Hexa-peri-hexabenzocoronene precursor compound, preparation and use thereof

Abstract

This invention relates to the field of materials, providing hexabenzo[a] ...

Description

Technical Field

[0001] This invention relates to the field of materials, and more specifically to a hexabenzo[a]corona] precursor compound and its preparation, and to the application of such compounds in releasing hexabenzo[a]corona molecules under specific conditions. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs) are a very important class of organic compounds with wide applications in organic optoelectronic materials, biological probes, and supramolecular chemistry. As a classic organic PAH molecule, the highly symmetrical hexa-peri-hexabenzocoronene (HBC, approximately 1.4 nm in diameter), composed of 42 carbon atoms, is a typical graphene fragment, consisting entirely of sp... 2 Composed of a hybrid six-membered carbon ring, hexabenzo[a] ...

[0003] However, as a delocalized planar aromatic compound, the strong π-π interactions between molecules cause hexabenzo[a]col to form a strong close packing (H-packing) between molecules, resulting in very low solubility in various solvents. This greatly limits its application in solution-based material preparation or in biomaterials that require a certain degree of water solubility.

[0004] Given the promising applications and structural characteristics of hexabenzo[a]cor, the construction of hexabenzo[a]cor molecules has been a research hotspot in recent years. Hexabenzo[a]cor molecules are a series of compounds modified from bulk molecules. To increase their solubility, the most common method is to introduce long-chain functional groups onto the benzene ring of hexabenzo[a]cor, but the solubility still cannot be significantly improved. Introducing non-six-membered rings, such as five-, seven-, eight-, and even nine-membered rings, into planar structures constructed solely of six-membered rings yields molecules with curved surface properties, such as bowl-shaped molecules with embedded aza-five-membered rings [Angew.Chem.Int.Ed.2015,54,7256.] and saddle-shaped molecules with negative curvature [J.Am.Chem.Soc.2012,134,13796.]. The introduction of large eight- and nine-membered rings yields chiral graphene nanoparticles with spirocyclic olefins [Angew.Chem.Int.Ed.2021,60,6094.]. Many of these structures alter the planar properties of hexabenzo[a]col]oxane. Nanoscale graphene structures with precise insertion of single or multiple nitrogen atoms have also been designed and synthesized. Simultaneously, different types of hexabenzo[a]oxane "oligomers" have been constructed, such as hexabenzo[a]oxane "dimers," "trimers," and "tetramers." The successful preparation of these hexabenzo[a]oxane-like molecules has greatly enriched structural diversity, and the properties and potential applications of these new structures are also more diverse, such as the polarization optical properties of chiral molecules and the specific supramolecular interactions of three-dimensional structures. Some of these hexabenzo[a]oxane-like compounds have solved the problem of low solubility in bulk molecules; however, because they alter their planar structure and aromaticity distribution, they have to some extent lost their excellent photoelectric properties. Summary of the Invention

[0005] The purpose of this invention is to provide a hexabenzo[a]corona] precursor compound, its preparation method, and a method for releasing hexabenzo[a]corona molecules under specific conditions. The aim of this invention is to provide a solution to the problem of poor solubility of hexabenzo[a]corona molecules in various solvents, which limits their application in materials, while retaining the good photoelectric properties of the precursor.

[0006] This invention is achieved through the following scheme: a hexabenzo[a]corona] precursor compound, characterized in that: a group VIA main element atom is inserted into the fjord region of the hexabenzo[a]corona] molecule, comprising a fully cyclic molecule including a seven-membered heterocycle and an incompletely cyclic molecule and its oxidized compound, the structural formula of which is as follows:

[0007]

[0008] In the structural formula, the element X inserted into the hexabenzo[a] ...

[0009]

[0010] When a selenium atom is inserted into the fjord region of a hexabenzo[a]methyl ether molecule, its structural formula is as follows:

[0011]

[0012] The present invention also provides a method for preparing the compound, comprising the following synthetic steps:

[0013]

[0014] (a) It reacts with 2,3,4,5-tetrachloro-1λ6-thiophene-1,1-dione or 2,3,4,5-tetrabromo-1λ6-thiophene-1,1-dione in a DA reaction to produce (b) The halogen site in the compound undergoes a Suzuki coupling reaction with phenylboronic acid compounds to form... (c) A ring-closure reaction occurs to generate target compounds 1-9. (d) Compounds 1-9 can be further oxidized to compounds 1o-9o and 1o2-9o2. Specifically, the ring-closure reaction in step (c) is carried out in the presence of dichlorodicyanobenzoquinone (DDQ) and trifluoromethanesulfonic acid. More specifically, the oxidation in step (d) is carried out in the presence of m-chloroperoxybenzoic acid, or in the presence of potassium peroxymonosulfate complex salt (OXONE).

[0015] This invention provides an application of the hexabenzo[a] ...

[0016] The hexabenzo[a]cobala precursor compounds of this invention can remove group VIA element atoms under heating conditions to generate incompletely cyclized spirocyclic hexabenzo[a]cobala molecules. Under air and acidic conditions, group VIA elements can be removed and further cyclized to generate fully cyclized hexabenzo[a]cobala molecules.

[0017] This invention provides hexabenzo[a]coazone compounds with VIA group element atoms inserted into the edge of the hexabenzo[a]coazone molecule, including molecules in the oxidized state of VIA group element atoms, and provides methods for their preparation. These molecules can undergo a reaction to remove VIA group element atoms under heating, light, and acidic conditions, generating incompletely cyclic-closed and fully cyclic-closed hexabenzo[a]coazone molecules. Since R groups can be introduced onto the outer benzene ring of these hexabenzo[a]coazone molecules, the introduction of R groups can alter the solubility of the molecule. For example, introducing an aliphatic carbon chain can increase the solubility of the molecule in organic solvents according to the principle of "like dissolves like." Furthermore, the hexabenzo[a]coazone molecules we provide include incompletely cyclic-closed molecules. Due to molecular distortion, the solubility of incompletely cyclic-closed compounds is also increased compared to planar hexabenzo[a]coazone molecules. These molecules can remove VIA group element atoms under specific conditions to generate incompletely and fully cyclic-closed hexabenzo[a]coazone molecules, providing a solution to the limitation of applications caused by the poor solubility of hexabenzo[a]coazone molecules. Attached Figure Description

[0018] Figure 1 The 1H NMR spectrum of compound 4;

[0019] Figure 2 The 1H NMR spectrum of compound 5;

[0020] Figure 3 The 1H NMR spectrum of compound 4O2;

[0021] Figure 4 The 1H NMR spectrum of compound 5o;

[0022] Figure 5 The 1H NMR spectrum of compound 10;

[0023] Figure 6 The 1H NMR spectrum of compound 11;

[0024] Figure 7 UV spectra of compounds 4°, 5° and 5° for the heating removal reaction, starting material and product. Detailed Implementation

[0025] The following detailed description is provided in conjunction with specific examples.

[0026] Example 1

[0027] Synthesis of compound 4:

[0028]

[0029] (10Z)-Dibenzo[1,2-b:1',2'-f]thiacycloheptan (210 mg, 1.0 mmol, 1 equiv) and 2,3,4,5-tetrachloro-1λ6-thiophene-1,1-dione (381 mg, 1.5 mmol, 1.5 equiv) were dissolved in toluene and refluxed for 12 hours. The mixture was then cooled to room temperature, and dichlorodicyanoquinone (DDQ) (340 mg, 1.5 mmol, 1.5 equiv) was added. The mixture was stirred for 30 minutes, the solvent was removed under reduced pressure, and column chromatography was performed to obtain a pale yellow solid, 1,2,3,4-tetrachlorotribenzo[1,2-b:1',2'-d:1”,2”-f]thiacycloheptan (519 mg), with a yield of 75%. 1,2,3,4-Tetrachlorotribenzo[1,2-b:1',2'-d:1”,2”-f]thiacycloheptan (460 mg, 0.8 mmol, 1.0 equiv), 4-tert-butylphenylboronic acid (1140 mg, 6.4 mmol, 8.0 equiv), palladium dichlorodiacetonitrile (31 mg, 0.12 mmol, 0.15 equiv), 2-bicycloethylphosphine-2',6'-dimethoxybiphenyl (SPhos, 99 mg, 0.24 mmol) 0.3 mmol (ol, 0.3 equiv) and potassium phosphate (2.71 g, 12.8 mmol, 16.0 equiv) were dissolved in toluene. The air in the reaction flask was replaced with argon, and the reaction was refluxed for 12 hours. The solid was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. Column chromatography was used to separate the solid compound 1,2,3,4-tetra[4-(2-methylpropyl-2-yl)phenyl]tribenzo[1,2-b:1',2'-f:1”,2”-d]thiacycloheptan (397 mg), with a yield of 63%. Compound 1,2,3,4-tetra[4-(2-methylpropyl-2-yl)phenyl]tribenzo[1,2-b:1',2'-f:1”,2”-d]thiacycloheptan (80 mg, 0.1 mmol, 1.0 equiv) and dichlorodicyanobenzoquinone (DDQ) (227 mg, 1 mmol, 10.0 equiv) were dissolved in 20 mL of dichloromethane. The air in the reaction flask was replaced with argon, and the reaction flask was placed in an ice-water bath. Trifluoromethanesulfonic acid ( CF3SO3H (0.1 mL, 1.3 mmol, 13 equiv) was added to the above reaction flask, and the mixture was stirred for 5 minutes. Triethylamine (1.0 mL, 7.2 mmol, 72 equiv) was added, followed by methanol (1.0 mL, 24.7 mmol, 247 equiv) to quench the reaction. The solvent was removed under reduced pressure, and column chromatography was used to obtain a yellow solid compound 4 (63 mg), with a yield of 80%. NMR and mass spectrometry data are as follows: 1HNMR(400MHz, CDCl3)δ9.22(s,1H),9.18(s,1H),9.13(s,1H),9.09(s,1H),9.03(s,1H ),8.91(s,1H),8.83(d,J=6.0Hz,1H),8.78(s,1H),8.19(d,J=6.0Hz,1H),8.09(d,J=8 .0Hz,1H),7.89(d,J=6.0Hz,1H),7.72(t,J=6.0Hz,1H),7.33–7.29(m,2H),6.90(t,J= 6.0Hz,1H),6.31(d,J=6.0Hz,1H),1.79(s,9H),1.77(s,9H),1.71(s,9H),1.50(s,9H); 13 C NMR (101MHz, CDCl3) δ149.3,149.2,149.1,149.1,137.8,135.1,133.6,133.5,132.8,132. 6,131.3,131.1,130.8,130.5,130.4,130.4,130.2,130.1,129.9,128.9,128.5,128.3,12 7.9,127.3,127.0,124.8,124.2,123.6,123.2,123.1,123.0,122.7,121.3,119.9,119.1, 119.0,118.3,35.7,35.7,35.60,35.0,32.0,31.9,31.9,31.4; HRMS(MALDI-TOF)m / z:[M+H] + Calcd for C 58 H 53 S 781.3862; Found 781.3881. The 1H NMR spectrum is attached. Figure 1 .

[0030] Example 2

[0031] Synthesis of compound 5:

[0032]

[0033] (10Z)-5H-dibenzo[1,2-b:1',2'-f]selenocycloheptan (257 mg, 1.0 mmol, 1 equiv) and 2,3,4,5-tetrabromo-1λ6-thiophene-1,1-dione (647 mg, 1.5 mmol, 1.5 equiv) were dissolved in xylene and refluxed for 12 hours. The mixture was then cooled to room temperature, and dichlorodicyanoquinone (DDQ) (340 mg, 1.5 mmol, 1.5 equiv) was added. The mixture was stirred for 30 minutes, the solvent was removed under reduced pressure, and column chromatography was used to obtain a pale yellow solid, 1,2,3,4-tetrabromo-9H-tribenzo[1,2-b:1',2'-d:1”,2”-f]selenocycloheptan (348 mg), with a yield of 56%. 1,2,3,4-Tetrabromo-9H-tribenzo[1,2-b:1',2'-d:1”,2”-f]selenocycloheptan (498 mg, 0.8 mmol, 1.0 equiv), 4-tert-butylphenylboronic acid (1140 mg, 6.4 mmol, 8.0 equiv), palladium dichloroacetonitrile (31 mg, 0.12 mmol, 0.15 equiv), 2-bicycloethylphosphine-2',6'-dimethoxybiphenyl (SPhos, 99 mg, 0.24 mmol) 0.3 mmol (ol, 0.3 equiv) and potassium phosphate (2.71 g, 12.8 mmol, 16.0 equiv) were dissolved in xylene. The air in the reaction flask was replaced with argon, and the mixture was refluxed for 12 hours. The solid was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. Column chromatography was used to separate the solid compound 1,2,3,4-tetra[4-(2-methylpropyl-2-yl)phenyl]-9H-tribenzo[1,2-b:1',2'-f:1”,2”-d]selenocycloheptan (361 mg), with a yield of 54%. Compound 1,2,3,4-tetra[4-(2-methylpropyl-2-yl)phenyl]-9H-tribenzo[1,2-b:1',2'-f:1”,2”-d]selenocycloheptan (84 mg, 0.1 mmol, 1.0 equiv) and dichlorodicyanobenzoquinone (DDQ) (227 mg, 1 mmol, 10.0 equiv) were dissolved in 20 mL of dichloromethane. The air in the reaction flask was replaced with argon, and the flask was placed in an ice-water bath. Trifluoromethanesulfonic acid (0.1 mL, 1.3 mmol, 13 equiv) was added to the above reaction flask, and the reaction was stirred for 5 minutes. Triethylamine (1.0 mL, 7.2 mmol, 72 equiv) was added, followed by methanol (1.0 mL, 24.7 mmol, 247 equiv) to quench the reaction. The solvent was removed from the reaction solution under reduced pressure, and column chromatography was used to obtain a yellow solid compound 5 (50 mg), with a yield of 60%. 1H NMR (400MHz, CDCl3) δ9.22(s,1H),9.18(s,1H),9.12(s,1H),9.07(s,1H),9.04(s,1H),8.91 (s,1H),8.83(d,J=6.0Hz,1H),8.80(s,1H),8.34(d,J=6.0Hz,1H),8.19(d,J=8.0Hz,1H),8.0 0(d,J=6.0Hz,1H),7.65(t,J=6.0Hz,1H),7.33(d,J=6.0Hz,1H),7.26(t,J=6.0Hz,1H),6.88 (t,J=6.0Hz,1H),6.24(d,J=6.0Hz,1H),1.80(s,9H),1.77(s,9H),1.71(s,9H),1.50(s,9H); 13 C NMR (101MHz, CDCl3) δ149.9,149.2,149.1,149.1,135.7,134.8,134.4,133.7,133.3,13 2.9,131.6,131.4,130.9,130.8,130.5,130.3,130.1,129.9,129.0,128.3,128.2,127.8 ,127.3,124.9,124.2,123.6,123.2,123.1,122.8,121.1,120.0,119.1,119.0,119.0,1 18.9,118.3,35.7,35.7,35.6,34.9,32.0,31.9,31.9,31.4; HRMS(MALDI-TOF)m / z:[M+H] + Calcd for C 58 H 53 Se 829.3307 Found 829.3304. The 1H NMR spectrum is attached. Figure 2 .

[0034] Example 3

[0035] Synthesis of compound 4o:

[0036]

[0037] Compound 4 (38 mg, 0.05 mmol, 1.0 equiv) was dissolved in 10 mL of dichloromethane, and potassium persulfate complex salt (Oxone, 307 mg, 0.5 mmol, 10.0 equiv) was added. The mixture was stirred for 2 hours, and the reaction was quenched by adding 10% sodium sulfite aqueous solution (1.4 mL, 1 mmol, 20 equiv). The solvent was removed from the reaction solution under low pressure, and compound 4 was obtained by column chromatography. O (38mg), Compound 4 O It is a yellow solid with a yield of 96%. 1 H NMR(400MHz, CDCl3)δ9.24(s,1H),9.21(s,1H),9.17(s,1H),9.15(s,1H),9.07(s,1H) ,8.99(s,1H),8.98(d,J=6.0Hz,1H),8.82(s,1H),8.49(d,J=6.0Hz,1H),8.11–8.08(m ,2H),8.03(t,J=8.0Hz,1H),7.57(t,J=6.0Hz,1H),7.35(d,J=6.0Hz,1H),7.02(t,J=6 .0Hz,1H),6.38(d,J=6.0Hz,1H),1.80(s,9H),1.77(s,9H),1.72(s,9H),1.51(s,9H); 13 C NMR (101MHz, CDCl3) δ150.0,149.7,145.5,145.0,136.2,133.2,132.9,131.5,130.7,130. 7,130.6,130.5,130.4,130.2,129.9,129.6,129.2,128.8,128.6,128.2,128.0,125.3,12 5.0,124.5,123.5,123.3,122.8,122.4,122.3,120.4,119.4,119.3,119.2,119.2,119.1, 119.0,118.7,118.6,35.7,35.7,35.7,35.0,31.9,31.9,31.8,31.3; HRMS(ESI)m / z:[M+H] + Calcd for C 58 H 53 OS 797.3812; found 797.3833.

[0038] Example 4

[0039] Synthesis of compound 4O2:

[0040]

[0041] Compound 4o (40 mg, 0.05 mmol, 1.0 equiv) and m-chloroperoxybenzoic acid (m-CPBA, 34 mg, 0.2 mmol, 4.0 equiv) were dissolved in 10 mL of dichloromethane and stirred for 24 hours. The reaction was quenched by adding 10% sodium sulfite aqueous solution (0.6 mL, 0.4 mmol, 8 equiv). The solvent was removed from the reaction solution under reduced pressure, and compound 4o2 (37 mg) was obtained by column chromatography as a yellow solid with a yield of 92%. 1 H NMR (600MHz, CDCl3) δ9.22 (s, 1H), 9.19 (d, J = 6.0Hz, 1H), 9.17 (s, 2H), 9.15 (s, 1H), 9.03 (s,1H),8.96(s,1H),8.76(d,J=6.0Hz,1H),8.74(s,1H),8.37(d,J=6.0Hz,1H),8.17(d,J =8.0Hz,1H),7.95(t,J=8.0Hz,1H),7.55(t,J=8.0Hz,1H),7.29(d,J=6.0Hz,1H),7.17(d, J=6.0Hz,1H),6.63(d,J=6.0Hz,1H),1.80(s,9H),1.76(s,9H),1.72(s,9H),1.48(s,9H); 13 C NMR (151MHz, CDCl3) δ149.8,149.7,149.5,149.5,141.7,141.3,140.2,135.7,134.6,133.6,13 2.4,132.0,131.5,131.0,130.5,130.4,130.2,130.0,129.3,128.8,128.7,128.6,128.1,127.2 ,126.9,126.2,124.3,124.3,124.1,123.8,123.3,123.0,122.2,121.8,120.9,119.4,119.2,1 19.2,119.1,119.0,118.4,35.7,35.7,35.6,34.9,31.9,31.9,31.8,31.3; HRMS(ESI)m / z:[M+H] + Calcd for C 58 H 53 O2S 813.3761; found 813.3762. See attached 1H NMR spectrum. Figure 3 .

[0042] Example 5

[0043] Compound 5 O Synthesis

[0044]

[0045] Compound 5 (41 mg, 0.05 mmol, 1.0 equiv) was dissolved in 10 mL of dichloromethane, and m-chloroperoxybenzoic acid (m-CPBA, 10 mg, 0.06 mmol, 1.2 equiv) was added. The mixture was stirred for 2 hours, and the reaction was quenched by adding 0.2 mL of 10% sodium sulfite aqueous solution (0.1 mmol, 7 equiv). The solvent was removed from the reaction solution under low pressure, and compound 5 was obtained by column chromatography. O (40mg), Compound 5 O It is a yellow solid with a yield of 95%. 1 H NMR(400MHz, CDCl3)δ9.24(s,1H),9.21(s,1H),9.15(s,1H),9.12(s,1H),9.06(s,1H),8.96 (s,1H),8.94(d,J=6.0Hz,1H),8.83(s,1H),8.56(d,J=6.0Hz,1H),8.13(d,J=6.0Hz,1H),8.0 6(d,J=8.0Hz,1H),8.00(t,J=6.0Hz,1H),7.58(t,J=6.0Hz,1H),7.31(d,J=8.0Hz,1H),7.03 (t,J=6.0Hz,1H),6.33(d,J=6.0Hz,1H),1.80(s,9H),1.77(s,9H),1.72(s,9H),1.50(s,9H); 13 C NMR (151MHz, CDCl3) δ150.1,149.9,149.9,149.8,144.1,143.4,139.7,133.6,133.5,131.7 ,130.6,130.6,130.5,130.4,130.2,130.2,130.1,129.7,129.3,129.2,128.8,128.2,128.1 ,126.9,125.7,125.6,124.6,123.6,123.1,122.8,122.7,122.3,120.6,120.5,119.6,119. 4,119.2,119.2,118.7,35.7,35.7,35.7,35.0,31.9,31.9,31.8,31.3; HRMS(ESI)m / z:[M+H] + Calcd for C 58 H53 OSe 845.3256; found 845.3260. See attached 1H NMR spectrum. Figure 4 .

[0046] Example 6

[0047] Heating removal reaction of compound 4o:

[0048]

[0049] Compound 40 (40 mg) was added to a reaction tube and heated to 250 °C for 2 hours. Dichloromethane was added to dissolve the compound, and the UV spectrum was measured. The sample was recovered and separated by column chromatography, yielding 40 mg of the compound (greater than 99%). Its structure was identified by NMR spectroscopy; the 1H NMR spectrum is attached. Figure 5 4o, UV spectral data for product and compound 10 are attached. Figure 7 . 1 H NMR (400MHz, CDCl3) δ9.24 (s, 2H), 9.22 (s, 2H), 9.20 (s, 1H), 9.16 (d, J = 8.0Hz, 1H) ,9.07(s,1H),8.97(d,J=8.0Hz,1H),8.74(s,1H),8.73(d,J=8.0Hz,1H),8.57(d,J= 8.0Hz,1H),8.45(d,J=8.0Hz,1H),8.17(t,J=8.0Hz,1H),7.60(t,J=8.0Hz,1H),7. 36(d,J=8.0Hz,1H),7.27(t,J=8.0Hz,1H),1.80(s,18H),1.79(s,9H),1.55(s,9H); 13 C NMR (101MHz, CDCl3) δ149.9,149.4,149.2,131.9,131.7,131.4,130.6,130.5,130.5,130. 5,130.3,130.2,130.1,130.1,129.9,129.2,127.0,126.6,125.3,125.1,124.0,123.5,12 3.4,123.1,123.1,123.0,122.7,122.6,121.9,121.2,120.6,120.5,119.7,119.3,119.0, 119.0,118.9,118.8,118.4,35.8,35.7,35.7,35.1,32.0,31.4; HRMS(MALDI-TOF)m / z:[M] + Calcd forC 58 H 52748.4069Found 748.4090.

[0050] Example 7

[0051] Heating removal reaction of compound 5:

[0052]

[0053] Compound 5 (41 mg, 0.05 mmol, 1.0 equiv) was added to a reaction tube, heated to 200 °C for 5 minutes, dissolved in dichloromethane, and its UV spectrum was measured. The test sample was recovered, and 41 mg of the compound was obtained by column chromatography with a yield greater than 99%. The structure was identified by NMR spectroscopy. UV spectral data for compound 5, the product, and compound 10 are attached. Figure 7 .

[0054] Example 8

[0055] Compound 5O removal reaction upon heating:

[0056]

[0057] Compound 5O (40 mg) was added to a reaction tube and heated to 200°C for 5 minutes. Dichloromethane was then added to dissolve the compound, and the UV spectrum was measured. The sample was recovered, and 40 mg of the resulting compound was obtained by column chromatography with a yield greater than 99%. Its structure was identified as compound 10 by NMR spectroscopy. The UV spectra of 5O, the product, and compound 10 were measured; the UV spectral data are attached. Figure 7 .

[0058] Example 9

[0059] Removal reaction of compound 5° under acidic conditions:

[0060]

[0061] Compound 5O (42 mg, 0.05 mmol, 1.0 equiv) was dissolved in a mixed solution of 10 mL dichloromethane and 10 mL trifluoroacetic acid. The mixture was stirred for 24 hours. The reaction solution was washed with water, and the solvent was removed from the organic phase under reduced pressure. Column chromatography was used to separate the compound into a yellow solid of 33 mg, with a yield of 90%. The product was identified by NMR as compound 11 [Chem.-Asian J. 2019, 14, 1106]. NMR spectral data: 1H NMR(400MHz, CDCl3)δ9.30(s,2H),9.25(s,2H),9.18(s,2H),9.03(s,2H),8.88(d,J= 8.0Hz,2H),8.73(d,J=8.0Hz,2H),7.88(t,J=8.0Hz,2H),1.89(s,18H),1.80(s,18H); 13 C10 NMR (151MHz, CDCl3) δ 148.7, 148.5, 130.4, 130.3, 130.0, 130.0, 129.8, 129.8, 126.0, 124.9, 123.7, 123.3, 121.3, 121.3, 120.2, 120.2, 120.1, 118.8, 118.7, 118.7, 118.6, 35.7, 35.6, 32.1, 32.0. (See attached 1H NMR spectrum.) Figure 6 .

[0062] Example 10

[0063] Removal reaction of compound 4 under acidic conditions:

[0064]

[0065] Compound 4 (40 mg) was dissolved in a mixed solution of 10 mL dichloromethane and 10 mL trifluoromethanesulfonic acid. The mixture was stirred for 24 hours. The reaction solution was washed with water, and the solvent was removed from the organic phase under reduced pressure. Column chromatography was used to separate the compound into a yellow solid of 28 mg, with a yield of 70%. The product was identified by NMR as compound 11.

[0066] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principle of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A hexabenzocortin precursor compound, characterized in that: Inserting a group VIA element atom into the edge of a hexabenzo[a]methyl ether molecule results in a surface molecule comprising a seven-membered heterocycle and an incompletely cyclized molecule and its oxidation state compound, with the following structural formula: ， R1-R4 are tert-butyl substituents.

2. The hexabenzo[a]corona] precursor compound as described in claim 1, characterized in that: The hexabenzo[a]corona] precursor compounds are incompletely cyclized spirocyclic molecules and their oxidized compounds, with sulfur atoms inserted at the edges of the hexabenzo[a]corona] molecules. Their structural formulas are as follows: ； ； 。 3. The hexabenzo[a]corona] precursor compound as described in claim 1, characterized in that: The hexabenzo[a]corona] precursor compounds are molecules with incompletely cyclized spirocyclic structures and their oxidized compounds. Selenium atoms are inserted at the edges of the hexabenzo[a]corona] molecules, and their structural formulas are as follows: ； ； 。 4. The method for preparing a hexabenzo[a]corona] precursor compound according to claim 1, characterized in that: The synthesis steps include the following: (a) It reacts with 2,3,4,5-tetrachloro-1λ6-thiophene-1,1-dione or 2,3,4,5-tetrabromo-1λ6-thiophene-1,1-dione in a DA reaction to produce ; (b) The halogen site in the compound undergoes a Suzuki coupling reaction with phenylboronic acid compounds to form... ; (c) A ring-closing reaction occurs to generate compounds 1-9; (d) The compounds 1-9 are further oxidized to compounds 1o-9o.

5. The application of the hexabenzo[a]corona] precursor compound according to claim 1, characterized in that: The hexabenzo[a]corona] precursor compounds are heated to 100-250°C to remove the doped Group VIA elements, producing hexabenzo[a]corona molecules.

6. The application of the hexabenzo[a]corona] precursor compound according to claim 1, characterized in that: The hexabenzo[a]corona] precursor compounds, under acidic conditions, undergo the removal of Group VIA elements and further cyclization to produce hexabenzo[a]corona molecules.

7. The application of the hexabenzo[a]corona] precursor compound as described in claim 6, characterized in that: The acidic conditions are a solution containing at least one of trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

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