A chiral cyclo[8]isophenyl macrocyclic compound and its synthesis method

Abstract

The present invention relates to the technical field of organic chemistry, and in particular to a chiral cyclo[8]isobenzene macrocyclic compound and a synthesis method thereof. The specific technical scheme is: a synthesis method of a chiral cyclo[8]isobenzene macrocyclic compound, wherein compound 3 and NBS are reacted for 6 to 10 hours under light conditions with ethylene dichloride as a reaction solvent, and then anhydrous aluminum chloride and perylene are added, and the reaction is continued for 3 to 8 hours at room temperature under an argon atmosphere; the compound 3 is cyclo[8][1,3-(4,6-dimethyl)]-benzene. The present invention introduces a controllable number of planar units of the aromatic molecule-perylene into a fully carbon-hydrogen-rich carbon macrocyclic ring, thereby giving the entire structure a new property-chirality.

Description

Technical Field

[0001] The present invention relates to the technical field of organic chemistry, and in particular to a chiral cyclo[8]isobenzene macrocyclic compound and a synthesis method thereof. Background Art

[0002] Chiral cyclo[n]isophenyl macrocycles are a class of compounds with special structures and chiral properties, which have important research significance and application value in the fields of organic chemistry and materials science. With the continuous development of supramolecular chemistry in recent years, a number of chiral intercyclic carbon-rich macrocyclic molecules with novel structures and excellent functions have emerged, including a series of classic macrocyclic molecules such as catenane, crown ether, calixarene, imidazolate macrocycle, calixpyrrole, etc.; also include macrocyclic compounds with chiral properties and applications such as cycloparaben, triptycene macrocycle, helicene and super helicene, molecular tubes, carbon nanobelts and carbon nanorings that have emerged in recent years. These macrocyclic molecules have demonstrated their unique research value and broad application prospects in the fields of molecular recognition and assembly, molecular machine construction, material synthesis and application, environmental ecological protection, biomedical research, etc. Their asymmetric structure and chiral characteristics make them an ideal model for studying phenomena such as chiral recognition, chiral transfer and chiral separation. However, the current synthesis of these structurally specific carbon-rich macrocycles often faces difficulties such as multi-step reactions, the addition of a large number of reaction reagents and the scarcity of synthetic routes. Summary of the invention

[0003] In view of the shortcomings of the prior art, the present invention provides a chiral cyclo[8]isophenyl macrocyclic compound and a method for synthesizing the same, which solves the problem in the prior art that the number of polyaromatic ring planar units cannot be successfully introduced into a fully carbon-hydrogen-rich carbon structure.

[0004] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0005] The present invention discloses a chiral cyclo[8]isophenyl macrocyclic compound, the structural formula of which is as follows:

[0006] .

[0007] Correspondingly, a method for synthesizing the above compound comprises reacting compound 3 and NBS with dichloroethane as a reaction solvent under light conditions for 6 to 10 hours, adding anhydrous aluminum chloride and perylene, and continuing the reaction at room temperature for 3 to 8 hours under an argon atmosphere to obtain the compound;

[0008] The compound 3 is cyclo[8][1,3-(4,6-dimethyl)]-benzene.

[0009] Preferably, the equivalent ratio of the compound 3 to NBS is 0.5-3:0.2-2, and the equivalent ratio of the aluminum chloride to perylene is 1-3:0.5-3.

[0010] Preferably, the synthesis process of the compound 3 is as follows: under argon protection, reacting the reaction raw materials 1 and 2 with a palladium catalyst and a base in a solvent at a temperature of 80 to 120° C. for 20 to 32 hours to obtain compound 3;

[0011] The structures of the raw material 1 and the raw material 2 are respectively:

[0012] , .

[0013] Preferably, the equivalent ratio of the raw material 1 to the raw material 2 is 0.5-3:1-3.5, the amount of the palladium catalyst is 0.002-0.100 equivalents, and the amount of the base is 5-15.00 equivalents.

[0014] Preferably, the palladium catalyst is any one of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, tetrakistriphenylphosphine palladium, palladium acetate, tris(dibenzylideneacetone)dipalladium, and palladium chloride; the base is any one of cesium carbonate, potassium carbonate, potassium acetate, sodium hydroxide, sodium tert-butoxide, cesium fluoride, and sodium fluoride; and the solvent is any one of dioxane, N,N-dimethylformamide, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran.

[0015] Preferably, the synthesis process of the raw material 1 is:

[0016] (1) 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane), 1,5-dibromo-2,4-dimethylbenzene and potassium carbonate were mixed with a mixed solvent of tetrahydrofuran / water, and reacted at 80°C for 24 hours under argon protection to obtain 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl;

[0017] (2) Mix 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl with Pd(dppf)2Cl2•CH2Cl2, potassium acetate and diboric acid pinacol ester, use argon as reaction gas and dioxane as reaction solvent, and react at 100°C for 24 hours to obtain the product.

[0018] Preferably, in step (1), the amount of 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) is 0.05 to 2.50 equivalents, the amount of 1,5-dibromo-2,4-xylene is 0.05 to 2.50 equivalents, and the amount of potassium carbonate is 2.00 to 7.50 equivalents;

[0019] In step (2), the amount of 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl is 0.05 to 2.50 equivalents, the amount of Pd(dppf)2Cl2•CH2Cl2 is 0.02 to 0.10 equivalents, the amount of potassium acetate is 2.00 to 4.50 equivalents, and the amount of pinacol diboron is 1.00 to 3.00 equivalents.

[0020] Preferably, the synthesis process of the raw material 2 is:

[0021] (1) Mixing raw material 1, [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, potassium acetate and diboric acid pinacol ester with dioxane as solvent, reacting at 100°C for 30 hours under argon protection to obtain 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane);

[0022] (2) 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane), raw material 1, potassium carbonate and a mixed solvent of tetrahydrofuran / water were mixed, and the mixture was reacted at 80°C for 24 hours under argon protection to obtain the product.

[0023] Preferably, in step (1), the amount of the raw material 1 is 0.05 to 2.50 equivalents, the amount of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 0.002 to 0.50 equivalents, the amount of potassium acetate is 2.00 to 4.50 equivalents, and the amount of biboric acid pinacol ester is 1.00 to 3.00 equivalents;

[0024] In step (2), the amount of 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) is 0.05 to 2.50 equivalents, the amount of raw material 1 is 0.05 to 2.50 equivalents, and the amount of potassium carbonate is 2.00 to 7.00 equivalents.

[0025] The present invention has the following beneficial effects:

[0026] The present invention designs and constructs an intrinsically chiral macrocyclic compound, and studies its structural composition and possible chemical properties. First, cyclo[8][1,3-(4,6-dimethyl)]-benzene (CDMB-8) is obtained by a fragment coupling method. On this basis, after a halogenation reaction with N-bromosuccinimide (NBS) under light conditions, it continues to undergo a Friedel-Crafts alkylation reaction with perylene under the action of anhydrous aluminum chloride, successfully introducing the planar perylene into the macrocyclic skeleton to obtain a stable chiral cyclo[8]isobenzene intrinsically chiral compound (CDMB-8-Py). The structure and properties of the synthesized macrocyclic compound are confirmed and preliminarily explored by characterization methods such as nuclear magnetic hydrogen spectrum, carbon spectrum, 2D nuclear magnetic spectrum (including variable temperature ¹H, NOESY, COSY), high-resolution mass spectrometry, ultraviolet-visible spectrum and fluorescence spectrum. The conversion of the synthesized macrocyclic diastereomers is achieved by high temperature. It is hoped that based on the inherent chiral characteristics of the synthesized cyclo[8]isophenyl chiral compounds, chiral binding with tetrahydropyrrolopyrrolidine backbone molecules can be achieved, and then a chiral host-guest composite material can be developed. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The H NMR spectrum of CDMB-8-Py (500 MHz, TCE- d 2,363 K);

[0028] Figure 2 The NMR spectrum of CDMB-8-Py (500 MHz, TCE- d 2, 363 K);

[0029] Figure 3 The COSY spectrum of CDMB-8-Py (a);

[0030] Figure 4 for Figure 3 The enlarged image of the part (the red box in a) (b) (500 MHz, TCE- d 2,363 K);

[0031] Figure 5 The NOESY spectrum of CDMB-8-Py (a);

[0032] Figure 6 for Figure 5 Enlarged view of the local part (the red box part in a) (b) (500 MHz, TCE-d2, 363 K);

[0033] Figure 7 The full picture of MALDI-TOF high-resolution mass spectrum of CDMB-8-Py (a);

[0034] Figure 8is the isotope expansion diagram of CDMB-8-Py (b);

[0035] Fig. 9 CDMB-8-Py n-hexane solution (2×10 -5 M) UV-Visible spectrum;

[0036] Fig.10 CDMB-8-Py(2×10 -5 M) fluorescence excitation spectrum (a) and fluorescence emission spectrum (b) (λ ex =375nm;λ em =470 nm, the width of the exit / entry slits are both 5 nm);

[0037] Fig.11 For raw material 1 1 H NMR (400 MHz, CDCl3, 273 K);

[0038] Fig.12 For raw material 2 1 H NMR (400 MHz, CDCl3, 273 K);

[0039] Fig.13 For CDMB-8 1 H NMR (400 MHz, CDCl3, 273 K). DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0042] 1. The present invention discloses a chiral cyclo[8]isophenyl macrocyclic compound, the structural formula of which is as follows:

[0043] .

[0044] 2. The present invention discloses a method for synthesizing the above-mentioned compound, which is specifically: after reacting compound 3 and NBS with dichloroethane as a reaction solvent under light conditions for 6 to 10 hours, anhydrous aluminum chloride and perylene are added, and the reaction is continued for 3 to 8 hours at room temperature under an argon atmosphere to obtain the compound;

[0045] The compound 3 is cyclo[8][1,3-(4,6-dimethyl)]-benzene, and has the structural formula:

[0046] .

[0047] Among them, the equivalent ratio of the compound 3 to NBS is 0.5-3:0.2-2, and the equivalent ratio of the aluminum chloride to perylene is 1-3:0.5-3.

[0048] Furthermore, the synthesis process of the compound 3 is as follows: under argon protection, reacting the reaction raw materials 1 and 2 with a palladium catalyst and a base in a solvent at a temperature of 80 to 120° C. for 20 to 32 hours to obtain compound 3;

[0049] The structures of the raw material 1 and the raw material 2 are respectively:

[0050] , .

[0051] The equivalent ratio of the raw material 1 to the raw material 2 is 0.5-3:1-3.5, the amount of the palladium catalyst is 0.002-0.100 equivalents, and the amount of the base is 5-15.00 equivalents.

[0052] Further, the palladium catalyst is any one of [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium ([Pd(dppf)2Cl2•CH2Cl2]), tetrakistriphenylphosphine palladium (Pd[(PPh3)]4), palladium acetate (Pd(OAc)2), tris(dibenzylideneacetone) dipalladium (Pd2(dba)3), and palladium chloride (PdCl2), and the base is cesium carbonate (Cs2CO3), potassium carbonate (K2CO3), potassium acetate (CH3COOK), sodium hydroxide, sodium tert-butoxide ( t The solvent is any one of dioxane (C4H8O2), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene, acetonitrile (CH3CN), and tetrahydrofuran (THF).

[0053] Further, the synthesis process of the raw material 1 is:

[0054] (1) 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane), 1,5-dibromo-2,4-xylene and potassium carbonate were mixed with a mixed solvent of tetrahydrofuran / water, and reacted at 80°C for 24 hours under argon protection to obtain 5,5''-dibromo-2,2'',4,4'',4'',6'-hexahydrofuran Methyl-1,1':3',1''-terphenyl; the amount of 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) is 0.05 to 2.50 equivalents, the amount of 1,5-dibromo-2,4-xylene is 0.05 to 2.50 equivalents, and the amount of potassium carbonate is 2.00 to 7.50 equivalents.

[0055] (2) 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl is mixed with Pd(dppf)2Cl2•CH2Cl2, potassium acetate and diboric acid pinacol ester, and reacted at 100°C for 24 hours using argon as reaction gas and dioxane as reaction solvent. The amount of 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl is 0.05 to 2.50 equivalents, the amount of Pd(dppf)2Cl2•CH2Cl2 is 0.02 to 0.10 equivalents, the amount of potassium acetate is 2.00 to 4.50 equivalents, and the amount of diboric acid pinacol ester is 1.00 to 3.00 equivalents.

[0056] Further, the synthesis process of the raw material 2 is:

[0057] (1) After mixing the raw material 1, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, potassium acetate and biboric acid pinacol ester with a solvent of dioxane, the mixture is reacted at 100°C for 30 hours under argon protection to obtain 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane); the amount of the raw material 1 is 0.05 to 2.50 equivalents, the amount of the [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride is 0.002 to 0.50 equivalents, the amount of the potassium acetate is 2.00 to 4.50 equivalents, and the amount of the biboric acid pinacol ester is 1.00 to 3.00 equivalents;

[0058] (2) After mixing 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane), raw material 1, potassium carbonate and a mixed solvent of tetrahydrofuran / water, the mixture is reacted at 80°C for 24 hours under argon protection to obtain the product. The amount of 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) is 0.05 to 2.50 equivalents, the amount of raw material 1 is 0.05 to 2.50 equivalents, and the amount of potassium carbonate is 2.00 to 7.00 equivalents.

[0059] The present invention will be further described below in conjunction with specific embodiments.

[0060] Example 1 Synthesis of Compound 3

[0061] 1. Using 2,2'-(4,4',4'',6,6',6''-hexamethyl-[1,1':3',1''-terphenyl]-3,3''-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) (1) and 5,5''''-dibromo-2,2'''',4,4',4'',4''',4'''',6',6'',6'''-decamethyl-1,1':3',1'':3'',1''':3''',1''''-pentaphenyl (2) as reaction substrates, CDMB-8 (cyclo[8][1,3-(4,6-dimethyl)]-benzene), i.e., compound 3. The synthetic route is:

[0062]

[0063] The specific synthesis process is as follows: Add reaction material 1, raw material 2, palladium catalyst, base and reaction solvent to a 15mL Schlenk tube. Under argon protection, the temperature is 100°C and the reaction time is 24 hours. After the reaction is completed, cool to room temperature. After rotary evaporation to remove toluene, wash with dichloromethane (15mL×3) and distilled water (15mL×3). After vacuum concentrating the organic phase, use eluent ethyl acetate and petroleum ether (1 / 4, v / v ) was subjected to silica gel (200-300 mesh) column chromatography to obtain compound 3 (white solid).

[0064] 2. Effect of palladium catalyst type on the reaction

[0065] The experiment was carried out according to the above synthesis process, and the results are shown in Table 1. The specific reaction conditions are: raw material 1 (0.30 g, 0.44 mmol, 1.00 equiv.), raw material 2 (0.25 g, 0.44 mmol, 1.00 equiv.), [Pd] (0.044 mmol%, 0.010 equiv.), cesium carbonate (1.40 g, 4.40 mmol, 10.00 equiv.), acetonitrile (2.00 mL), argon, 100° C., 24 h, and silica gel column chromatography.

[0066] Table 1 Effect of palladium catalyst type

[0067] Serial number Palladium catalyst Yield (%) 1 <![CDATA[Pd(dppf)2Cl2•CH2Cl2]]> 13 2 <![CDATA[Pd[(PPh3)]4]]> <5 3 <![CDATA[Pd(OAc)2]]> <5 4 <![CDATA[Pd2(dba)3]]> 9 5 <![CDATA[PdCl2]]> ND

[0068] 3. According to Table 1, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride was selected as the reaction catalyst to investigate the effect of the type of base on the reaction. The results are shown in Table 2. The specific reaction conditions are: raw material 1 (0.30 g, 0.44 mmol, 1.00 equiv.), raw material 2 (0.25 g, 0.44 mmol, 1.00 equiv.), Pd(dppf)2Cl2•CH2Cl2 (35.00 mg, 0.044 mmol, 0.010 equiv.), base (4.4 mmol, 10 equiv.), acetonitrile (2.00 mL), argon, 100°C, 24 h. Silica gel column chromatography separation.

[0069] Table 2 Effect of alkali type

[0070] Serial number Alkali Yield (%) 1 <![CDATA[Cs2CO3]]> 17 2 <![CDATA[K2CO3]]> 10 3 <![CDATA[CH3COOK]]> 8 4 NaOH <5 5 <![CDATA[ t Good]]> <5 6 Cf 12 7 NaF <5

[0071] 4. According to Table 2, cesium carbonate was selected as the base, and the effect of the type of solvent on the reaction was investigated. The results are shown in Table 3. The specific reaction conditions are: raw material 1 (0.30 g, 0.44 mmol, 1.00 equiv.), raw material 2 (0.25 g, 0.44 mmol, 1.00 equiv.), Pd(dppf)2Cl2•CH2Cl2 (35.0 mg, 0.044 mmol, 0.010 equiv.), cesium carbonate (1.40 g, 4.40 mmol, 10.00 equiv.), solvent (2.00 mL), argon, 100°C, 24 h. Silica gel column chromatography separation.

[0072] Table 3 Effect of solvent type on reaction

[0073] Serial number Solvents Yield (%) 1 THF 6 2 Toluene 23 3 Dioxane <5 4 <![CDATA[CH3CN]]> 15 5 DMF <5 6 DMSO <5

[0074] 5. Based on the above optimal conditions, the best reaction is as follows:

[0075] To a 15mL Schlenk tube, add reaction material 1 (0.30g, 0.44mmol, 1.00equiv.), raw material 2 (0.38g, 1.50mmol, 1.50equiv.), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (35.00mg, 0.044mmol, 0.010equiv.) and cesium carbonate (1.40g, 4.40mmol, 10.00equiv.), and the reaction solvent is toluene (2.00mL). Under argon protection, the temperature is 100°C and the reaction time is 24 hours. After the reaction is completed, cool to room temperature. After removing toluene by rotary evaporation, wash with dichloromethane (15mL×3) and distilled water (15mL×3). After vacuum concentration of the organic phase, eluent ethyl acetate and petroleum ether (1 / 4, v / v ) was subjected to silica gel (200-300 mesh) column chromatography to obtain compound 3 (white solid, 80.5 mg, 22%). Its nuclear magnetic resonance spectrum is Fig.13 shown.

[0076] The NMR data are: 1 H NMR (400 MHz, CDCl3, 273 K) δ (ppm): 2.52 (s, 3H), 6.08 (s, 2H), 6.04 – 6.03 (m, 4H), 5.95 (s, 1H), 5.91 – 5.89 (m, 3H), 5.83 (s, 2H), 5.75 (s, 1H), 1.17 (s, 5H), 1.13 (s, 11H), 1.09–1.06 (m, 22H), 1.01 (s, 10H).

[0077] Example 2 Synthesis of target compound

[0078] 14-[(6b,10-dihydroperylene-2-yl)methyl]-1 6 ,2 4 ,2 6 ,3 4 ,3 6 ,4 4 ,4 6 ,5 4 ,5 6 ,6 4 ,6 6 ,7 4 ,7 6 ,8 4 ,8 6 The specific synthesis route of -pentadecamethyl-1,2,3,4,5,6,7,8(1,3)-octaphenylcyclooctane (CDMB-8-Py,4) is as follows:

[0079]

[0080] The specific synthesis process is as follows: Compound 3 (83.2 mg, 0.10 mmol, 1.00 equiv.) and NBS (8.90 mg, 0.050 mmol, 0.50 equiv.) were added to a 15 ml Schlenk tube, and dichloroethane (4.00 mL) was used as the reaction solvent. The reaction system was placed under light conditions for reaction for 8 hours. After the light source was turned off, the reaction system was cooled, and then anhydrous aluminum chloride (26.6 mg, 0.20 mmol, 2.00 equiv.) and perylene (25.2 mg, 0.10 mmol, 1.00 equiv.) were added to the system. The reaction system was replaced with argon three times, and the reaction was continued at room temperature for 5 hours. After the organic phase was concentrated in vacuo, CDMB-8-Py (yellow solid, 10.1 mg, <5%) was obtained by silica gel (200-300 mesh) column chromatography using cyclohexane as the eluent.

[0081] Example 3 Characterization of CDMB-8-Py

[0082] CDMB-8-Py was characterized by a series of methods including H NMR, C NMR, COSY, NOESY, H high-resolution mass spectrometry (MALDI-TOF), UV-visible spectroscopy and fluorescence spectroscopy. Figure 1 , Figure 2 As shown; COSY full spectrum and NOESY full spectrum are as shown Figure 3-Figure 6 As shown, according to a series of COSY and NOESY spectra, the hydrogen-hydrogen correlation and long-range carbon-hydrogen interactions of the CDMB-8-Py molecule are very strong.

[0083] MALDI-TOF high resolution mass spectrometer Figure 7 , Figure 8 As shown, the results show the signal peak of CDMB-8-Py (theoretical calculated value m / z = 1082.579, actual detected m / z = 1082.790).

[0084] UV-Visible spectroscopy Fig. 9 The fluorescence excitation spectrum is shown in Fig.10 The results show that the ultraviolet absorption peak of the macrocyclic molecule is between 300-400nm. The fluorescence luminescence performance is preliminarily characterized by fluorescence excitation and emission spectra, and it is found that the molecule has a maximum excitation peak at 375nm and a maximum emission peak at 470nm, which is consistent with the luminescence in the perylene molecule solution. This shows that the introduction of perylene molecules gives CDMB-8 specific optical properties.

[0085] The specific relevant results are as follows:

[0086] The information analysis of nuclear magnetic hydrogen spectrum, carbon spectrum and high-resolution mass spectrum is as follows: 1 H NMR (500 MHz, TCE- d 2, 363K) δ (ppm): 8.15-8.10 (m, 3H), 8.07 (d, J = 8.0 Hz, 1H), 7.70 (d, J = 8.5 Hz,1H), 7.65 (d, J = 7.5 Hz, 2H), 7.47 - 7.43 (m, 2H), 7.36 (t, J = 7.5 Hz, 1H),7.22 (d, J = 7.5 Hz, 1H), 7.09 - 7.08 (m, 6H), 7.06 (s, 1H), 7.00 (d, J = 9.5Hz, 2H), 6.94 (s, 1H), 6.91 (s, 1H), 6.82 – 6.80 (m, 5H), 4.15 (d, J = 5.5Hz, 2H), 2.15 (s, 2H), 2.12 (s, 1H), 2.08 - 2.06 (m, 30H), 2.04 (s, 6H), 1.97(s, 3H), 1.88 (s, 3H); 13 C NMR (125 MHz, TCE- d 2, 363 K) δ (ppm): 138.9, 138.4,138.2, 138.1, 138.0, 137.7, 136.0, 135.8, 134.3, 134.1, 134.0, 133.9, 133.7,133.6, 133.5, 133.0, 131.1, 131.0, 130.5, 130.4, 130.3, 130.1, 129.9, 129.8,129.8, 129.1, 128.6, 128.1, 127.8, 127.2, 126.9, 126.1, 126.1, 125.8, 123.9,119.7, 119.6, 119.4, 35.6, 29.1, 26.4, 18.7; MALDI-TOF HRMS ( m / z ): [M] +•calcd. for C 84 H 74 , 1082.579; found, 1082.790 (TCE- d 2 is deuterated tetrachloroethane).

[0087] Example 4 Synthesis of Raw Material 1

[0088] In a 250 mL three-necked flask, add 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) (2.685 g, 7.5 mmol, 1.00 equiv.), 1,5-dibromo-2,4-dimethylbenzene (1.965 g, 7.5 mmol, 1.00 equiv.) and potassium carbonate (5.175 g, 37.5 mmol, 5.00 equiv.), a mixed solvent of tetrahydrofuran / water (THF / H2O, 150 mL, 4 / 1, v / v ). Under argon protection, the reaction was carried out at 80°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature. After vacuum concentration, 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl was obtained by silica gel (200-300 mesh) column chromatography. Add 5,5''-dibromo-2,2'',4,4'',4'',6'-hexamethyl-1,1':3',1''-terphenyl (3.525 g, 7.5 mmol, 1.00 equiv.), Pd(dppf)2Cl2•CH2Cl2 (60.75 mg, 0.075 mmol, 0.01 equiv.), potassium acetate (2.94 g, 30 mmol, 3.20 equiv.) and biboric acid pinacol ester (2.85 g, 11.25 mmol, 1.50 equiv.) into a 250 mL three-necked flask. Use argon as the reaction gas and dioxane as the reaction solvent, and react at 100 °C for 24 hours. After the reaction is completed, cool to room temperature. Wash with dichloromethane (100 mL×3), then wash with distilled water (100 mL×3). After vacuum concentration, use petroleum ether / ethyl acetate (1 / 1, v / v ) as eluent for silica gel (200-300 mesh) column chromatography to obtain raw material 1 (white solid, 2.55 g, 60%). Its nuclear magnetic resonance spectrum is Fig.11 shown.

[0089] The NMR data are: 1 H NMR (400 MHz, CDCl3, 273 K) δ(ppm): 7.52 – 7.49 (m,2H), 7.10 – 7.04 (m, 3H), 6.81 (s, 1H), 2.52 (s, 6H), 2.08 – 2.04 (m, 10H), 1.53 (s, 3H), 1.30 (s, 23H).

[0090] Example 5 Synthesis of Raw Material 2

[0091] Add raw material 1 (100 g, 38 mmol, 1.00 equiv.), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (308.00 mg, 0.38 mmol, 0.010 equiv.), potassium acetate (15.68 g, 160 mmol, 3.20 equiv.) and biboric acid pinacol ester (14.48 g, 57 mmol, 1.50 equiv.) to a 2L three-necked flask. Under argon protection, the reaction temperature was 100 ° C, the solvent was dioxane, and the reaction was carried out for 30 hours. 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) was obtained. Then, 2,2'-(4,6-dimethyl-1,3-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) (3.58 g, 10 mmol, 1.00 equiv.), raw material 1 (2.62 g, 10 mmol, 1.00 equiv.), potassium carbonate (6.9 g, 50 mmol, 5.00 equiv.) were added to a 250 mL three-necked flask, and finally 200 mL of a mixed solvent of tetrahydrofuran / water (4 / 1, v / v ). Under argon protection, react at 80°C for 24 hours. After the reaction is completed, cool to room temperature. After removing tetrahydrofuran by rotary evaporation, wash with dichloromethane (50mL×3) and distilled water (50mL×3). After vacuum concentration, silica gel (200-300 mesh) column chromatography with petroleum ether as eluent is used to obtain raw material 2 (white solid, 452.0mg, 20%). Its nuclear magnetic resonance spectrum is Fig.12 shown.

[0092] The NMR data are: 1 H NMR (400 MHz, CDCl3, 273 K) δ (ppm):7.33 (d, J = 9.6Hz, 2H), 7.18 – 7.12 (m, 5H), 6.95 – 6.91(m, 1H), 6.87 (s, 2H), 2.42 – 2.40(m, 6H), 2.14 – 2.01 (m, 24H).

[0093] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A chiral cyclo[8]isophenyl macrocyclic compound, characterized in that: Its structural formula is as follows: 。 2. A method for synthesizing the compound according to claim 1, characterized in that: Compound 3 and NBS were reacted with dichloroethane as the reaction solvent under light conditions for 6 to 10 hours, the light source was turned off, anhydrous aluminum chloride and perylene were added after cooling, and the reaction was continued at room temperature under argon atmosphere for 3 to 8 hours to obtain the product; The compound 3 is cyclo[8][1,3-(4,6-dimethyl)]-benzene.

3. The method for synthesizing a chiral cyclo[8]isophenyl macrocyclic compound according to claim 2, characterized in that: The equivalent ratio of the compound 3 to NBS is 0.5-3:0.2-2, and the equivalent ratio of the aluminum chloride to perylene is 1-3:0.5-3.

4. The method for synthesizing a chiral cyclo[8]isophenyl macrocyclic compound according to claim 2, characterized in that: The synthesis process of the compound 3 is as follows: under argon protection, reacting the reaction raw materials 1 and 2 with a palladium catalyst and a base in a solvent at a temperature of 80 to 120° C. for 20 to 32 hours to obtain compound 3; the palladium catalyst is any one of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, tetrakistriphenylphosphine palladium, palladium acetate, and tris(dibenzylideneacetone)dipalladium; The structures of the raw material 1 and the raw material 2 are respectively: 、 。 5. The method for synthesizing a chiral cyclo[8]isophenyl macrocyclic compound according to claim 4, characterized in that: The equivalent ratio of the raw material 1 to the raw material 2 is 0.5-3:1-3.5, the amount of the palladium catalyst is 0.002-0.100 equivalents, and the amount of the base is 5-15.00 equivalents.

6. A method for synthesizing a chiral cyclo[8]isophenyl macrocyclic compound according to claim 4 or 5, characterized in that: The base is any one of cesium carbonate, potassium carbonate, potassium acetate, sodium hydroxide, sodium tert-butoxide, cesium fluoride, and sodium fluoride; the solvent is any one of dioxane, N,N-dimethylformamide, dimethyl sulfoxide, toluene, acetonitrile, and tetrahydrofuran.

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