JP2022087523A - EASILY SOLUBLE DIBENZO[g,p]CHRYSENE DERIVATIVE - Google Patents

Abstract

To provide a dibenzo[g,p]chrysene derivative that has four or more substituent groups making it easier to dissolve in an organic solvent and a halogeno group selectively at four or more positions making it easier to react.SOLUTION: Provided is a dibenzo[g,p]chrysene derivative that has 4 or more substituent groups selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, a polyoxyalkylene group and/or a hydroxyl group, and 4 halogeno 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 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, the 3rd, 6th, 11th and 14th positions of dibenzo [g, p] chrysene, the 2nd, 7th, 10th and 15th positions, the 9th, 11th, 14th and 16th positions. When a halogeno group, especially a bromo group, is selectively introduced into four symmetrical positions at the positions, 8-position, 9-position, 16-position and 1-position, it is easy to convert into various substituents, so that it is a functional material. It can be expected to be a useful compound as an intermediate. However, the polycyclic aromatic hydrocarbon has a problem that it is difficult to dissolve in an organic solvent.

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, the compound having four bromo groups is not disclosed. 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 with one bromo group are not disclosed.

Patent Document 1 discloses a dibenzo [g, p] chrysene derivative having a plurality of substituents, but only a derivative having three iodine groups and having four or more halogeno groups. The method for producing the derivative is also not disclosed. Patent Document 2 discloses a dibenzo [g, p] chrysene derivative having a plurality of substituents, but a derivative having four iodine groups is disclosed, but a derivative having other substituents is disclosed. It is not disclosed, nor is its manufacturing method disclosed.

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

International Publication 2015/170734 Japanese Unexamined Patent Publication No. 2013-227307

It is an object of the present invention to provide a dibenzo [g, p] chrysene derivative having four or more substituents that make it easily soluble in an organic solvent and four or more positions that make it easy to react, selectively having a halogeno group. do.

That is, the present invention comprises four or more substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, a polyoxyalkylene group and / or a hydroxyl group, and a halogeno group. It relates to a dibenzo [g, p] chrysen derivative having four.

または

で表される化合物であることが好ましい。 The following formula

or

It is preferably a compound represented by.

The present invention also relates to a dibenzo [g, p] chrysene derivative having 6 or more alkoxy groups and / or polyoxyalkylene groups and 4 halogeno groups.

で表される化合物であることが好ましい。 The following formula

It is preferably a compound 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 a variety of various functional groups, such as a cross-coupling reaction and lithium-. By performing a precise substitution reaction by a halogen exchange reaction, it becomes possible to produce a new compound. In the present invention, scaffolding molecules (compounds 1 to 5, 14) of a 6-substitution type dibenzo [g, p] chrysene derivative having 6 kinds of substitution position patterns were specifically synthesized. Therefore, the dibenzo [g, p] chrysene derivative of the present invention is an opportunity to produce a new functional material based on dibenzo [g, p] chrysene.

(A) In the ORTEP diagram of compound 8 synthesized in Example 3, it is a diagram showing a twist angle determined by four carbon atoms (C8, C9, C17, C18). (B) It is a top view of the ORTEP diagram of compound 3. (C) It is a side view from the butyl group side fjord region described in the twist angle 44.59 °. (D) It is a side view from the bay area area. (A) In the ORTEP diagram of compound 4 synthesized in Example 4, it is a diagram showing a twist angle determined by four carbon atoms (C06, C07, C13, C14). (B) It is a top view of the ORTEP diagram of compound 4. (C) It is a side view from the butyl group side fjord region described in the twist angle 55.89 °. (D) It is a side view from the bay area area. (A) In the ORTEP diagram of compound 5 synthesized in Example 5, it is a diagram showing a twist angle determined by four carbon atoms (C01, C02, C03, C04). (B) It is a top view of the ORTEP diagram of compound 4. (C) It is a side view from the butyl group side fjord region described in the twist angle 53.97 °. (D) It is a side view from the bay area area.

The first dibenzo [g, p] chrysene derivative of the present invention is
It is characterized by having 4 or more substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, a polyoxyalkylene group and / or a hydroxyl group, and 4 halogeno groups. And.

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

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

The lower limit of the number of substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, a polyoxyalkylene group, and / or a hydroxyl group is 4 or more, but an upper limit. Is preferably 8 or less. The lower limit of the number of halogeno groups is 4 or more, but the upper limit is preferably 8 or less.

Among the alkyl group, alkenyl group, alkynyl group, alkanoyl group, alkenoyl group, alkinoyl group, and hydroxyl group, the alkyl group and the hydroxyl group are preferable in terms of solubility in a wide variety of organic solvents.

The positions of substituents such as alkyl groups are not particularly limited, but at least four alkyl groups and the like have positions at the 2-position, 7-position, 10-position and 15-position, 2-position, 7-position, 10-position and 15-position, and the like. It is preferable that the positions are substituted at the 3rd, 8th, 11th and 12th positions.

The positions of the substituents of the halogeno group are not particularly limited, but at least four halogeno groups are located at the 3-position, 6-position, 11-position and 14-position, 2-position, 7-position, 10-position and 15-position, and 4-position. It is preferable that the positions are substituted at the 5th, 12th and 13th positions, and the 8th, 9th, 16th and 1st positions.

Examples of the alkyl group 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, iso-propyl, n-butyl, iso-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n. -Decil, n-undecyl, n-dodecyl and the like, including n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl is 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 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.

The polyoxyalkylene group is a homopolymer of an alkylenediol or a substituent obtained by removing hydrogen at the terminal of the copolymer. By introducing such a substituent, it becomes easy to dissolve in water or a water-soluble organic solvent. Examples of the polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxybutylene and the like. The degree of polymerization is preferably 4 to 450 in the case of polyethylene glycol, and preferably 450 to 10000 in the case of polyethylene oxide.

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

（化合物１）

（化合物２）

（化合物３）

（化合物４）
および

（化合物５）
で表される化合物が好ましい。 Among the dibenzo [g, p] chrysene derivatives, the following formula

(Compound 1)

(Compound 2)

(Compound 3)

(Compound 4)
and

(Compound 5)
The compound represented by is preferable.

Synthetic dibenzo [g, p] chrysen of compound 1 is brominated with a brominating agent such as bromine, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and the positions 2, 7, 10, and 15. After synthesizing a brominated product having a bromine atom in, the bromine atom was lithiated with n-BuLi or the like and reacted with n-BuBr to cause dibenzo [g, p] chrysen (compound 6) in which four butyl groups were substituted. ) Is synthesized. Despite being suspended, it can be synthesized in high yield. Compound 6 is not only soluble in most organic solvents, but is also a colorless and transparent viscous substance at room temperature. Then, compound 1 is synthesized by brominating with a brominating agent such as bromine, N-bromosuccinimide, and 1,3-dibromo-5,5-dimethylhydantoin.

Compound 1 dissolves in toluene at room temperature. On the other hand, the brominated product in which bromine is substituted at the 3-position, 6-position, 11-position, and 14-position having no butyl group is hardly dissolved in toluene.

Synthesis of Compound 2 Dimerize 2,7-dibromo-9-fluorenone to synthesize dibenzo [g, p] chrysene with bromine atoms substituted at positions 3, 6, 11 and 14. Using the compound, the bromine atom is lithiated with n-BuLi or the like and reacted with n-BuBr in the same manner as in Compound 1, to synthesize dibenzo [g, p] chrysene substituted with four butyl groups. 4 The brominated product is very difficult to dissolve in an organic solvent, but the lithiolysis reaction proceeds. Then, compound 2 is synthesized by brominating with a brominating agent such as bromine, N-bromosuccinimide, and 1,3-dibromo-5,5-dimethylhydantoin.

Compound 2 is dissolved in toluene, hexane, methylene chloride, chloroform and tetrahydrofuran at room temperature. On the other hand, the brominated product in which bromine is substituted at the 2-position, 7-position, 10-position and 15-position having no butyl group is hardly dissolved in any of these solvents.

Synthesis of Compound 3 Dibenzo [g, p] chrysen and alkanoyl halide are reacted in the presence of Lewis acids such as aluminum trichloride and iron trichloride to synthesize 10,15-dialkanoyl dibenzochrycene, followed by hydrogenation and hydrogenation. 2,7-Dibromo-10,15-dialkyl by reducing with a reducing agent such as sodium boron or lithium aluminum hydride and halogenating with 1,3-dibromo-5,5-dimethylhydantin, N-bromosuccinimide, etc. Synthesize dibenzocrysen. Here, as the brominating agent, 1,3-dibromo-5,5-dimethylhydantin is preferable in terms of reactivity. The bromo group of the compound is lithiolated and then reacted with, for example, dimethylsilane chloride to form a bisdimethylsilane form, then reacted with, for example, methanol to form a dimethoxysilyl form, and further with hydrogen peroxide, for example, Fleming-Tamao oxidation. By doing so, 2,7-dihydroxy-10,15-dialkyldibenzoglycene is synthesized. Then, by brominating with 1,3-dibromo-5,5-dimethylhydantoin or the like, compound 3 having brominated positions 1, 3, 6 and 8 is synthesized.

The synthetic compound 2 of the compound 4 was reacted with sodium methoxide in the presence of a copper reagent such as CuI to replace the bromine atom with a methoxy group. The methoxy group of the compound is demethylated by using a reagent such as BBr ₃ , alkanethiol, thereby substituting the methoxy group with a hydroxyl group. Then, compound 4 is synthesized by brominating with a brominating agent such as Br ₂ , 1,3-dibromo-5,5-dimethylhydantin and N-bromosuccinimide. Direct bromination is possible even at the 1st (8th, 9th, 16th) or 4th place where the steric hindrance is very large.

The synthetic compound 1 of the compound 5 was reacted with sodium methoxide in the presence of a copper reagent such as CuI to replace the bromine atom with a methoxy group. The methoxy group of the compound is demethylated by using a reagent such as BBr ₃ or alkanethiol to replace the methoxy group with a hydroxyl group. Then, compound 5 is synthesized by brominating with a brominating agent such as Br ₂ , 1,3-dibromo-5,5-dimethylhydantin and N-bromosuccinimide.

The second dibenzo [g, p] chrysene derivative of the present invention is characterized by having 6 or more alkoxy groups and / or polyoxyalkylene groups and 4 halogeno groups.

The lower limit of the number of alkoxy groups and / or polyoxyalkylene groups is 6 or more, but the upper limit is preferably 10 or less. The lower limit of the number of halogeno groups is 4 or more, but the upper limit is preferably 8 or less.

The positions of the substituents of the alkoxy group and / or the polyoxyalkylene group are not particularly limited, but at least 6 alkyl groups and the like are located at the 2-position, 3-position, 6-value, 7-position, 10-position, 11-position and 14-position. It is preferable that it is replaced with.

The position of the substituent of the halogeno group is not particularly limited, but it is preferable that at least four halogeno groups are substituted at the 1-position, 5-position, 9-position and 13-position.

Examples of the alkoxy group include a linear or branched alkoxy group which may have a substituent. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. For example, methoxy, ethoxy, n-propoxy, n-butoxy, iso-butoxy, n-pentoxy, 2,2-dimethylpropoxy, n-hexitoxy, n-heptoxy, n-octoxy, n-nonyloxy, n-decyloxy, Examples thereof include n-undecyloxy and n-dodecyloxy. Of these, n-propoxy, n-butoxy, iso-butoxy, n-pentoxyl, 2,2-dimethylpropoxy, n-hexitoxy, n-heptoxy, and n-octoxy are preferable.

Examples of the polyoxyalkylene group and the halogeno group include those described above.

（化合物１４）
で表される化合物が好ましい。 Among the dibenzo [g, p] chrysene derivatives, the following formula

(Compound 14)
The compound represented by is preferable.

Synthesis of Compound 14 Brominated 3,6,11,14-tetramethoxydibenzo [g, p] chrysen with a brominating agent such as bromine, 1,3-dibromo-5,5-dimethylhydantin, N-bromosuccinimide, etc. After synthesizing a brominated product having a bromine atom at the 2, 7, 10, 15 position, it is etherified with sodium methoxide or the like in the presence of a copper catalyst such as CuI, and is 2, 3, 6, 7, 10 , 11, 14, 15-Octamethoxydibenzo [g, p] chrysen. Compound 14 is synthesized by brominating with a brominating agent such as Br ₂ , 1,3-dibromo-5,5-dimethylhydantin, N-bromosuccinimide and the like.

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 of a thin film, a light emitting element of an organic light emitting diode, or a compound of 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., 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).

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 shown in 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.

Example 1 (Synthesis of 3,6,11,14-Tetrabromo-2,7,10,15-Tetrabutyldibenzo [g, p] chrysene (Compound 1))

Synthesis of Compound 6 Under an argon atmosphere, DBC (2-Br) ₄ (3.86 g, 6 mmol) was suspended in anhydrous tetrahydrofuran (100 mL) and at −78 ° C., normal butyllithium (22.5 mL, 36 mmol, 1. 59M hexane solution) was added dropwise over 5 minutes. After stirring for 30 minutes, 1-bromobutane (5.8 mL, 54 mmol) was added over 5 minutes, the temperature was naturally raised to room temperature, and the mixture was stirred for 1 hour. After the reaction was stopped using water (40 mL) at 0 ° C., the organic layer was separated and the aqueous layer was extracted with toluene (20 mL × 3). The combined organic layer was washed with saturated brine (40 mL), dried over Glauber's salt, and vacuum dried to obtain a crude product of an orange viscous substance. A column purification operation using silica gel (developing solvent was hexane / toluene = 19/1) was carried out to obtain 2.74 g (83%) of compound 6 as a colorless viscous substance.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.59 (d, J = 8.5Hz, 4H), 8.47 (d, J = 1.4Hz, 4H), 7.44 (dd, J = 8.5) 1.4Hz, 4H), 2.91 (t, J = 7.6Hz, 8H), 1.80 (tt, J = 7.6,7.6Hz, 8H), 1.48 (tq, J = 7) .6,7.6Hz, 8H), 1.00 (t, J = 7.6Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 141.1, 130.9, 129.0, 127.8, 127.4, 126.7, 123.1, 36.3, 34.2, 22.8, 14. 3ppm
MS (DART-TOFMS) m / z: 553 [MH] ⁺
IR (neat): 2952, 2925, 2857, 1610, 1499, 1455, 1436, 376, 826 cm ^-1
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₉ : 553.3829 [H] ⁺ , Found: 553.3848
Anal. Calcd for C ₄₂ H ₄₈ : C, 91.25; H, 8.75. Found: C, 91.24; H, 8.71.

Synthesis of Compound 1 Under an argon atmosphere, Compound 6 (2.74 g, 5.0 mmol) and methylene chloride (20 mL) were added to a 100 mL bite flask. Bromine (10.2 mL, 43 mmol, 4.2 M methylene chloride solution) was added dropwise at -20 ° C over 3 minutes, and after stirring for 2 hours (brown suspension), saturated sodium thiosulfate (20 mL) was added at 0 ° C. In addition, the reaction was stopped. The reaction solution was poured into a beaker containing methanol (180 mL) and stirred for 30 minutes. The precipitated solid was washed with water (250 mL), and then the obtained solid was dissolved in chloroform. This chloroform solution was washed with saturated brine (40 mL), dried with sardine and vacuum dried to obtain a yellowish white crude product. A recrystallization operation (toluene / ethyl acetate = 1/2, v / v) was carried out to obtain 2.28 g (61%) of Compound 1 as a white solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.71 (s, 4H), 8.40 (s, 4H), 3.00 (t, J = 7.6,8H), 1.78 (tt, J = 7) .6,7.6Hz, 8H), 1.5 (tq, J = 7.6,7.6Hz, 8H), 1.05 (t, J = 7.6Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 140.8, 131.8, 129.3, 128.2, 125.3, 124.6, 124.0, 36.5, 32.6, 22.9, 14. 2ppm
MS (DART-TOFMS) m / z: 868 [M] ⁺
IR (neat): 2949, 2917, 2857, 1606, 1435, 1061, 868 cm ^-1
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₄ Br ₄ : 868.0136 [M] ⁺ , Found: 868.0122
Anal. Calcd for C ⁴² H ₄₄ Br ₄ : C, 58.09; H, 5.11. Found: C, 57.86; H, 5.10

The brominated product in which bromine was substituted at the 3-position, 6-position, 11-position, and 14-position was hardly dissolved in toluene. On the other hand, 100 mg of compound 1 was dissolved in 22 mL of toluene at room temperature.

Example 2 (Synthesis of 2,7,10,15-Tetrabromo-3,6,11,14-Tetrabutyldibenzo [g, p] chrysene (Compound 2))

Synthesis of Compound 7 Under an argon atmosphere, DBC (3-Br) 4 (4.64 g, 7.2 mmol) was suspended in anhydrous tetrahydrofuran (140 mL) and at −78 ° C., normal butyllithium (27.2 mL, 1. 59M hexane solution) was added dropwise over 5 minutes. After stirring for 30 minutes, 1-bromobutane (7.0 mL, 65 mmol) was added over 5 minutes, and the mixture was naturally heated to room temperature and then stirred for 1 hour. After the reaction was stopped with water (40 mL), the organic layer was separated and the aqueous layer was extracted with toluene (20 mL × 3). The combined organic layers were washed with saturated brine (40 mL), dried over Glauber's salt and vacuum dried to obtain a crude yellow product. Column purification using silica gel (developing solvent was hexane / methylene chloride = 4/1) was performed to obtain 2.60 g of an orange-white solid. After the reprecipitation operation (methylene chloride / methanol = 1/8, v / v), a recrystallization operation (18 mL / g) was performed on 2.58 g of the obtained white solid using distilled propionitrile. .16 g (54%) of compound 7 was obtained as white crystals.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.57 (d, J = 8.4Hz, 4H), 8.50 (d, J = 1.5Hz, 4H), 7.49 (dd, J = 8.4) 1.5Hz, 4H), 2.8 (t, J = 7.5Hz, 8H), 1.75 (tt, J = 7.5, 7.5Hz, 8H), 1.44 (tq, J = 7) .5, 7.5Hz, 8H), 0.96 (t, J = 7.5Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 140.8, 129.4, 129.1, 128.5, 127.9, 127.5, 123.5, 36.2, 34.1, 22.6, 14. 3ppm
MS (DART-TOFMS) m / z: 553 [MH] ⁺
IR (neat): 2952,2921,385,1610,1464,1376,802,739cm ^-1
HRMS (DART-TOF) calcd for C ₄₂ H ₄₉ [MH] ⁺ : 553.3829, Found: 553.3838
Anal. Calcd for C ₄₂ H ₄₈ ; C, 91.25; H, 8.75. Found: C, 91.26; H, 8.90.

Synthesis of Compound 2 Under an argon atmosphere, Compound 7 (2.32 g, 4.2 mmol) and methylene chloride (20 mL) were added to a 100 mL bite flask. At room temperature, bromine (1.0 mL, 20 mmol, 4.2 M methylene chloride solution) was added dropwise over 3 minutes, and after stirring for 2 hours, the reaction was stopped at 0 ° C. using a 3 M aqueous sodium thiosulfate solution (20 mL). Was done. The organic layer was separated, and the aqueous layer was subjected to an extraction operation with methylene chloride (20 mL × 3). The combined organic layers were washed with saturated brine (40 mL), dried over Glauber's salt and vacuum dried to obtain a yellowish white crude product. A recrystallization operation (55 mL / g) using ethyl acetate was carried out to obtain 1.91 g (52%) of compound 2 as white crystals.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.63 (s, 4H), 8.25 (s, 4H), 2.84 (t, J = 7.6Hz, 8H), 1.70 (tt, J = 7) .6,7.6Hz, 8H), 1.48 (tq, J = 7.6,7.6Hz, 8H), 0.99 (t, J = 7.6Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 140.1, 128.7, 128.5, 127.5, 127.4, 126.1, 123.8, 36.4, 32.5, 22.9, 14. 2ppm
MS (DART-TOFMS) m / z: 868 [M] ⁺
IR (neat): 2955, 2924, 2857, 1460, 1393, 1013, 871, 728, 468 cm ^-1
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₄ Br ₄ : 868.0136 [M] ⁺ , Found: 868.0163
Anal. Calcd for C ₄₂ H ₄₄ Br ₄ ; C, 58.09; H, 5.11. Found: C, 57.66; H, 5.07

100 mg of Compound 2 was dissolved at room temperature in 0.4 mL of toluene, 4 mL of hexane, 1.3 mL of methylene chloride, 0.3 mL of chloroform and 0.3 mL of tetrahydrofuran, respectively. On the other hand, the 2-position, 7-position, 10-position, and 15-position brominated products having no butyl group were hardly dissolved in any of these solvents.

Example 3 (Synthesis of 9,11,14,16-Tetrabromo-2,7-dibutyl-10,15-dimethoxybenzo [g, p] chrysene (Compound 8))

Synthesis of Compound 3 Under an argon atmosphere, 1,3-dibromo-5,5-dimethylhydantoin (DBDMH, 629 mg, 2.2 mmol) was added to a solution of diol (473 mg, 1.0 mmol) in anhydrous chloroform (8 mL) at room temperature. Added in. After stirring for 4 hours, the reaction was stopped with saturated aqueous sodium thiosulfate solution (5 mL) and 1 M hydrochloric acid (10 mL). An extraction operation (10 mL × 3) was carried out on the aqueous layer with methylene chloride, and the combined organic layer was washed with saturated brine (10 mL), dried with sardine and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was toluene) was carried out to obtain 550 mg (70%) of compound 3 as a green solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.99 (d, J = 1.7Hz, 2H), 8.55 (s, 2H), 8.43 (d, J = 8.4Hz, 2H), 7.48 (Dd, J = 8.4, 1.7Hz, 2H) 6.53 (s, 2H), 2.85 (t, J = 7.3Hz, 4H), 1.76 (tt, J = 7.3) , 7.3Hz, 4H), 1.45 (tq, J = 7.3, 7.3Hz, 4H), 0.96 (t, J = 7.3Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 148.8, 139.9, 131.1, 130.2, 128.9, 128.38, 128.36, 127.9, 127.8, 125.5, 123. 6,109.5,108.4,36.0,22.7,14.3ppm
MS (DART-TOFMS) m / z: 789 [MH] ⁺
IR (neat): 3470, 2921, 1575, 1412, 1176, 826 cm ^-1
HRMS (DART-TOF) calcd for C ₃₄ H ₂₉ Br ₄ O ₂ [MH] ⁺ : 788.8860, Found: 788.88868

Synthesis of Compound 8 Methyl iodide (0.57 mL, 10 mmol) is added to a solution of Compound 3 (398 mg, 0.5 mmol) in acetone (10 mL), and diazabicycloundecene (DBU, 0.68 mL, 5 mmol) is added for 3 minutes. Dropped over. After stirring at room temperature for 15 hours, the reaction was stopped with a 3M aqueous hydrochloric acid solution (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 combined organic layers were washed with saturated brine (10 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was toluene / hexane = 1/1) was carried out to obtain 298 mg (73%) of Compound 8 as a yellowish white solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 9.09 (d, J = 1.6Hz, 2H), 8.59 (s, 2H), 8.41 (d, J = 8.3Hz, 2H), 7.48 (Dd, J = 8.3, 1.6Hz, 2H), 4.06 (s, 6H), 2.86 (t, J = 7.5Hz, 4H), 1.77 (tt, J = 7. 5,7.5Hz, 4H), 1.45 (tq, J = 7.5,7.5Hz, 4H), 0.98 (t, J = 7.5Hz, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 153.4, 140.1, 131.3, 130.9, 130.3, 129.6, 129.2, 128.52, 128.48, 128.2, 127. 8, 123.4, 117.5, 116.8, 61.1, 36.0, 33.7, 22.5, 14.2 ppm
MS (DARTTOFMS) m / z: 817 [MH] ⁺
IR (neat): 2952,2932,2857,1606,1369,997,827cm ^-1
HRMS (DART-TOF) calcd for C ₃₆ H ₃₃ Br ₄ O ₂ [MH] ⁺ : 816.9168, Found: 816.9144
Anal. Calcd for C ₃₆ H ₃₂ Br ₄ O ₂ ; C, 52.97; H, 3.95. Found: C, 52.83; H, 3.91

Since compound 3 is vulnerable to heat, X-ray structural analysis was performed on compound 8. The result is shown in FIG. The helix angle was as large as 44.59 °. It was also found that DBC having a phenolic hydroxyl group specifically promotes bromination at the ortho position even at a position having a large steric requirement such as the bay area.

Example 4 (Synthesis of 1,8,9,16-Tetrabromo-3,6,11,14-Tetrabutyl-2,7,10,15-Tetrahydroxycibenzo [g, p] chrysene (Compound 4))

Synthesis of Compound 9 Under an argon atmosphere, Compound 2 (2.5 g, 2.9 mmol) was suspended in dimethylformamide (240 mL), and copper iodide (3.3 g, 17.3 mmol) and sodium methoxide (57 mL, 288 mmol) were suspended. , 28% methanol solution) was added. The reaction solution was stirred at 120 ° C. for 2 hours, and then the reaction was stopped with a 3M aqueous hydrochloric acid solution (100 mL). The obtained sample was diluted with methylene chloride, and the aqueous layer was subjected to an extraction operation (50 mL × 3) with methylene chloride. The combined organic layers were washed with saturated brine (100 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was hexane / toluene = 4/1) was carried out to obtain 1.28 g (66%) of compound 9 as a white solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.44 (s, 4H), 7.87 (s, 4H), 4.11 (s, 12H), 2.81 (t, J = 7.8Hz, 8H), 1.70 (tt, J = 7.8, 7.8Hz, 8H), 1.45 (tq, J = 7.8, 7.8Hz, 8H), 0.96 (t, J = 7.8Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 152.0, 126.7, 125.8, (two peaks are overlapped), 125.3, 119.3, 98.5, 51, 28, 1, 26.2 , 18.6, 9.9ppm
MS (DART-TOFMS) m / z: 673 [MH] ⁺
IR (neat): 2956,2921,3853,1603,1459,1408,1129,1025,838cm ^-1
HRMS (DARTTOF) calcd for C ₄₆ H ₅₇ O ₄ [MH] ⁺ : 673.4252, Found: 673.4238
Anal. Calcd for C ₄₆ H ₅₇ O ₄ ; C, 82.10; H, 8.39. Found: C, 82.09; H, 8.37.

Synthesis of Compound 10 Under an argon atmosphere, compound 9 (659 mg, 0.98 mmol) and methylene chloride (14 mL) were added to a 100 mL flask. 1M Boron tribromide (5.9 mL, 5.9 mmol, methylene chloride solution) was added dropwise at 0 ° C. over 5 minutes, and the mixture was stirred for 10 minutes. The temperature was naturally raised to room temperature, and after stirring for 2 hours, the reaction was stopped using water (20 mL). The obtained sample was diluted with ethyl acetate, and the aqueous layer was subjected to an extraction operation (15 mL × 3) with ethyl acetate. The combined organic layers were washed with saturated brine (15 mL), dried over Glauber's salt and vacuum dried to give 592 mg (98%) of compound 10 as a purple solid. The resulting sample was subjected to the next bromination experiment without further purification.

^{1 1} HNMR (400MHz, CD ₃ CN) 8.32 (s, 4H), 7.84 (s, 4H), 7.24 (brs, 4H), 2.76 (t, J = 7.5Hz, 8H) , 1.70 (tt, J = 7.5, 7.5Hz, 8H), 1.45 (tq, J = 7.5, 7.5Hz, 8H), 0.96 (t, J = 7.5Hz) , 12H) ppm
¹³ CNMR (100MHz, DMSO-d ₆ ) 154.0, 129.4, 129.1, 129.0, 123.1, 122.0, 107.0, 31.8, 29.9, 22.2 14.0ppm
MS (DART-TOFMS) m / z: 617 [MH] ⁺
IR (neat): 3331,295,2925,2857,1615,1423,1217,842cm ^-1
HRMS (DARTTOF) calcd for C ₄₂ H ₄₉ O ₄ [MH] ⁺ : 617.3625, Found: 617.3610
Anal. Calcd for C ₄₂ H ₄₈ O ₄ ; C, 81.78; H, 7.84. Found: C, 81.78; H, 7.78

Synthesis of Compound 4 Under an argon atmosphere, compound 10 (617 mg, 1.0 mmol) and methylene chloride (25 mL) were added to a 100 mL flask. At 0 ° C., bromine (7.4 mL, 32 mmol, 4.2 M methylene chloride solution) was added dropwise over 5 minutes and then stirred for 15 minutes. The temperature was naturally raised to room temperature, and after stirring for 17 hours, the reaction was stopped using a saturated aqueous sodium thiosulfate solution (50 mL) and a 3M aqueous hydrochloric acid solution (50 mL) at 0 ° C. The obtained sample was diluted with methylene chloride, and the aqueous layer was subjected to an extraction operation (20 mL × 3) with methylene chloride. The combined organic layers were washed with saturated brine (20 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was hexane / methylene chloride = 2/1) was carried out to obtain 550 mg (60%) of Compound 4 as a yellowish white solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.20 (s, 4H), 6.14 (s, 4H), 2.93 (dt, J = 14.4, 7.3Hz, 4H), 2.77 (dt) , J = 14.4, 7.3Hz, 4H), 1.73 (ddt, J = 7.3, 7.3, 7.3Hz, 8H), 1.49 (tq, J = 7.3, 7) .3Hz, 8H), 0.99 (t, J = 7.3Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 150.3, 131.6, 129.2, 128.1, 126.7, 126.2, 111.2, 32.2, 31.7, 23.4, 14. 7ppm
MS (DART-TOFMS) m / z: 933 [MH] ⁺
IR (neat): 2949 (OH, sharp), 2917, 2857, 1606, 1435, 1061, 868 cm-1
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₅ Br ₄ O ₄ : 933.0010 [MH] ⁺ , Found: 932.9393
Anal. Calcd for C ₄₂ H ₄₄ Br ₄ O ₄ : C, 54.10; H, 4.76. Found: C, 54.08; H, 4.52

X-ray structure analysis was performed on compound 4. The result is shown in FIG. The helix angle was 55.89 °, which was a very large value. It can be understood that the compound 4 has a undulating and non-planar structure. The effect of this dense functional group was also confirmed by IR spectroscopic analysis, and the peak of the hydroxyl group was confirmed as a sharp ruled line at 2949 cm ^-1 . It means that the hydroxyl group does not associate with other hydroxyl groups, which is a proof that the area around the hydroxyl group is sterically very crowded.

Example 5 (Synthesis of 1,8,9,16-Tetrabromo-3,6,11,14-Tetrabutyl-2,7,10,15-Tetrahydroxycibenzo [g, p] chrysene (Compound 5))

Synthesis of Compound 11 Under an argon atmosphere, Compound 1 (2.6 g, 3.0 mmol) was suspended in dimethylformamide (240 mL), and copper iodide (6.8 g, 36 mmol) and sodium methoxide (90 mL, 450 mmol, 28) were suspended. % Methanol solution) was added. The reaction solution was stirred at 120 ° C. for 2 hours, and then the reaction was stopped with a 3M aqueous hydrochloric acid solution (150 mL). The obtained sample was diluted with toluene, and the aqueous layer was subjected to an extraction operation (80 mL × 3) with toluene. The combined organic layers were washed with saturated brine (150 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was hexane / toluene = 9/1) was carried out to obtain 1.09 g (55%) of compound 11 as a white-yellow solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.35 (s, 4H), 8.20 (s, 4H), 3.96 (s, 12H), 2.90 (t, J = 7.7Hz, 8H), 1.78 (tt, J = 7.7, 7.7Hz, 8H), 1.52 (tq, J = 7.7, 7.7Hz, 8H), 1.03 (t, J = 7.7Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 156.2, 131.9, 128.4, 127.7, 124.8, 124.6, 108.4, 55.9, 32.8, 31.0, 23. 2,14.5ppm
MS (DART-TOF) m / z: 673 [MH] ⁺
IR (neat): 2952, 2925, 2857, 1619, 1496, 1455, 1412, 1249, 1145, 1049, 842 cm ^-1
HRMS (DART-TOF) calcd for C ₄₆ H ₅₇ O ₄ [MH] ⁺ : 673.4251, Found 673.4270
Anal. Calcd for C ₄₆ H ₅₆ O ₄ ; C, 82.10; H, 8.39. Found: C, 82.09; H, 8.66

Synthesis of Compound 12 Under an argon atmosphere, compound 11 (1.09 g, 1.6 mmol) and methylene chloride (10 mL) were added to a 50 mL flask. After dropping 1 M boron tribromide (9.6 mL, 9.6 mmol, methylene chloride solution) at 0 ° C. over 5 minutes, the purple solution was stirred at 0 ° C. for 10 minutes. The temperature was naturally raised to room temperature, and after stirring for 2 hours, the reaction was stopped at 0 ° C. using water (15 mL). The obtained sample was diluted with ethyl acetate, and the aqueous layer was subjected to an extraction operation (20 mL × 3) with ethyl acetate. The combined organic layers were washed with saturated brine (20 mL), dried over Glauber's salt and vacuum dried to give 964 mg (98%) of compound 12 as a green-yellow solid. The resulting sample was subjected to the next bromination experiment without further purification.

^{1 1} HNMR (400MHz, CD ₃ CN) 8.37 (s, 4H), 8.15 (s, 4H), 7.28 (s, 4H), 2.84 (t, J = 7.5Hz, 8H) , 1.74 (tt, J = 7.5, 7.5Hz, 8H), 1.48 (tq, J = 7.5, 7.5Hz, 8H), 1.00 (t, J = 7.5Hz) , 12H) ppm
¹³ CNMR (100MHz, CD ₃ CN) 153.9, 130.8, 128.8, 127.3, 125.4, 125.2, 112.9, 33.1, 31.1, 23.4, 14 .3ppm
MS (DART-TOFMS) m / z: 617 [MH] ⁺
IR (neat): 3339, 2952, 2925, 2857, 1623, 1499, 1423, 1236, 1137, 989, 870 cm ^-1
HRMS (DART-TOF) calcd for C ₄₂ H ₄₉ O ₄ [MH] ⁺ : 617.3625, Found: 617.3652

Synthesis of Compound 5 Under an argon atmosphere, compound 12 (617 mg, 1.0 mmol) and methylene chloride (20 mL) were added to a 100 mL flask. Bromine (4.8 mL, 4.8 mmol, 1 M methylene chloride solution) was added dropwise at −20 ° C. over 5 minutes. After stirring for 15 minutes (brown suspension), the temperature was naturally raised to room temperature and the mixture was stirred for 7 hours. The reaction was stopped at 0 ° C. with a saturated aqueous solution of sodium thiosulfate (20 mL) and a 1 M aqueous solution of hydrochloric acid (40 mL). The obtained sample was diluted with methylene chloride, and the aqueous layer was subjected to an extraction operation (20 mL × 3) with methylene chloride. The combined organic layers were washed with saturated brine (20 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was hexane / toluene = 4/1) was carried out to obtain 573 mg (61%) of compound 5 as a yellow solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.31 (s, 4H), 6.11 (s, 4H), 2.96 (t, J = 7.5Hz, 8H), 1.80 (tt, J = 7) .5, 7.5Hz, 8H), 1.52 (tq, J = 7.5, 7.5Hz, 8H), 1.02 (t, J = 7.5Hz, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 149.5, 133.1, 130.2, 127.8, 124.11, 124.09, 110.2, 32.2, 31.7, 23.0, 22. 9,14.2 ppm
MS (DART-TOFMS) m / z: 933 [MH] ⁺
IR (neat): 3450, 2952, 2925, 2857, 1606, 1459, 1408, 1176, 1137, 1021, 870 cm ^-1
HRMS (DART-TOFMS) calcd for C ₄₂ H ₄₅ Br ₄ O ₄ : 933.0010 [MH] ⁺ , Found: 993.0013
Anal. Calcd for C ₄₂ H ₄₄ Br ₄ O ₄ : C, 54.10; H, 4.76. Found: C, 54.09; H, 4.52.

X-ray structure analysis was performed on compound 5. The result is shown in FIG. The helix angle was 53.97 °, which was a very large value. It can be understood that the compound 5 has a undulating and non-planar structure. The helix angle is about the same as 55.89 ° of compound 4, and it can be said that the structural strain that the fjord region gives to the DBC and the structural strain that the bay area region gives to the DBC are about the same.

Example 6 (Synthesis of 1,5,9,14-Tetrabromo-2,3,6,7,10,11,14,15-Octamethoxy-benzo [g, p] chrysene (Compound 14))

Synthesis of Compound 13 Under an argon atmosphere, 2,7,10,15-tetrabromo-3,6,11,14-tetramethoxy-benzo [g, p] chrysen (1.53 g, 2.0 mmol) was added to dimethylformamide (80 mL). ), And copper iodide (3.37 g, 24 mmol) and sodium methoxide (60 mL, 300 mmol, 28% methanol solution) were added. The reaction solution was stirred at 120 ° C. for 2 hours, and then the reaction was stopped with a 3M aqueous hydrochloric acid solution (100 mL). The obtained sample was diluted with methylene chloride, and the aqueous layer was subjected to an extraction operation (40 mL × 3) with methylene chloride. The combined organic layers were washed with saturated brine (100 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was methylene chloride / ethyl acetate = 19/1) was carried out to obtain 751 mg (66%) of compound 13 as a white-brown solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.21 (s, 4H), 7.89 (s, 4H), 4.18 (s, 12H), 4.01 (s, 12H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 149.0, 148.5, 125.6, 124.9, 123.7, 109.7, 104.8, 56.4, 56.3ppm
MS (DART-TOFMS) m / z: 569 [MH] ⁺
IR (neat): 2992, 2965, 2928, 2829, 1503, 1458, 1411, 1248, 1180, 1140, 1041,845,746 cm ^-1
HRMS (DART-TOFMS) calcd for C ₃₄ H ₃₃ O ₈ : 569.2175 [MH] ⁺ , Found: 569.2156

Synthesis of Compound 14 Under an argon atmosphere, compound 13 (100 mg, 0.18 mmol) was suspended in a mixed solvent of methylene chloride and acetic acid (1 / 1v / v, v = 2 mL), and bromine (2.8 mL, 2.8 mmol) was suspended. , 1M methylene chloride solution) was added dropwise over 3 minutes. After stirring at room temperature for 24 hours, the reaction was stopped at 0 ° C. with a saturated aqueous sodium thiosulfate solution (5 mL). The obtained sample was diluted with methylene chloride, and the aqueous layer was subjected to an extraction operation (10 mL × 3) with methylene chloride. The combined organic layers were washed with saturated brine (10 mL), dried over Glauber's salt and vacuum dried to obtain a crude product. A filtration column purification operation using silica gel (developing solvent was hexane / ethyl acetate = 4/1) was carried out to obtain 43 mg (28%) of compound 14 as a yellow solid.

^{1 1} HNMR (400MHz, CDCl ₃ ) 8.94 (s, 2H), 7.36 (s, 2H), 4.15 (s, 6H), 3.98 (s, 6H), 3.94 (s, 6H), 3.93 (s, 6H) ppm
¹³ CNMR (100MHz, CDCl ₃ ) 152.0, 150.7, 147.4, 146.7, 131.1, 129.1, 128.6, 123.8, 122.5, 116.5, 115. 9, 113.1, 111.4, 61.1, 61.0, 56.7, 56.4 ppm
MS (DART-TOFMS) m / z: 884 [MH] ⁺
IR (neat): 2997,2933,2829,1587,1459,1391,1272,1141,1053,1038,993,858cm ^-1
HRMS (DART-TOFMS) calcd for C ₃₄ H ₂₈ Br ₄ O ₈ : 883.8555 [MH] ⁺ , Found: 884.85565
Anal. Calcd for C ₃₄ H ₂₈ Br ₄ O ₈ : C, 46.19; H, 3.19. Found: C, 46.37; H, 3.11

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 (4)

Dibenzo [g] having 4 or more substituents selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkanoyl group, an alkenoyl group, an alkinoyl group, a polyoxyalkylene group and / or a hydroxyl group, and 4 halogeno groups. , P] Chrysen derivative. The following formula

or

The dibenzo [g, p] chrysene derivative according to claim 1. A dibenzo [g, p] chrysene derivative having 6 or more alkoxy groups and / or polyoxyalkylene groups and 4 halogeno groups. The following formula

The dibenzo [g, p] chrysene derivative according to claim 3.

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