Axialaryl group-containing tribenzotriquinacene and method for producing the same

Abstract

To provide a tribenzotriquinacene containing an axial aryl group and a method for preparing the same.SOLUTION: The present invention provides a tribenzotriquinacene containing an axial aryl group, having a structure shown in formula (1): R1 and R2 are independently hydrogen, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C1-C12 fluoroalkyl group, a C1-C12 fluorine-containing alkoxy group, a C1-C12 ester group, a halogen group, a nitro group, an amine group, a cyano group, or a hydroxy group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to axial aryl group-containing tribenzotriquinacene (TBTQ) and a method for producing the same. [Background technology]

[0002] Tribenzotriquinacene is C 3v Tribenzotriquinacene is a bowl-shaped molecule with the symmetry C. Due to its special configuration, tribenzotriquinacene has a wide range of applications. For example, it is used in the production of organic nanocubes, C 60 Molecules and C 70 It can be applied to molecular host-guest chemistry, the synthesis of microporous materials, and the assembly of large meshes of molecules. Summary of the Invention [Problem to be solved by the invention]

[0003] However, the method for producing tribenzotriquinacene has a problem of low yield, and it is difficult to modify a specific position of tribenzotriquinacene with a functional group, which limits the applicability of tribenzotriquinacene. [Means for solving the problem]

[0004] The subject matter of the present disclosure has the structure shown in formula (1): [ka] R1 and R2 are independently hydrogen, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C1-C12 fluoroalkyl group, a C1-C12 fluorine-containing alkoxy group, a C1-C12 ester group, a halogen group, a nitro group (-NO2), an amino group, a cyano group (-CN), or a hydroxy group (-OH), providing an axial aryl group-containing tribenzotriquinacene (TBTQ).

[0005] In some embodiments, the tribenzotriquinacene has the structure shown in formula (2). [ka]

[0006] In some embodiments, the tribenzotriquinacene has the structure shown in formula (3). [ka]

[0007] In some embodiments, R1 and R2 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, nitro, amino, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, trifluoroethoxy, fluoro, chloro, bromo, cyano, hydroxy, or -CO2CH3.

[0008] In some embodiments, R1 and R2 have the same structure.

[0009] The present disclosure provides a method for producing an axialaryl group-containing tribenzotriquinacene, the method comprising reacting a reagent having the structure shown in Formula (4) in the presence of a superacid to produce the axialaryl group-containing tribenzotriquinacene of any of the above embodiments. [ka]

[0010] In some embodiments, the superacid comprises trifluoromethanesulfonic acid (TfOH), fluorosulfonic acid (HS0F), fluoroantimonic acid, magic acid, carborane acid, or a combination thereof.

[0011] In some embodiments, the reaction time of the reagents in the presence of the superacid is from 1 hour to 24 hours.

[0012] In some embodiments, the reaction temperature of the reagents in the presence of a superacid is between 0°C and 100°C.

[0013] In some embodiments, the method further includes adding the superacid and the reagent to a solvent comprising benzene, toluene, chlorobenzene, dichlorobenzene, dichloromethane (DCM), 1,2-dichloroethane, chloroform, or a combination thereof, prior to reacting the reagent in the presence of the superacid. [Effects of the Invention]

[0014] The preparation method has the advantages of simple process, mild reaction conditions and high synthesis yield, and the axial position of tribenzotriquinacene can be easily modified with an aryl group, and the benzene ring of tribenzotriquinacene can be easily modified, thereby improving the applicability of tribenzotriquinacene. [Brief explanation of the drawings]

[0015] A more complete understanding of the present disclosure can be obtained by reading the following detailed description of the embodiments and by referring to the drawings, in which: [Figure 1] 1 is an X-ray single crystal diffraction crystal structure of tribenzotriquinacene having formula (a). DETAILED DESCRIPTION OF THE INVENTION

[0016] To make the contents of the present disclosure more detailed and complete, the following briefly describes the embodiments and specific examples of the contents of the present disclosure, but this is not the only way to implement or use the specific examples of the contents of the present disclosure. The respective examples disclosed below may be combined with or substituted for each other, or other examples may be added to some examples, if beneficial, without the need for further description or explanation.

[0017] Although the methods disclosed herein are described below using a series of operations or steps, the order depicted in these operations or steps should not be construed as a limitation of the content of the present disclosure. For example, some operations or steps may be performed in different orders and / or simultaneously with other steps. Moreover, not all illustrated operations, steps, and / or features need to be performed to implement embodiments of the present disclosure. Furthermore, each operation or step described herein may include multiple sub-steps or operations.

[0018] Tribenzotriquinacene has wide applicability and great development potential in chemical research. To address the problems of low yields in the preparation of tribenzotriquinacene and the difficulty of modifying functional groups at specific positions (e.g., axial positions) of tribenzotriquinacene, the present disclosure provides an axial aryl group-containing tribenzotriquinacene (TBTQ) and a method for preparing the same. In the preparation method, a reagent having a benzofulvene structure or a structure similar to benzofulvene is used as a reactant to synthesize the axial aryl group-containing tribenzotriquinacene, which is also called an axial aryl group-containing tribenzotriquinacene-based compound. In other words, the apical position of the bowl-shaped structure of tribenzotriquinacene is modified with an aryl group, thereby possessing an aryl group at the axial position. The axial aryl group-containing tribenzotriquinacene can be applied in fields such as, but not limited to, the pharmaceutical industry, the chemical industry (e.g., the petrochemical industry), and the biomedical industry. For example, tribenzotriquinacene can be applied to products such as, but not limited to, natural essential oils, food additives, rubber, polymeric materials, building materials, computer and communication equipment, protective clothing, packaging materials, or biosensing platforms.

[0019] The present disclosure provides an axial aryl group-containing tribenzotriquinacene having the structure shown in formula (1). [ka] R1 can be bonded to any one carbon atom of the benzene ring, and R2 can be bonded to any one carbon atom of the benzene ring. R1 and R2 are independently hydrogen, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C1-C12 fluoroalkyl group, a C1-C12 fluorine-containing alkoxy group, a C1-C12 ester group, a halogen group, a nitro group (-NO2), an amino group, a cyano group (-CN), or a hydroxy group (-OH). For example, the C1-C12 alkyl group, the C1-C12 alkoxy group, the C1-C12 fluoroalkyl group, the C1-C12 fluorine-containing alkoxy group, and the C1-C12 ester group each have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In some embodiments, the C1-C12 alkyl group is a methyl group (-Me), an ethyl group (-Et), an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, or an n-hexyl group. In some embodiments, the C1-C12 alkoxy group is a methoxy group (-OMe) or an ethoxy group (-OEt). In some embodiments, the C1-C12 fluoroalkyl group has 1, 2, 3, 4, 5, or 6 fluorine atoms, and the C1-C12 fluoroalkyl group is, for example, a trifluoromethyl group (-CF3). In some embodiments, the C1-C12 fluorine-containing alkoxy group has 1, 2, 3, 4, 5, or 6 fluorine atoms, and the C1-C12 fluorine-containing alkoxy group is, for example, a trifluoromethoxy group (-OCF3) or a trifluoroethoxy group. In some embodiments, the C1-C12 ester group is —CO2R a and R ais a C1-C12 alkyl group, and the C1-C12 alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In some embodiments, the C1-C12 ester group is -CO2CH3. In some embodiments, the halogen group is a fluoro group (-F), a chloro group (-Cl), or a bromo group (-Br). In some embodiments, the amino group is -NH2, -NHR b or -NR b R c and R b and R c may be a C1-C12 alkyl group, and the C1-C12 alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. In some embodiments, R1 and R2 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, nitro, amino, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, trifluoroethoxy, fluoro, chloro, bromo, cyano, hydroxy, or —CO2CH3. In some embodiments, R1 and R2 have the same structure, and therefore the tribenzotriquinacene has high symmetry. In some embodiments, R1 and R2 have different structures.

[0020] In some embodiments, the tribenzotriquinacene has the structure shown in formula (2). [ka]

[0021] In some embodiments, the tribenzotriquinacene has the structure shown in formula (3). [ka]

[0022] The present disclosure provides a method for producing an axialaryl group-containing tribenzotriquinacene, the method comprising reacting a reagent having the structure shown in Formula (4) in the presence of a superacid to produce the axialaryl group-containing tribenzotriquinacene of any of the above embodiments. [ka]

[0023] More specifically, a superacid and a reagent undergo an acid-mediated reaction. The superacid can protonate and cyclize the reagent to produce tribenzotriquinacene. This reagent has a benzofulvene structure or a structure similar to benzofulvene, which has the advantages of easy synthesis, good stability, low cost, and low toxicity. Furthermore, since this reagent has no asymmetric center and is highly pure, when synthesizing tribenzotriquinacene using this reagent as a starting material, there is no need to worry about the stereochemistry affecting the synthesis reaction. Furthermore, the benzene ring or bridgehead of this reagent can be easily modified with different functional groups (R1, R2), broadening the applicability of tribenzotriquinacene. In some embodiments, when reacting the reagent in the presence of a superacid, the addition of a transition metal catalyst is not required, and the product is transition metal-free. The production method of the present disclosure has the advantages of simple process, mild reaction conditions, and high synthesis yield.

[0024] In some embodiments, the superacid comprises trifluoromethanesulfonic acid, fluorosulfonic acid, fluoroantimonic acid, magic acid, carborane acid, or a combination thereof, where trifluoromethanesulfonic acid has the property of being difficult to degrade. In some embodiments, the reaction time of the reagents in the presence of the superacid is 1 hour to 24 hours. For example, the reaction time is 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, or 24 hours. In some embodiments, the reaction temperature of the reagents in the presence of the superacid is 0°C to 100°C. For example, the reaction temperature is 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100°C. Therefore, the production method of the present disclosure has the advantages of simple processes and mild reaction conditions.

[0025] In some embodiments, the method further includes adding the superacid and the reagent to a solvent comprising benzene, toluene, chlorobenzene, dichlorobenzene, dichloromethane, 1,2-dichloroethane, chloroform, or a combination thereof, prior to reacting the reagent in the presence of the superacid. In some embodiments, the solvent is an anhydrous solvent.

[0026] The bonding positions of R1 and R2 in the reagent are further explained below. In the structure of formula (4), the carbon atoms on the benzene ring are numbered, see formula (4-1) below. [ka] In formula (4-1), R1 can be bonded to any one carbon atom of the benzene ring, and R2 can be bonded to any one carbon atom of the benzene ring. More specifically, R1 can be bonded to the carbon atom numbered 1, 2, 3, 4, 5, or 6. These R2 on different benzene rings are bonded to the carbon atoms numbered i, o, m, or p, respectively. These R2 can all be bonded to the carbon atom with the same number, or these R2 can be bonded to carbon atoms with different numbers.

[0027] In some embodiments, in a reagent having the structure shown in formula (4-1), R1 is bonded to carbon numbered 3 and R2 are all bonded to carbon numbered p, so that the reagent has the structure shown in formula (5). [ka] In the presence of a superacid, a reagent having the structure shown in formula (5) can react to produce tribenzotriquinacene having the structure shown in formula (2).

[0028] In some embodiments, in a reagent having the structure shown in formula (4-1), R1 is bonded to carbon numbered 3 and R2 are all bonded to carbon numbered m, so that the reagent has the structure shown in formula (6). [ka] In the presence of a superacid, a reagent having the structure shown in formula (6) can react to produce tribenzotriquinacene having the structure shown in formula (3).

[0029] The features of the present disclosure will be explained in more detail below with reference to Experimental Examples 1 to 10. Although the following experimental examples have been described, the materials used, their amounts and ratios, processing details, processing processes, etc. can be appropriately changed without departing from the scope of the present disclosure. Therefore, the experimental examples described below should not be interpreted as limiting the contents of the present disclosure.

[0030] Experimental Example 1: Synthesis of tribenzotriquinacene having formula (a)

[0031] A 25 mL glass tube equipped with a stir bar was charged with a reagent (0.1 mmol) having the structure shown in formula (5), TfOH (0.1 mL, 20 equivalents), and DCM (1.0 mL) to form a reaction mixture. In formula (5), R1 and R2 are all fluoro groups (-F), so the reagent had the structure shown in formula (5-1) below. [ka]

[0032] The glass tube was sealed with a screw cap in an air atmosphere, and the reaction mixture was stirred at room temperature (30 °C) for 24 hours. More specifically, TfOH and the reagents were reacted in a TfOH-mediated reaction. The reaction mixture was then quenched with crushed ice and then with cold aqueous sodium bicarbonate solution. The product was then extracted with DCM. The DCM was removed under reduced pressure to obtain a residue, which was purified by flash column chromatography, where the extractant contained hexane and ethyl acetate, with a volume ratio of hexane to ethyl acetate of 50:1. After purification, a product having the structure shown in formula (a) below was obtained. [ka]

[0033] The product was a white solid, and the crude yield was 91%. After purification, the weight of the product was 31.6 mg, and the product yield was 74%. The melting point of the product was 242°C to 246°C. When hexane was used as a developing solvent, the R f The value was 0.26. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.40-7.35 (m, 5H), 7.14 (dd, J = 2.0, 8.8 Hz, 3H), 7.07-7.02 (m, 2H), 6.99 (td, J = 2.4, 88 Hz, 3H), and 5.00 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shift (δ) (unit: ppm) of C NMR (CDCl3, 100 MHz) was 164.3 (d, 1 J C-F =244.0Hz), 161.8(d, 1 J C-F =244.4Hz), 146.6(d, 3 J C-F =7.6Hz), 143.7(d,4 J C-F =3.4Hz), 139.5(d, 4 J C-F =2.6Hz), 126.4(d, 3 J C-F =7.6Hz), 125.3(d, 3 J C-F =8.8Hz), 115.8(d, 2 J C-F =21.3Hz), 115.3(d, 2 J C-F =22.8Hz), 111.0(d, 2 J C-F =22.1Hz), 70.7, 63.4(d, 4 J C-F = 1.9 Hz). The product was mixed with KBr to prepare a sample, and the Fourier-transform infrared spectroscopy (FTIR) spectrum of the sample was measured. The wave numbers (unit: cm) corresponding to the peaks in the spectrum were -1 ) were 3067, 2870, 1608, 1279, 1096, and 964. The theoretical molecular weight of the product was 428.1188. When measured by high resolution mass spectrometer (HRMS), the molecular weight of the product was 428.1191, which was very close to the theoretical value. The X-ray single crystal diffraction crystal structure of tribenzotriquinacene of formula (a) is shown in Figure 1. The above test results prove that Experimental Example 1 can produce tribenzotriquinacene of formula (a), whose structure is (4bR,8bR,12bR)-2,6,10-trifluoro-4b 1 -(4-fluorophenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-trifluoro-4b 1 -(4-fluorophenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0034] Experimental Example 2: Synthesis of tribenzotriquinacene having formula (b)

[0035] Tribenzotriquinacene having the following formula (b) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 2, the reagent had the structure shown in Formula (5) and R1 and R2 were all hydrogen (-H). [ka]

[0036] The product was a white solid, and the crude yield was 98%. After purification, the product weight was 25.6 mg, and the product yield was 72%. The melting point of the product was 230°C to 232°C. When hexane was used as a developing solvent, the R f The value was 0.25. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.50-7.45 (m, 8H), 7.34 (t, J = 7.6 Hz, 2H), 7.28-7.20 (m, 7H), and 5.16 (s, 3H). 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 100 MHz) were 149.0, 145.0, 128.9, 127.7, 126.3, 125.1, 124.1, 68.9, and 64.3. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The wave numbers (unit: cm) corresponding to the peaks in the spectrum were -1 ) were 3054, 2924, 1587, 1267, and 1013. The theoretical molecular weight of the product was 356.1565. Measured by HRMS, the molecular weight of the product was 356.1568, which was very close to the theoretical value. The above test results prove that Experimental Example 2 can produce tribenzotriquinacene having the formula (b), whose structure is (4bR,8bR,12bR)-4b 1 -phenyl-4b,4b 1,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-4b 1 -phenyl-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0037] Experimental Example 3: Synthesis of tribenzotriquinacene having formula (c)

[0038] Tribenzotriquinacene having the following formula (c) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 3, the reagent had the structure shown in Formula (5), and R1 and R2 were all chloro groups (-Cl). [ka]

[0039] The product was a white solid, and the crude yield was 95%. After purification, the product weight was 35.9 mg, and the product yield was 73%. The melting point of the product was 230°C to 232°C. When hexane was used as a developing solvent, the R f The value was 0.25. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.39 (s, 3H), 7.37 (d, J = 8.4 Hz, 3H), 7.33-7.28 (m, 4H), 7.24 (dd, J = 1.8, 8.0 Hz, 3H), and 4.98 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 100 MHz) were 146.1, 146.0, 142.2, 134.0, 132.5, 129.1, 128.4, 126.2, 125.3, 124.2, 69.9, and 63.3. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers (unit: cm) of the peaks in the spectrum were -1) were 3054, 2923, 1373, 1012, and 954. The theoretical molecular weight of the product was 492.0006. Measured by HRMS, the molecular weight of the product was 492.0011, which was very close to the theoretical value. The above test results prove that Experimental Example 3 can produce tribenzotriquinacene having the formula (c), whose structure is (4bR,8bR,12bR)-2,6,10-trichloro-4b 1 -(4-chlorophenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-trichloro-4b 1 -(4-chlorophenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0040] Experimental Example 4: Synthesis of tribenzotriquinacene having formula (d)

[0041] Tribenzotriquinacene having the following formula (d) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 4, the reagent had the structure shown in Formula (5), and R1 and R2 were all bromo groups (-Br). [ka]

[0042] The product was a white solid, and the crude yield was 98%. After purification, the weight of the product was 53.4 mg, and the product yield was 80%. The melting point of the product was 250°C to 252°C. When hexane was used as a developing solvent, the R f The value was 0.26. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.54 (s, 3H), 7.49 (td, J = 2.4, 9.2 Hz, 2H), 7.40 (dd, J = 1.2, 8.0 Hz, 3H), 7.32 (d, J = 8.0 Hz, 3H), 7.24 (td, J = 2.4, 9.8 Hz, 2H), and 4.96 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the CNMR (CDCl3, 100 MHz) were 146.5, 146.2, 142.7, 132.1, 131.3, 127.2, 126.6, 125.7, 122.0, 120.6, 69.6, and 63.3. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The wave numbers (unit: cm) corresponding to the peaks in the spectrum were -1 ) were 3021, 2850, 1894, 1062, and 953. The theoretical molecular weight of the product was 667.7986. Measured by HRMS, the molecular weight of the product was 667.7992, which was very close to the theoretical value. The above test results prove that Experimental Example 4 can produce tribenzotriquinacene having the formula (d), whose structure is (4bR,8bR,12bR)-2,6,10-tribromo-4b 1 -(4-bromophenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-tribromo-4b 1 -(4-bromophenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0043] Experimental Example 5: Synthesis of tribenzotriquinacene having formula (e)

[0044] Tribenzotriquinacene having the following formula (e) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 5, the reagent had the structure shown in Formula (5), and R1 and R2 were all trifluoromethoxy groups (-OCF3). [ka]

[0045] The product was a white solid, and the crude yield was 95%. After purification, the weight of the product was 56.1 mg, and the product yield was 81%. The melting point of the product was 218°C to 220°C. When hexane was used as a developing solvent, the R f The value was 0.24. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.50 (d, J = 8.4 Hz, 3H), 7.46 (dd, J = 2.0, 6.8 Hz, 2H), 7.33 (s, 3H), 7.26 (d, J = 6.8 Hz, 2H), 7.19 (d, J = 9.6 Hz, 3H), and 5.12 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of C NMR (CDCl3, 100 MHz) were 149.5, 149.5, 148.0, 146.1, 146.0, 142.3, and 127.3 (q, J C-F =297.5Hz), 125.2, 124.3(q,J C-F = 256.1 Hz), 121.1, 119.2, 117.0, 70.5, and 63.4. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers of the peaks in the spectrum (unit: cm -1 ) were 2956, 2849, 1905, 1160, and 985. The theoretical molecular weight of the product was 692.0857. Measured by HRMS, the molecular weight of the product was 692.0852, which was very close to the theoretical value. The above test results prove that Experimental Example 5 can produce tribenzotriquinacene having the formula (e), whose structure is (4bR,8bR,12bR)-2,6,10-tris(trifluoromethoxy)-4b 1-(4-(trifluoromethoxy)phenyl)-4b,4b1,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-tris(trifluoromethoxy)-4b 1 The compound was named -(4-(trifluoromethoxy)phenyl)-4b,4b1,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0046] Experimental Example 6: Synthesis of tribenzotriquinacene having formula (f)

[0047] Tribenzotriquinacene having the following formula (f) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 6, the reagent had the structure shown in Formula (5), and R1 and R2 were all methyl groups (-Me). [ka]

[0048] The product was a white solid, and the crude yield was 49%. After purification, the product weight was 13.1 mg, and the product yield was 32%. The melting point of the product was 226°C to 228°C. When hexane was used as a developing solvent, the R f The value was 0.34. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.17-7.12 (m, 7H), 7.11-7.09 (m, 3H), 6.95 (s, 3H), 4.81 (s, 3H), 2.34 (s, 6H), and 2.29 (s, 6H). The NMR carbon spectrum of the product ( 13The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 175 MHz) were 153.1, 153.0, 137.1, 136.4, 136.2, 134.7, 129.5, 128.0, 127.4, 125.4, 119.0, 50.5, 21.5, and 21.1. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The wave numbers (unit: cm) corresponding to the peaks in the spectrum were -1 ) were 2920, 2730, 1940, 1413, and 966. The theoretical molecular weight of the product was 412.2191. Measured by HRMS, the molecular weight of the product was 412.2196, which was very close to the theoretical value. Based on the above test results, it can be proven that Experimental Example 6 can produce tribenzotriquinacene having the formula (f), whose structure is (4bR,8bR,12bR)-2,6,10-trimethyl-4b 1 -(p-Tolyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-trimethyl-4b 1 -(p-tolyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0049] Experimental Example 7: Synthesis of tribenzotriquinacene having formula (g)

[0050] Tribenzotriquinacene having the following formula (g) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 7, the reagent had the structure shown in Formula (5), and R1 and R2 were all methoxy groups (-OMe). [ka]

[0051] The product was a white solid, and the crude yield was 61%. After purification, the weight of the product was 24.7 mg, and the product yield was 52%. The melting point of the product was 226°C to 228°C. When hexane was used as a developing solvent, the R f The value was 0.34. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.17-7.12 (m, 7H), 7.11-7.09 (m, 3H), 6.95 (s, 3H), 4.81 (s, 3H), 2.34 (s, 6H), and 2.29 (s, 6H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 175 MHz) were 159.7, 146.9, 141.3, 136.9 (2C), 126.0, 124.6, 114.1, 113.5, 109.2, 70.4, 63.6, 55.5, and 55.3. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers (unit: cm) of the peaks in the spectrum were -1 ) were 2920, 2730, 1940, 1413, and 966. The theoretical molecular weight of the product was 476.1988. Measured by HRMS, the molecular weight of the product was 476.1995, which was very close to the theoretical value. Based on the above test results, it can be proven that Experimental Example 7 can produce tribenzotriquinacene having the formula (g), whose structure is (4bR,8bR,12bR)-2,6,10-trimethoxy-4b 1 -(4-Methoxyphenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-trimethoxy-4b 1 -(4-methoxyphenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0052] Experimental Example 8: Synthesis of tribenzotriquinacene having formula (h)

[0053] Tribenzotriquinacene having the following formula (h) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 8, the reagent had the structure shown in Formula (5), and R1 and R2 were all isopropyl groups (- i Pr). [ka]

[0054] The product was a white solid, and the crude yield was 52%. After purification, the weight of the product was 23.5 mg, and the product yield was 45%. The melting point of the product was 198°C to 200°C. When hexane was used as a developing solvent, the R f The value was 0.35. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.38 (s, 5H), 7.29 (d, J = 10.8 Hz, 3H), 7.16 (d, J = 7.6 Hz, 2H), 7.08 (d, J = 7.6 Hz, 3H), 5.06 (s, 3H), 2.91-2.84 (m, 4H), and 1.40-1.20 (m, 24H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 175 MHz) were 148.2, 146.7, 146.6, 142.6, 126.3, 125.9, 125.8, 125.4, 123.8, 121.8, 69.5, 63.9, 34.1, 33.9, 33.6, 24.2, 24.0, and 23.9. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers (unit: cm) of the peaks in the spectrum were -1) were 2870, 1708, 1432, 1155, 1039, and 778. The theoretical molecular weight of the product was 524.3443. Measured by HRMS, the molecular weight of the product was 524.3442, which was very close to the theoretical value. The above test results prove that Experimental Example 8 can produce tribenzotriquinacene having the formula (h), whose structure is (4bR,8bR,12bR)-2,6,10-triisopropyl-4b 1 -(4-isopropylphenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bR,8bR,12bR)-2,6,10-triisopropyl-4b 1 -(4-isopropylphenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0055] Example 9: Synthesis of tribenzotriquinacene having formula (i)

[0056] Tribenzotriquinacene having the following formula (i) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 9, the reagent had the structure shown in Formula (6), and R1 and R2 were all chloro groups (-Cl). [ka]

[0057] The product was a white solid, and the crude yield was 45%. After purification, the product weight was 20.2 mg, and the product yield was 41%. The melting point of the product was 212°C to 214°C. When hexane was used as a developing solvent, the R f The value was 0.31. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.28-7.24 (m, 3H), 7.19 (d, J = 7.6 Hz, 2H), 7.12-7.09 (m, 6H), 7.04-7.02 (m, 2H), and 4.90 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 100 MHz) were 154.1, 150.2, 140.2, 139.6, 134.9, 133.5 (2C), 130.4, 127.8, 126.2, 125.9, 120.0, 56.4, and 50.2. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers (unit: cm) of the peaks in the spectrum were -1 ) were 3121, 2891, 1542, 1112, and 932. The theoretical molecular weight of the product was 492.0006. Measured by HRMS, the molecular weight of the product was 492.0001, which was very close to the theoretical value. The above test results prove that Experimental Example 9 can produce tribenzotriquinacene having the formula (i), whose structure is (4bS,8bS,12bS)-2,6,10-trichloro-4b 1 -(3-chlorophenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bS,8bS,12bS)-2,6,10-trichloro-4b 1 -(3-chlorophenyl)-4b,4b 1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0058] Experimental Example 10: Synthesis of tribenzotriquinacene having formula (j)

[0059] Tribenzotriquinacene having the following formula (j) was synthesized by referring to the manufacturing process of Experimental Example 1. In Experimental Example 10, the reagent had the structure shown in Formula (6), and R1 and R2 were all methoxy groups (-OMe). [ka]

[0060] The product was a white solid, and the crude yield was 58%. After purification, the weight of the product was 20.5 mg, and the product yield was 43%. The melting point of the product was 242°C to 244°C. When hexane was used as a developing solvent, the R f The value was 0.11. The nuclear magnetic resonance (NMR) hydrogen spectrum of the product ( 1 The chemical shifts (δ) (unit: ppm) of H-NMR (CDCl3, 400 MHz) were 7.34 (d, J = 8.4 Hz, 3H), 7.24 (d, J = 8.0 Hz, 1H), 7.02 (d, J = 7.6 Hz, 1H), 6.98 (s, 1H), 6.94 (s, 3H), 6.77-6.72 (m, 4H), 4.98 (s, 3H), 3.78 (s, 9H), and 3.74 (s, 3H). The NMR carbon spectrum of the product ( 13 The chemical shifts (δ) (unit: ppm) of the C NMR (CDCl3, 100 MHz) were 160.0, 159.7, 150.8, 146.8, 136.8, 129.8, 124.6, 117.5, 113.6, 111.8, 110.5, 109.2, 71.0, 63.4, 55.5, and 55.2. The product was mixed with KBr to prepare a sample, and the FTIR of the sample was measured. The corresponding wave numbers (unit: cm) of the peaks in the spectrum were -1 ) were 3066, 2853, 1332, 1023, and 962. The theoretical molecular weight of the product was 476.1988. Measured by HRMS, the molecular weight of the product was 476.1985, which was very close to the theoretical value. The above test results prove that Experimental Example 10 can produce tribenzotriquinacene having the formula (j), whose structure is (4bS,8bS,12bS)-2,6,10-trimethoxy-4b 1 -(3-methoxyphenyl)-4b,4b 1 ,8b,12b-Tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene ((4bS,8bS,12bS)-2,6,10-trimethoxy-4b 1 -(3-methoxyphenyl)-4b,4b1 ,8b,12b-tetrahydrodibenzo[2,3:4,5]pentaleno[1,6-ab]indene).

[0061] As described above, the present disclosure provides an axial aryl group-containing tribenzotriquinacene and a method for producing the same. The method has the advantages of a simple process, mild reaction conditions, and a high synthesis yield. It is also easy to modify the axial position of tribenzotriquinacene with an aryl group, and it is also easy to modify the benzene ring of tribenzotriquinacene, thereby broadening the applicability of tribenzotriquinacene.

[0062] Although the subject matter of the present disclosure has been described in considerable detail with reference to certain embodiments, other embodiments are possible, and therefore, the spirit and scope of the scope of the appended patent application should not be limited to the description of the embodiments contained herein.

[0063] It will be apparent to those skilled in the art that various modifications and variations can be made in the structure of the present disclosure without departing from the scope or spirit of the disclosure. In view of the above, it is intended that the present disclosure cover modifications and variations of the present disclosure provided they fall within the scope of the appended claims.

Claims

1. It has a structure shown in formula (1), 【Chemical 1】 Here, R １ and R ２ are independently hydrogen, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C1 to C12 fluoroalkyl group, a C1 to C12 fluorine-containing alkoxy group, a C1 to C12 carboxylic acid ester group having a carbon number of C1 to C12 including the C in —CO 2 constituting the ester bond, a halogen group, a nitro group, an amino group, a cyano group, or an axial aryl group-containing tribenzotriquinacene which is a hydroxy group.

2. The axial aryl group-containing tribenzotriquinacene according to claim 1, characterized in that the axial aryl group-containing tribenzotriquinacene has a structure represented by formula (2): 【Chemistry 2】

3. The axial aryl group-containing tribenzotriquinacene according to claim 1, characterized in that the axial aryl group-containing tribenzotriquinacene has a structure represented by formula (3): 【Chemistry 3】

4. R １ and R ２ are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, nitro, amino, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, trifluoroethoxy, fluoro, chloro, bromo, cyano, hydroxy, or —CO ２ CH ３ The axial aryl group-containing tribenzotriquinacene according to claim 1, characterized in that:

5. R １ and R ２ The axial aryl group-containing tribenzotriquinacene according to claim 1, characterized in that:

6. 2. A method for producing the axial aryl group-containing tribenzotriquinacene of claim 1, comprising reacting a reagent having a structure represented by formula (4) in the presence of a super strong acid to produce the axial aryl group-containing tribenzotriquinacene of claim 1. 【Chemistry 4】

7. 7. The method of claim 6, wherein the superacid comprises trifluoromethanesulfonic acid, fluorosulfonic acid, fluoroantimonic acid, magic acid, carborane acid, or a combination thereof.

8. 7. The method according to claim 6, wherein the reaction time for reacting the reagent in the presence of the superacid is 1 hour to 24 hours.

9. 7. The method according to claim 6, wherein the reaction temperature of the reagent in the presence of the superacid is 0°C to 100°C.

10. 7. The method of claim 6, further comprising adding the superacid and the reagent to a solvent comprising benzene, toluene, chlorobenzene, dichlorobenzene, dichloromethane, 1,2-dichloroethane, chloroform, or a combination thereof, prior to reacting the reagent in the presence of the superacid.

Images