groups can be synthesized.

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, a dibenzo[g,p]chrysene derivative having 4 or more substituents such as an alkyl group having a branched structure, 4 or more alkoxy groups as oxygen atom-containing functional groups, and 4 or less halogeno groups is obtained. Can be synthesized.

Ether compounds such as compounds 1 and 2 can be directly synthesized by the production method of the present invention. Compound 3 is an ether compound such as compound 1 or 2 with a Lewis acid such as aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, boron triiodide, boron tribromide, boron trichloride, boron trifluoride. It can be synthesized by de-etherification with reagents. A hydroxyether compound such as compound 4 can be synthesized by reacting an alcohol compound such as compound 3 with a hydroxyethylating agent such as 2-chloroethanol, 2-bromoethanol, or ethyl carbonate. A cyclic ether compound such as compound 5 can be synthesized by reacting an alcohol compound such as compound 3 with a dihalomethane such as bromochloroethane, bromoiodoethane, or iodochloroethane.

Diindeno (1,2,3,4-defg:1′,2′,3′) obtained by addition reaction to the central 6:6-carbon-carbon double bond of derivatives such as compound 6 and compound 7 ,4′-mnop) chrysene derivatives are synthesized by reacting azomethine ylide generated from N-methylglycine and formaldehyde in a reaction system of toluene solvent, or by reacting bromoform, benzyltriethylammonium chloride and 50% sodium hydroxide. It can be synthesized by reacting an aqueous solution with a dibromocarbene species generated in a reaction system of a benzene solvent.

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.

Synthesis Example 1 (Synthesis of 3,6,11,14-tetramethoxy-2,7,10,15-tetraisopropyl-4,5,12,13-tetrabromo-dibenzo[g,p]chrysene)
Under an argon atmosphere, aluminum chloride (6.40 g, 48 mmol) was added to a solution of 3,6,11,14-tetramethoxydibenzo[g,p]chrysene (4.49 g, 10 mmol) in anhydrous methylene chloride (50 mL) at room temperature. 2-Chloropropane (14.6 mL, 160 mmol) was added. After stirring at room temperature for 89 hours, the reaction was quenched with 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 3,6,11,14-tetramethoxy-2,7,10,15. -tetraisopropyl-dibenzo[g,p]chrysene (compound a) was obtained as a yellow solid.

Data for compound a:
¹ H NMR (400 MHz, _CDCl3 ) 8.42 (s, 4H), 8.19 (s, 4H), 3.96 (s, 12H), 3.53 (sept, J = 6.9 Hz, 4H), 1.45 (d, J = 6.9 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.

Under an argon atmosphere, 1M boron tribromide (66 mL, 66 mmol, methylene chloride solution) was added dropwise at 0° C. to a solution of compound a (6.8 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 3,6,11,14-tetrahydroxy-2,7,10,15. -tetraisopropyl-dibenzo[g,p]chrysene (compound b) was obtained as a green solid.

Data for compound b:
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.

Under an argon atmosphere, a solution of compound b (5.89 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 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 (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 is only toluene) was performed, and 7.39 g (80%) of 3,6,11,14-tetrahydroxy-2,7,10,15-tetraisopropyl-4, 5,12,13-Tetrabromodibenzo[g,p]chrysene (compound c) was obtained as a yellow solid.

Data for compound c:
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 (DART-TOF) 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.

Under an argon atmosphere, compound c (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 for 12 hours at room temperature, the reaction was quenched with 3M aqueous hydrochloric acid (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 (100 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 3,6,11,14-tetramethoxy-2,7,10,15- Tetraisopropyl-4,5,12,13-tetrabromodibenzo[g,p]chrysene (compound d) was obtained as a yellow solid.

Data for compound d:
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 1 (3,4,9,10-tetramethoxy-2,5,8,11-tetraisopropyl-diindeno(1,2,3,4-defg: 1′,2′,3′,4′- mnop) Synthesis of Chrysene (Compound 1))
Under an argon atmosphere, N,N-diisopropylethylamine (0.2 mL, 1.2 mmol), bis(tri-tert-butylphosphine) palladium(0) ( 77 mg, 0.15 mmol) and tri-tert-butylphosphine (0.87 mL, 0.3 mmol, 10 w % hexane solution) were added. It was immersed in an oil bath at room temperature and gradually heated to 125°C. After that, the mixture was stirred for 23 hours, cooled to room temperature naturally, and then filtered through a glass filter packed with celite (developing solvent was toluene). Transferred to a 200 mL separatory funnel, washed with saturated saline (10 mL), dried over Glauber's salt, and dried in a vacuum to obtain a brown-yellow crude product. Column purification using silica gel (developing solvent: hexane/toluene, 2:1) was performed to obtain 63 mg (68%) as a yellow solid.

Data for compound 1:
¹ H NMR (400 MHz, _CDCl3 ) 8.22 (s, 4H), 4.09 (s, 12H), 3.67 (sept, J = 6.8 Hz, 4H), 1.44 (d, J = 6 .8Hz, 24H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 155.5, 145.1, 138.2, 135.7, 130.1, 129.4, 123.7, 64.9, 28.7, 25.2 ppm;
MS (DART-TOF) m/z: 613 [MH] ⁺ ;
IR (neat) 2955, 2865, 1456, 1405, 1309, 1049, 1029, 989, 867 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₂ H ₄₅ O ₄ : 613.3318 [MH] ⁺ , found; 613.3314;
Anal. _Calcd for _C42H44O4 ; C, _82.32 ; H, 7.24. Found:, 82.32; H, 7.15.

Synthesis Example 2 (Synthesis of 3,6,11,14-tetramethoxy-2,7,10,15-tert-butyl-4,5,12,13-tetrabromo-dibenzo[g,p]chrysene)
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 at room temperature for 10 minutes, 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 quenched with water (70 mL) at 0°C. 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. A filtration column purification operation using silica gel (developing solvent is hexane/toluene, 9:1) was performed to obtain 4.95 g (92%) of 3,6,11,14-tetramethoxy-2,7,10,15- Tetra-tert-butyl-dibenzo[g,p]chrysene (compound e) was obtained as a pale yellow solid.

Data for compound e:
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.

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 e (6.30 g, 9.36 mmol) was added. After heating to 145° C. and stirring for 17 hours, the reaction was stopped 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 3,6,11,14-tetrahydroxy-2,7,10,15. -tetra-tert-butyl-dibenzo[g,p]chrysene (compound f) was obtained as a green-yellow solid.

Data for compound f:
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.

Under an argon atmosphere, bromine (48 mL, 48 mmol, 1M methylene chloride solution) was added dropwise over 15 minutes to a solution of compound f (6.17 g, 10 mmol) in anhydrous methylene chloride (104 mL) at −78° C., followed by stirring for 30 minutes. did. 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. A filtration column purification operation using silica gel (developing solvent is hexane/toluene, 4:1) was performed to obtain 4.31 g (46%) of 3,6,11,14-tetrahydroxy-2,7,10,15- Tetra-tert-butyl-4,5,12,13-tetrabromodibenzo[g,p]chrysene (compound g) was obtained as a yellow solid.

Data for compound g:
¹ H 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.

Under an argon atmosphere, compound g (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 quenched with 1M aqueous hydrochloric acid (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. A filtration column purification operation using silica gel (developing solvent is hexane/toluene, 2:1) was performed, and 10.3 g (87%) of 3,6,11,14-tetramethoxy-2,7,10,15- Tetra-tert-butyl-4,5,12,13-tetrabromodibenzo[g,p]chrysene (compound h) was obtained as a white-yellow solid.

Data for compound h:
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 2 (3,4,9,10-tetramethoxy-2,5,8,11-tetra-tert-butyl-diindeno(1,2,3,4-defg: 1′,2′,3′, 4′-mnop) Synthesis of Chrysene (Compound 2))
Bis(tri-tert-butylphosphine)palladium (0) (77 mg, 0.15 mmol) and tri-tert- Butylphosphine (0.3 mL, 0.3 mmol, 1M hexane solution) was added. It was immersed in an oil bath at room temperature and gradually heated to 125°C. After stirring for 2 hours, the mixture was naturally cooled to room temperature, and filtered through a glass filter packed with celite (developing solvent was toluene). Transferred to a 200 mL separatory funnel, washed with saturated brine (20 mL), dried over Glauber's salt, and dried in a vacuum to obtain a brown-yellow crude product. Column purification using silica gel (developing solvent: hexane/toluene, 2:1) was performed to obtain 25 mg (25%) as a yellow solid.

Data for compound 2:
¹ H NMR (400 MHz, _CDCl3 ) 8.30 (s, 4H), 4.04 (s, 12H), 1.62 (s, 36H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 157.6, 145.9, 138.3, 135.0, 130.1, 127.9, 123.6, 63.6, 37.0, 31.6 ppm;
MS (DART-TOF) m/z: 669 [MH] ⁺ ;
IR (neat) 2952, 1395, 1292, 1244, 1221, 993 cm ^-1 ;
HRMS (DART _- TOF) calcd for _C46H53O4 : _669.3944 [MH] ⁺ found; 669.3934;
Anal. _Calcd for _C46H52O4 ; C, _82.60 ; H, 7.84. Found: C, 82.60; H, 7.84.

Example 3 (3,4,9,10-tetrahydroxy-2,5,8,11-tetraisopropyl-diindeno(1,2,3,4-defg: 1′,2′,3′,4′- mnop) Synthesis of chrysene (compound 3))
Under an argon atmosphere, 3,4,9,10-tetramethoxy-2,5,8,11-tetraisopropyl-diindeno (1,2,3,4-defg: 1′,2′,3′,4′- mnop) To a CH ₂ Cl ₂ (10 mL) solution of chrysene compound 1 (612 mg, 1.0 mmol) was added dropwise 1 M boron tribromide (4.8 mL, 4.8 mmol) at 0° C. over 4 minutes, and Stirred. After that, the temperature was naturally raised to room temperature, the reaction was allowed to proceed for 4 hours, and the reaction was stopped using water (20 mL) at 0°C. The reaction solution was dissolved in ethyl acetate, and the aqueous layer was extracted with ethyl acetate (20 mL×3). The combined organic layer was washed with saturated brine (20 mL), dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Column purification using silica gel (developing solvent: toluene/ethyl acetate, 19:1) was performed to obtain 419 mg (74%) of compound 3 as a yellowish green solid.

Data for Compound 3
¹ H NMR (400 MHz, _CDCl3 ) 8.05 (s, 4H), 7.04 (s, 4H), 3.39 (sept, J = 6.8 Hz, 4H), 1.45 (d, J = 6 .8Hz, 24H) ppm;
¹³ C NMR (100 MHz, DMSO-d6) 148.2, 139.0, _137.0 , 136.3, 127.7, 124.7, 123.0, 27.5, 23.6 ppm;
MS (DART-TOF) m/z: 557 [MH] ⁺ ;
IR (neat) 3391, 2955, 2928, 1433, 1286, 1190, 1160, 1049, 863, 634, 582 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₃₈ H ₃₇ O ₄ : 557.2692 [MH] ⁺ , found; 557.2692.

Example 4 2,2′,2″,2′″-(2,5,8,11,tetraisopropyldiindeno(1,2,3,4-defg:1′,2′,3′ ,4′-mnop)chrysene-1,6,7,12-tetrayl)tetrakis(oxy))tetrakis(ethan-1-ol) (compound 4) synthesis)
Under an argon atmosphere, potassium carbonate (332 mg, 2.4 mmol) and 2-chloroethanol (0.6 mL, 7.2 mmol) were added to a MeOH (12 mL) solution of compound 3 (111 mg, 0.2 mmol). The mixture was stirred at 50°C for 46 hours and quenched with 1M hydrochloric acid (10 mL) at 0°C. The reaction solution was dissolved in ethyl acetate, and the aqueous layer was subjected to an extraction operation (10 mL×3) with ethyl acetate. The combined organic layer was washed with saturated brine (10 mL×3), dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Column purification using silica gel (developing solvent: ethyl acetate/hexane, 2:1) was performed to obtain 88 mg (61%) of compound 4 as a yellow solid.

Data for Compound 4
¹ H NMR (400 MHz, _CDCl3 ) 8.26 (s, 4H), 4.28 (t, J = 4.0 Hz, 8H), 4.01 (t, J = 4.0 Hz, 8H), 3.86 (brs, 4H), 3.64 (sept, J=6.8Hz, 4H), 1.45 (d, J=6.8Hz, 24H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 152.2, 144.6, 137.6, 135.0, 130.2, 129.0, 124.0, 78.8, 62.0, 28.0, 24. 7 ppm;
MS (DART-TOF) m/z: 733 [MH] ⁺ ;
IR (neat) 3347, 2956, 2921, 1425, 1284, 1180, 1053, 870 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₆ H ₅₂ O ₈ : 733.3740 [MH] ⁺ , found; 733.3724.

Example 5 (10,16,21,27-tetrakis(isopropyl)-12,14,23,25-tetraoxadecacyclo(17.13.0.0 ^{2,30.0 3,7.0 4,18} .0 ^5,15 .0 ^6,11 .0 ^8,29 .0 ^22,32 .0 ^28,31 ) Dotria contour 1 (32),2,4,6,8,10,15,17,19,21 ,26,28,30-tridecaene (compound 5) synthesis)
Potassium carbonate (166 mg, 1.2 mmol) and bromochloroethane (1.5 mL, 6.0 mmol) were added to a solution of compound 3 (168 mg, 0.3 mmol) in DMSO (3.0 mL) and toluene (0.75 mL) under an argon atmosphere. was added. The mixture was stirred at 55°C for 2 hours and quenched with water (3 mL) at 0°C. The reaction solution was dissolved in methylene chloride, and the aqueous layer was subjected to an extraction operation (10 mL×3) with methylene chloride. The combined organic layer was washed with saturated brine (10 mL×3), dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Filtration column purification using silica gel (developing solvent: hexane/ethyl acetate, 9:1) was performed to obtain 148 mg (85%) of compound 5 as a yellow solid.

Data for Compound 5
¹ H NMR (400 MHz, _CDCl3 ) 7.82 (s, 4H), 6.68 (d, J = 7.3 Hz, 2H), 6.18 (d, J = 7.3 Hz, 2H), 3.42 (qq, J = 6.9, 6.9 Hz, 4H), 1.44 (d, J = 6.9 Hz, 12H), 1.22 (d, J = 6.9 Hz, 12H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 156.4, 141.8, 141.4, 137.8, 132.0, 126.7, 122.4, 96.6, 28.9, 24.2, 23. 7 ppm;
MS (DART-TOF) m/z: 581 [MH] ⁺ ;
IR (neat) 2955, 1460, 1420, 1298, 1223, 938 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₀ H ₃₇ O ₄ : 581.2692 [MH] ⁺ , found; 581.2662;
Anal. _Calcd for _C40H36O4 ; C, _82.73 ; H, 6.25. Found: C, 82.72; H, 6.41.

Example 6 (3,4,9,10-Tetramethoxy-2,5,8,11-tetraisopropyl-14-methyl-3a ² ,3b ² -(methanoiminomethano)diindeno(1,2,3,4 -defg: Synthesis of 1′,2′,3′,4′-mnop) chrysene (compound 6))
Under an argon atmosphere, N-methylglycine (18 mg, 0.2 mmol) and paraformaldehyde (15 mg, 0.5 mmol) were added to a toluene (30 mL) solution of tetramethoxydiindenochrysene compound 1 (61 mg, 0.1 mmol). rice field. Water formed in the reaction system was removed by attaching a Dean-Stark apparatus. After stirring at 125° C. for 15 minutes, N-methylglycine (18 mg, 0.2 mmol) and paraformaldehyde (15 mg, 0.5 mmol) were added at 15 minute intervals for a total of 23 additions. Then, after stirring for 24 hours and cooling to room temperature, the reaction solution was dissolved in toluene, and the organic layer was washed with water (10 mL x 3), washed with saturated brine (10 mL), dried over Glauber's salt, and dried in vacuum to obtain a crude product. got stuff Column purification using silica gel (developing solvent: hexane/ethyl acetate, 19:1) was performed to obtain 19 mg (29%) of compound 6 as a yellow solid.

Data for compound 6:
1H NMR (400 MHz, _CDCl3 ) 7.15 (s, 4H), 3.82 (s, 12H), 3.35 (qq, J = 6.9, 6.9 Hz, 4H), 3.26 (s, 4H), 2.30 (s, 3H), 1.26 (d, J = 6.9 Hz, 12H), 1.23 (d, J = 6.9 Hz, 12H) ppm;
¹³ C NMR (100 MHz, _CDCl3 ) 155.5, 153.9, 143.2, 131.6, 126.2, 119.9, 77.1, 64.2, 56.7, 42.1, 27. 7, 25.2, 24.4 ppm;
MS (DART-TOF) m/z: 670 [MH] ⁺ ;
IR (neat) 2956, 2925, 1451, 1404, 1268, 1228, 1073, 1013, 985 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₅ H ₅₂ NO ₄ : 670.3896 [MH] ⁺ , found; 670.3864.

Example 7 (13,13-dibromo-3,4,9,10-tetramethoxy-2,5,8,11-tetraisopropyl-3a ² ,3b ² -methanodiindeno (1,2,3,4-defg: Synthesis of 1′,2′,3′,4′-mnop)chrysene (compound 7))
Under atmospheric pressure, 50 v/v % aqueous sodium hydroxide solution (15 mL, 287 mmol) and benzyltriethylammonium chloride (34 mg, 0.15 mmol) were added to a benzene (30 mL) solution of tetramethoxydiindenochrysene compound 1 (183 mg, 0.3 mmol). ) and bromoform (0.8 mL, 9 mmol) were added. Stir at room temperature for 4 h and quench with saturated aqueous ammonium chloride (30 mL) at 0°C. The reaction solution was dissolved in ethyl acetate, and the aqueous layer was extracted with ethyl acetate (30 mL×3). The combined organic layer was washed with saturated brine (30 mL×3), dried over Glauber's salt, and dried in a vacuum to obtain a crude product. Filtration column purification using silica gel (developing solvent: hexane/methylene chloride, 2:1) was performed to obtain 115 mg (49%) of Compound 7 as a brownish yellow solid.

Data for compound 7:
¹ H NMR (400 MHz, _CDCl3 ) 7.44 (s, 4H), 3.90 (s, 12H), 3.43 (qq, J = 6.9, 6.9Hz, 4H), 1.33 (d , J=6.9 Hz, 12 H), 1.25 (d, J=6.9 Hz, 12 H) ppm;
¹³ _C NMR ₍ 100 MHz, CD2Cl2) 154.3, 144.6, 140.9, 132.9, 128.9, 121.0, 64.1, 55.4, 29.9, 27.9, 24.6, 23.7 ppm;
MS (DART-TOF) m/z: 785 [MH] ⁺ ;
IR (neat) 2960, 1455, 1225, 1206, 1077, 1001, 982, 868 cm ^-1 ;
HRMS (DART-TOF) calcd for C ₄₃ H ₄₅ Br ₂ O ₄ : 785.1664 [MH] ⁺ , found; 785.1681.

The diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivative of the present invention is an n-type semiconductor based on its high electron acceptor properties. It is expected to have functions and can be applied as small-molecule organic electronic materials, optoelectronic materials, and polymer materials that use electrons as carriers. The most important element of the present invention is that it has made it possible for the first time to positionally specifically introduce four bulky alkyl groups and four oxygen atom-containing functional groups into the derivative skeleton. The main effects are as follows.
(1) It is soluble in various organic solvents because it has bulky alkyl substituents and oxygen functional groups.
(2) Since it has an oxygen atom-containing functional group, it can be further functionalized and attached to polymeric materials.
(3) It has the potential to lead to the development of epoch-making functional materials.

Claims (4)

A diindeno (1,2,3,4 -defg: 1',2',3',4'-mnop) chrysene derivatives. The diindeno(1,2,3,4-defg:1′,2′,3′) according to claim 1, wherein the oxygen atom-containing functional group is a hydroxyl group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group. ,4′-mnop) chrysene derivatives. the following formula

,

,

,

,

,

,or,

3. The diindeno(1,2,3,4-defg:1′,2′,3′,4′-mnop)chrysene derivative according to claim 1 or 2. dibenzo[g,p] having 4 or more alkoxy groups, alkenyloxy groups, or alkynyloxy groups, 4 or more oxygen atom-containing functional groups, and 4 or less halogeno groups at positions 4, 5, 12, and 13 The diindeno (1,2 ,3,4-defg: 1′,2′,3′,4′-mnop) Method for producing chrysene derivatives.