A helical chiral multi-resonance thermally activated delayed luminescence material and its preparation method and application

Abstract

The present invention discloses a helical chiral thermal multiple resonance activated delayed luminescent material with narrow peak width emission, and its preparation method and application. The structural formula of the helical chiral multiple resonance thermally activated delayed luminescent material is shown in Formulas P1-P4 and M1-M4. The helical chiral multiple resonance thermally activated delayed luminescent material of the present invention can be used to prepare organic light-emitting diode devices, specifically as the light-emitting layer material of the device. The synthesis method of the CP-OLED light-emitting layer material based on the helical chiral helicene molecular skeleton of the present invention is simple, the product yield is high, and it can be prepared on a large scale; the organic film formed by the CP-OLED light-emitting layer material based on the helical chiral helicene molecular skeleton of the present invention has high surface smoothness, anti-oxidation and reduction properties, and high luminescence efficiency, and can be used as the light-emitting layer of an organic light-emitting diode. The organic light-emitting diode with an organic thin film layer formed by the CP-OLED light-emitting layer material based on the helical chiral helicene molecular skeleton as the light-emitting layer has the advantages of high efficiency, low driving voltage, high brightness and long life.

Description

Technical Field

[0001] The invention relates to a spiral chiral multiple resonance thermally activated delayed luminescent material and a preparation method and application thereof, belonging to the field of organic electroluminescent materials and devices. Background Art

[0002] Organic Light-Emitting Diode (OLED), also known as organic laser display or organic electroluminescence display (OLED), has significant application value in applications such as displays, lighting, automotive taillights, and healthcare. It has already achieved industrialization in these areas. With the large-scale application of OLED technology, the demand for OLED functional materials is also growing. In OLED devices, under the influence of an electric field, holes generated at the anode and electrons generated at the cathode migrate, injecting into the hole transport layer and electron transport layer, respectively, and then migrating to the light-emitting layer. When the two interact in the light-emitting layer, energetic excitons are generated, which excite luminescent molecules and ultimately produce visible light. Therefore, the material of the light-emitting layer plays a crucial role in device performance. Circularly polarized (CP) light has attracted considerable attention due to its potential applications in optical spintronics, such as optical quantum information, optical data storage, displays, chiral sensing, and bioreaction imaging. In traditional OLED devices, CP light is captured through a filter, which can result in a brightness loss of up to 50%.

[0003] Using chiral thermally activated delayed fluorescence (CP-TADF) as the light-emitting layer can generate electro-circularly polarized light while ensuring 100% exciton utilization. OLED devices based on CP-TADF offer advantages such as long device life, excellent stability, and high efficiency. Therefore, the design and preparation of high-performance CP-TADF materials with inexpensive raw materials, simple reaction conditions, and easy purification have significant application implications. Summary of the Invention

[0004] The purpose of the present invention is to provide a helical chiral multiple resonance thermally activated delayed luminescent material and its preparation method and application. The compound provided by the present invention is a helical chiral helicene skeleton material. The organic light-emitting diode formed by the organic thin film layer as the light-emitting layer has the advantages of high efficiency, low driving voltage, high brightness and long life.

[0005] The structural formula of the helical chiral multiple resonance thermally activated delayed luminescence material provided by the present invention is shown in Formula P1-P4 or M1-M4:

[0006]

[0007] In formulas P1-P4 and M1-M4, the group R represents a C1-C12 alkane or a C6-C12 aromatic hydrocarbon;

[0008] Specifically, the groups R are all dehydrogenated groups selected from at least one of benzene, toluene, tert-butylbenzene, isopropylbenzene, diphenylamine, cyano, trifluoromethyl, methoxy and derivatives thereof.

[0009] In the present invention, the structure of the group R is specifically as follows:

[0010]

[0011] The helical chiral multiple resonance thermally activated delayed luminescent material provided by the present invention is specifically any one of the formulas P-A01 to P-A18, P-B01 to P-B18, P-C01 to P-C18, P-D01 to P-D18, M-A01 to M-A18, M-B01 to M-B18, M-C01 to M-C18, and M-D01 to M-D18:

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020] Wherein, the groups represented by R1-R4 are shown as follows:

[0021]

[0022] The present invention also provides a method for preparing the helical chiral multiple resonance thermally activated delayed luminescent material, comprising the following steps:

[0023] S1. The compound represented by formula A is subjected to a Suzuki coupling reaction with the compound represented by formula B to obtain a compound represented by formula C;

[0024] S2, the compound represented by formula C is subjected to Scholl coupling reaction to obtain;

[0025]

[0026] Wherein, R is defined the same as in Formulas P1-P4 or M1-M4.

[0027] In the above preparation method, in step S1, the Suzuki coupling reaction is carried out in the presence of Pd(PPh3)4 and potassium carbonate;

[0028] The molar ratio of Pd(PPh3)4 to the compound represented by formula B is 0.02-0.1:1, specifically 0.02:1;

[0029] The molar ratio of potassium carbonate to the compound represented by formula B is 5 to 7:1, specifically 6:1;

[0030] The molar ratio of the compound represented by formula B to the compound represented by formula A is 1:2.2 to 2.4, specifically 1:2.2;

[0031] The solvent used in the Suzuki coupling reaction is a mixed solvent of toluene / ethanol / water with a mixing ratio of 2:1:1;

[0032] The temperature of the Suzuki coupling reaction is 80-100° C., and the reaction time is 12-24 hours, specifically 85° C. for 16 hours.

[0033] In the above preparation method, in step S2, the Scholl coupling reaction is carried out under the conditions of anhydrous ferric chloride and nitromethane;

[0034] The molar ratio of the anhydrous ferric chloride to the compound represented by formula C is 10 to 30:1, specifically 10:1;

[0035] The amount of nitromethane used is 5 to 20 ml per millimole of the compound represented by formula C, specifically 5 ml per millimole of the compound represented by formula C;

[0036] The solvent used in the Scholl coupling reaction is anhydrous DCM;

[0037] The Scholl coupling reaction is carried out at a temperature of 0 to 30° C. for 12 to 20 hours, and specifically at 25° C. for 16 hours.

[0038] The helical chiral multiple resonance thermally activated delayed luminescence material provided by the present invention can be used to prepare an organic light emitting diode device, specifically as a light emitting layer material of the device.

[0039] Based on the helical chiral multiple resonance thermally activated delayed luminescence material, the present invention further provides an organic light emitting diode device, wherein the material used in the light emitting layer includes the helical chiral multiple resonance thermally activated delayed luminescence material.

[0040] The structure of the organic light-emitting diode is as follows: the electron injection layer is composed of HAT-CN, the electron transport layer is composed of TAPC and TCTA, the blocking layer is composed of mCBP and PO-T2T, the electron transport layer is composed of ANT-BIZ, the electron injection layer is composed of Liq, and all of these are well known in the prior art; and the light-emitting layer is composed of a host DMIC-TRZ (or common hosts such as 3,5DCzPPy, DPEPO, etc.) and a compound represented by any of P1-P4 or M1-M4 in the present invention.

[0041] The present invention has the following beneficial technical effects:

[0042] (1) The synthesis method of the CP-OLED light-emitting layer material based on the helical chiral helicene skeleton of the present invention is simple, has a high product yield, and can be prepared on a large scale.

[0043] (2) The CP-OLED light-emitting layer material based on the helical chiral helicene skeleton of the present invention has a wide range of applications and can be applied to all common yellow light, green light, and red light CP-OLEDs.

[0044] (3) The organic film formed by the CP-OLED light-emitting layer material based on the helical chiral helicene skeleton of the present invention has high surface smoothness, anti-oxidation and reduction properties, and high luminescence efficiency, and can be used as the light-emitting layer of an organic light-emitting diode.

[0045] (4) Organic light-emitting diodes with an organic thin film layer formed by a CP-OLED light-emitting layer material based on a helical chiral helicene skeleton as the light-emitting layer have the advantages of high efficiency, low driving voltage, high brightness and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a schematic structural diagram of the organic light emitting diode prepared in the present invention. DETAILED DESCRIPTION

[0047] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0048] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0049] Example 1. Preparation of the compound represented by formula C-A01

[0050]

[0051] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 4.14 g (10 mmol) of compound A01, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene, ethanol, and water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 5.89 g of a pale yellow powder, C-A01, for a yield of 65%.

[0052] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 66 H 36 B2N4[M+H] + 908.37696, found 908.32605.

[0053] Example 2. Preparation of compounds represented by formula P-A01 and M-A01

[0054]

[0055] In an ice bath, 9.06 g (10 mmol) of compound C-A01, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane to afford 6.43 g of a pale yellow powder in a 71% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-A01 and M-A01.

[0056] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 66 H 34 B2N4[M+H] + 974.29696, found 974.30105.

[0057] Example 3. Preparation of the compound represented by formula C-A02

[0058]

[0059] In a glove box, a 500 mL double-necked round-bottom flask was charged with 4.70 g (10 mmol) of compound A02, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 6.31 g of a pale yellow powder, C-A02, for a yield of 65%.

[0060] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 52 B2N4[M+H] + 1018.42326, found 1016.40072.

[0061] Example 4. Preparation of compounds represented by formula P-A02 and M-A02

[0062]

[0063] In an ice bath, 10.1 g (10 mmol) of compound C-A02, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 8.08 g of a light yellow powder with a yield of 82%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A02 and M-A02.

[0064] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 50 B2N4[M+H] + 1016.42216, found 1016.40032.

[0065] Example 5. Preparation of the compound represented by formula C-A03

[0066]

[0067] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.38 g (10 mmol) of compound A03, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.48 g of a pale yellow powder, C-A03, for a yield of 70%.

[0068] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 98 H 100 B2N4[M+H] + 1354.74563, found 1354.60229

[0069] Example 6. Preparation of compounds of formula P-A03 and M-A03

[0070]

[0071] In an ice bath, 13.54 g (10 mmol) of compound C-A03, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 10.29 g of a light yellow powder in a 76% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A03 and M-A03.

[0072] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 98 H 98 B2N4[M+H] +1352.79663, found 1352.60129.

[0073] Example 7. Preparation of the compound represented by formula C-A04

[0074]

[0075] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 5.34 g (10 mmol) of compound A04, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.10 g of a pale yellow powder, C-A04, in a 62% yield.

[0076] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 52 B2N4O8[M+H] + 1146.37423, found 1146.13159.

[0077] Example 8. Preparation of compounds of formula P-A04 and M-A04

[0078]

[0079] In an ice bath, 11.46 g (10 mmol) of compound C-A04, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 8.02 g of a light yellow powder in a 70% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A04 and M-A04.

[0080] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C74 H 50 B2N4O8[M+H] + 1144.38123, found 1144.02159.

[0081] Example 9. Preparation of the compound represented by formula C-A05

[0082]

[0083] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.14 g (10 mmol) of compound A05, 7.26 g (22 mmol) of compound B-A, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.41 g of a pale yellow powder, C-A05, in a 67% yield.

[0084] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 28 B2N 12 [M+H] + 1106.27895, found 1106.03899.

[0085] Example 10. Preparation of compounds of formula P-A05 and M-A05

[0086]

[0087] In an ice bath, 11.06 g (10 mmol) of compound C-A05, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed by adding 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 5.97 g of a light yellow powder in a 54% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A05 and M-A05.

[0088] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 26 B2N 12 [M+H] + 1104.25895, found 1104.03659.

[0089] Example 11. Preparation of the compound represented by formula C-A06

[0090]

[0091] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.86 g (10 mmol) of compound A06, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.41 g of a pale yellow powder, C-A06, in a 58% yield.

[0092] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 28 B2F 24 N4[M+H] + 1450.48231, found 1450.03456.

[0093] Example 12. Preparation of compounds represented by formula P-A06 and M-A06

[0094]

[0095] In an ice bath, 14.50 g (10 mmol) of compound C-A06, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane as the eluent to afford 8.26 g of a pale yellow powder in a 57% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-A06 and M-A06.

[0096] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 26 B2F 24 N4[M+H] + 1448.48196, found 1448.01256.

[0097] Example 13: Preparation of the compound represented by formula C-A07

[0098]

[0099] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.82 g (10 mmol) of compound A07, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.32 g of a pale yellow powder, C-A07, in a 75% yield.

[0100] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 90 H 84 B2N4[M+H] + 1242.62319, found 1242.67534.

[0101] Example 14. Preparation of compounds represented by formula P-A07 and M-A07

[0102]

[0103] In an ice bath, 12.42 g (10 mmol) of compound C-A07, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed by adding 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane as the eluent to obtain 9.19 g of a light yellow powder in a 74% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A07 and M-A07.

[0104] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 90 H 82 B2N4[M+H] + 1240.67289, found 1240.40234.

[0105] Example 15. Preparation of the compound represented by formula C-A08

[0106]

[0107] In a glove box, a 500 mL double-necked round-bottom flask was charged with 10.82 g (10 mmol) of compound A08, 7.26 g (22 mmol) of compound B-A, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.66 g of a pale yellow powder, C-A01, in a 52% yield.

[0108] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 108 B2N 12 [M+H] +2242.82313, found 2242.96546.

[0109] Example 16. Preparation of compounds represented by formula P-A08 and M-A08

[0110]

[0111] To a 500mL double-necked round-bottom flask, 22.42g (10mmol) of compound C-A08, 16.2g (0.1mol) of anhydrous ferric chloride, 50ml of nitromethane, and 200ml of dichloromethane were added sequentially under an ice bath and allowed to react at room temperature for 16 hours. Extraction was then performed with 150ml of water and 100ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane as the eluent to afford 10.30g of a pale yellow powder in a 46% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-A08 and M-A08.

[0112] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 106 B2N 12 [M+H] + 2240.88493, found 2240.90156.

[0113] Example 17: Preparation of the compound represented by formula C-A09

[0114]

[0115] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.20 g (10 mmol) of compound A09, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.17 g of a pale yellow powder, C-A09, in a 54% yield.

[0116] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 114 H 68 B2N4[M+H] + 1516.53219, found 1516.12612.

[0117] Example 18. Preparation of compounds represented by formula P-A09 and M-A09

[0118]

[0119] In an ice bath, 15.14 g (10 mmol) of compound C-A09, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.62 g of a light yellow powder with a yield of 57%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-A09 and M-A09.

[0120] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 114 H 66 B2N4[M+H] + 1514.53489, found 1514.12694.

[0121] Example 19: Preparation of the compound represented by formula C-A10

[0122]

[0123] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.78 g (10 mmol) of compound A10, 7.26 g (22 mmol) of compound B-A, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.06 g of a pale yellow powder, C-A10, for a yield of 68%.

[0124] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 84 B2N4[M+H] + 1628.66127, found 1628.92306.

[0125] Example 20. Preparation of compounds represented by formula P-A10 and M-A10

[0126]

[0127] In an ice bath, 16.26 g (10 mmol) of compound C-A10, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.41 g of a light yellow powder with a yield of 64%. P-A10 and M-A10 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0128] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 82 B2N4[M+H] + 1626.66457, found 1626.98306.

[0129] Example 21. Preparation of the compound represented by formula C-A11

[0130]

[0131] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.44 g (10 mmol) of compound A11, 7.26 g (22 mmol) of compound B-A, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.58 g of a pale yellow powder, C-A11, in a 57% yield.

[0132] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 146 H 132 B2N4[M+H] + 1963.04578, found 1963.35629.

[0133] Example 22. Preparation of compounds represented by formula P-A11 and M-A11

[0134]

[0135] In an ice bath, compound C-A11 19.63g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 14.92g of a light yellow powder with a yield of 76%. P-A11 and M-A11 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0136] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 146 H 130 B2N4[M+H] + 1961.04278, found 1961.34589.

[0137] Example 23. Preparation of the compound represented by formula C-A12

[0138]

[0139] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.88 g (10 mmol) of compound A12, 7.26 g (22 mmol) of compound B-A, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.25 g of a pale yellow powder, C-A12, in a 57% yield.

[0140] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 210 H 140 B2N 12 [M+H] + 2851.12348, found 2851.075467.

[0141] Example 24. Preparation of compounds of formula P-A12 and M-A12

[0142]

[0143] In an ice bath, compound C-A12 28.51g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.11g of a light yellow powder with a yield of 53%. P-A12 and M-A12 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0144] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 210 H 138 B2N12 [M+H] + 2849.13698, found 2849.09867.

[0145] Example 25. Preparation of the compound represented by formula C-A13

[0146]

[0147] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.32 g (10 mmol) of compound A13, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.11 g of a pale yellow powder, C-A13, in a 54% yield.

[0148] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 122 H 60 B2F 23 N4[M+H] + 2058.44124, found 2059.01689.

[0149] Example 26. Preparation of compounds of formula P-A13 and M-A13

[0150]

[0151] In an ice bath, compound C-A13 20.58g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.22g of a light yellow powder with a yield of 74%. P-A13 and M-A13 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0152] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 122 H 58 B2F 23 N4[M+H] + 2056.44644, found 2057.03789.

[0153] Example 27, Preparation of the Compound of Formula C-A14

[0154]

[0155] In a glove box, a 500 mL double-necked round-bottom flask was charged with 8.20 g (10 mmol) of compound A14, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.14 g of a pale yellow powder, C-A14, in a 65% yield.

[0156] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 60 B2N 12 [M+H] + 1714.51735, found 1714.51675.

[0157] Example 28. Preparation of compounds represented by formula P-A14 and M-A14

[0158]

[0159] In an ice bath, compound C-A14 17.14g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 11.14g of a light yellow powder with a yield of 65%. P-A14 and M-A14 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0160] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 58 B2N 12 [M+H] + 1712.50935, found 1712.50935.

[0161] Example 29, Preparation of the Compound of Formula C-A15

[0162]

[0163] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.44 g (10 mmol) of compound A15, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 13.58 g of a pale yellow powder, C-A15, in a 53% yield.

[0164] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 86 H 140 B2N 12 [M+H] + 2563.13215, found 2562.91735.

[0165] Example 30, Preparation of compounds represented by formula P-A15 and M-A15

[0166]

[0167] In an ice bath, 25.61 g (10 mmol) of compound C-A15, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 17.41 g of a light yellow powder with a yield of 68%. P-A15 and M-A15 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0168] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 86 H 138 B2N 12 [M+H] + 2561.13515, found 2560.98335.

[0169] Example 31, Preparation of the Compound of Formula C-A16

[0170]

[0171] In a glove box, a 500 mL double-necked round-bottom flask was charged with 11.38 g (10 mmol) of compound A16, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 12.52 g of a pale yellow powder, C-A16, in a 52% yield.

[0172] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 92 B2N 12O8[M+H] + 2354.17129, found 2354.37239.

[0173] Example 32. Preparation of compounds of formula P-A16 and M-A16

[0174]

[0175] In an ice bath, 23.54 g (10 mmol) of compound C-A16, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.06 g of a light yellow powder with a yield of 64%. P-A16 and M-A16 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0176] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 12 O8[M+H] + 2352.17859, found 2352.37489.

[0177] Example 33. Preparation of the compound represented by formula C-A17

[0178]

[0179] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.08 g (10 mmol) of compound A17, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 14.15 g of a pale yellow powder, C-A17, in a 57% yield.

[0180] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 92 B2N 12 S8[M+H] + 2482.46267, found 2482.13123.

[0181] Example 34. Preparation of compounds represented by formula P-A17 and M-A17

[0182]

[0183] In an ice bath, 24.82 g (10 mmol) of compound C-A17, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.87 g of a light yellow powder with a yield of 68%. P-A17 and M-A17 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0184] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 12 S8[M+H] + 2480.46467, found 2480.13983.

[0185] Example 35. Preparation of the compound represented by formula C-A18

[0186]

[0187] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.96 g (10 mmol) of compound A18, 7.26 g (22 mmol) of compound BA, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.01 g of a pale yellow powder, C-A18, in a 56% yield.

[0188] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 92 B2N 12 Se8[M+H] + 2866.09123, found 2866.07543.

[0189] Example 36. Preparation of compounds of formula P-A18 and M-A18

[0190]

[0191] In an ice bath, 28.66 g (10 mmol) of compound C-A18, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 14.90 g of a light yellow powder with a yield of 54%. P-A18 and M-A18 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0192] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 12 Se8[M+H] + 2864.09654, found 2864.03783.

[0193] Example 37. Preparation of the compound represented by formula C-B01

[0194]

[0195] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 4.14 g (10 mmol) of compound A01, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene, ethanol, and water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 5.89 g of a pale yellow powder, C-B01, with a yield of 65%.

[0196] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 66 H 34 B2N6[M+H] + 908.37696, found 908.32605.

[0197] Example 38. Preparation of compounds represented by formula P-B01 and M-B01

[0198]

[0199] In an ice bath, 9.08 g (10 mmol) of compound C-B01, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 6.62 g of a light yellow powder with a yield of 73%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B01 and M-B01.

[0200] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 66 H 34 B2N6[M+H] +906.28120, found 906.10289.

[0201] Example 39, Preparation of the Compound of Formula C-B02

[0202]

[0203] In a glove box, a 500 mL double-necked round-bottom flask was charged with 4.70 g (10 mmol) of compound A02, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a toluene / ethanol / water (2:1:1) mixture. The mixture was reacted at 85°C for 16 hours. After heating and cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 6.31 g of a pale yellow powder, C-B02, for a yield of 65%.

[0204] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 50 B2N6[M+H] + 1018.42326, found 1016.40072.

[0205] Example 40. Preparation of compounds represented by formula P-B02 and M-B02

[0206]

[0207] In an ice bath, compound C-B02 10.20g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.56g of a light yellow powder with a yield of 84%. P-B02 and M-B02 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0208] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C74 H 50 B2N6[M+H] + 1018.41266, found 1018.41132.

[0209] Example 41, Preparation of the Compound of Formula C-B03

[0210]

[0211] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.38 g (10 mmol) of compound A03, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.48 g of a pale yellow powder, C-B03, for a yield of 70%.

[0212] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 98 B2N6[M+H] + 1356.78663, found 1356.61329.

[0213] Example 42, Preparation of compounds represented by formula P-B03 and M-B03

[0214]

[0215] In an ice bath, compound C-B03 13.56g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.17g of a light yellow powder with a yield of 75%. P-B03 and M-B03 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0216] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 96 B2N6[M+H] + 1354.78663, found 1354.61329.

[0217] Example 43: Preparation of the compound represented by formula C-B04

[0218]

[0219] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 5.34 g (10 mmol) of compound A04, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.10 g of a pale yellow powder, C-B04, in a 62% yield.

[0220] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 50 B2N6O8[M+H] + 1146.37423, found 1146.13159.

[0221] Example 44. Preparation of compounds represented by formula P-B04 and M-B04

[0222]

[0223] In an ice bath, compound C-B04 11.48g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.26g of a light yellow powder with a yield of 72%. P-B04 and M-B04 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0224] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 48 B2N6O8[M+H] + 1146.30123, found 1146.13159.

[0225] Example 45: Preparation of the compound represented by formula C-B05

[0226]

[0227] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 5.14 g (10 mmol) of compound A05, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.41 g of a pale yellow powder, C-B05, in a 67% yield.

[0228] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 26 B2N 14 [M+H] + 1104.25895, found 1104.03659.

[0229] Example 46. Preparation of compounds represented by formula P-B05 and M-B05

[0230]

[0231] In an ice bath, 11.08 g (10 mmol) of compound C-B05, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 5.98 g of a light yellow powder with a yield of 54%. P-B05 and M-B05 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0232] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 24 B2N 14 [M+H] + 1106.27895, found 1106.03559.

[0233] Example 47, Preparation of the Compound of Formula C-B06

[0234]

[0235] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.86 g (10 mmol) of compound A06, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.41 g of a pale yellow powder, C-B06, in a 58% yield.

[0236] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 26 B2F 24 N6[M+H] +1450.48231, found 1450.03456.

[0237] Example 48. Preparation of compounds represented by formula P-B06 and M-B06

[0238]

[0239] Under an ice bath, 14.52 g (10 mmol) of compound C-B06, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 8.56 g of a light yellow powder with a yield of 59%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B06 and M-B06.

[0240] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 74 H 24 B2F 24 N6[M+H] + 1450.44596, found 1450.014656.

[0241] Example 49, Preparation of the Compound of Formula C-A07

[0242]

[0243] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 5.82 g (10 mmol) of compound A07, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.32 g of a pale yellow powder, C-B07, in a 75% yield.

[0244] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 90 H 82 B2N6[M+H] + 1242.62319, found 1242.67534.

[0245] Example 50, Preparation of compounds represented by formula P-B07 and M-B07

[0246]

[0247] In an ice bath, 12.42 g (10 mmol) of compound C-B07, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 9.19 g of a light yellow powder with a yield of 74%. P-B07 and M-B07 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0248] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 90 H 80 B2N6[M+H] + 1240.67289, found 1240.40234.

[0249] Example 51, Preparation of the Compound of Formula C-B08

[0250]

[0251] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 10.82 g (10 mmol) of compound A08, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.66 g of a pale yellow powder, C-B01, in a 52% yield.

[0252] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 106 B2N 14 [M+H] + 2242.82313, found 2242.96546.

[0253] Example 52: Preparation of compounds represented by formula P-B08 and M-B08

[0254]

[0255] Under an ice bath, 22.44 g (10 mmol) of compound C-B08, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 10.09 g of a light yellow powder with a yield of 45%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B08 and M-B08.

[0256] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 106 B2N 14 [M+H] + 2242.6793, found 2242.71156.

[0257] Example 53: Preparation of the compound represented by formula C-B09

[0258]

[0259] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 7.20 g (10 mmol) of compound A09, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.17 g of a pale yellow powder, C-B09, in a 54% yield.

[0260] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 114 H 66 B2N6[M+H] + 1516.53219, found 1516.12612.

[0261] Example 54. Preparation of compounds represented by formula P-B09 and M-B09

[0262]

[0263] In an ice bath, 15.18 g (10 mmol) of compound C-B09, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.50 g of a light yellow powder with a yield of 57%. P-B09 and M-B09 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0264] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 114 H 66 B2N6[M+H] +1516.64489, found 1516.12694.

[0265] Example 55: Preparation of the compound represented by formula C-B10

[0266]

[0267] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.78 g (10 mmol) of compound A10, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.06 g of a pale yellow powder, C-B10, in a 68% yield.

[0268] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 82 B2N6[M+H] + 1628.66127, found 1628.92306.

[0269] Example 56. Preparation of compounds represented by formula P-B10 and M-B10

[0270]

[0271] Under an ice bath, 16.29 g (10 mmol) of compound C-B10, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.26 g of a light yellow powder with a yield of 63%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B10 and M-B10.

[0272] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C112 H 80 B2N6[M+H] + 1627.73457, found 1627.98306.

[0273] Example 57: Preparation of the compound represented by formula C-B11

[0274]

[0275] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.44 g (10 mmol) of compound A11, 7.30 g (22 mmol) of compound B-B, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.58 g of a pale yellow powder, C-B11, in a 57% yield.

[0276] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 146 H 130 B2N6[M+H] + 1963.04578, found 1963.35629.

[0277] Example 58. Preparation of compounds represented by formula P-B11 and M-B11

[0278]

[0279] In an ice bath, 19.64 g (10 mmol) of compound C-B11, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 14.73 g of a light yellow powder with a yield of 75%. P-B11 and M-B11 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0280] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 146 H 128 B2N6[M+H] + 1963.14278, found 1963.24589.

[0281] Example 59: Preparation of the compound represented by formula C-B12

[0282]

[0283] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.88 g (10 mmol) of compound A12, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.25 g of a pale yellow powder, C-A12, in a 57% yield.

[0284] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 210 H 138 B2N 14 [M+H] + 2851.12348, found 2851.075467.

[0285] Example 60, Preparation of Compounds of Formula P-B12 and M-B12

[0286]

[0287] In an ice bath, 28.52 g (10 mmol) of compound C-B12, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.54 g of a light yellow powder with a yield of 58%. P-B12 and M-B12 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0288] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 210 H 136 B2N 14 [M+H] + 2850.73698, found 2850.12867.

[0289] Example 61. Preparation of the compound represented by formula C-B13

[0290]

[0291] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.32 g (10 mmol) of compound A13, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.11 g of a pale yellow powder, C-B13, in a 54% yield.

[0292] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 122 H 58 B2F 23 N6[M+H] + 2058.44124, found 2059.01689.

[0293] Example 62, Preparation of compounds represented by formula P-B13 and M-B13

[0294]

[0295] In an ice bath, compound C-B13 20.60g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.03g of a light yellow powder with a yield of 73%. P-B13 and M-B13 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0296] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 122 H 56 B2F 23 N6[M+H] + 2057.34644, found 2057.05589.

[0297] Example 63. Preparation of the compound represented by formula C-B14

[0298]

[0299] In a glove box, a 500 mL double-necked round-bottom flask was charged with 8.20 g (10 mmol) of compound A14, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.14 g of a pale yellow powder, C-B14, in a 65% yield.

[0300] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 58 B2N14 [M+H] + 1714.51735, found 1714.51675.

[0301] Example 64. Preparation of compounds of formula P-B14 and M-B14

[0302]

[0303] In an ice bath, 17.16 g (10 mmol) of compound C-B14, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.64 g of a light yellow powder with a yield of 62%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B14 and M-B14.

[0304] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 56 B2N 14 [M+H] + 1714.30935, found 1714.55935.

[0305] Example 65: Preparation of the compound represented by formula C-B15

[0306]

[0307] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.44 g (10 mmol) of compound A15, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 13.58 g of a pale yellow powder, C-B15, in a 53% yield.

[0308] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 86 H 138 B2N 12 [M+H] + 2563.13215, found 2562.91735.

[0309] Example 66. Preparation of compounds represented by formula P-B15 and M-B15

[0310]

[0311] In an ice bath, 25.63 g (10 mmol) of compound C-B15, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.65 g of a light yellow powder with a yield of 65%. P-B15 and M-B15 were separated by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0312] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 86 H 136 B2N 12 [M+H] + 2563.02515, found 2562.88335.

[0313] Example 67, Preparation of the Compound of Formula C-B16

[0314]

[0315] In a glove box, a 500 mL double-necked round-bottom flask was charged with 11.38 g (10 mmol) of compound A16, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 12.52 g of a pale yellow powder, C-B16, in a 52% yield.

[0316] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 14 O8[M+H] + 2354.17129, found 2354.37239.

[0317] Example 68. Preparation of compounds represented by formula P-B16 and M-B16

[0318]

[0319] Under an ice bath, 23.55 g (10 mmol) of compound C-B16, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.07 g of a light yellow powder with a yield of 64%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-B16 and M-B16.

[0320] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 88 B2N 14 O8[M+H] + 2353.17859, found 2353.37489.

[0321] Example 69, Preparation of the Compound of Formula C-B17

[0322]

[0323] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.08 g (10 mmol) of compound A17, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 14.15 g of a pale yellow powder, C-B17, in a 57% yield.

[0324] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 14 S8[M+H] + 2482.46267, found 2482.13123.

[0325] Example 70, Preparation of compounds represented by formula P-B17 and M-B17

[0326]

[0327] In an ice bath, 24.83 g (10 mmol) of compound C-B17, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.88 g of a light yellow powder with a yield of 67%. P-B17 and M-B17 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0328] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 88 B2N14 S8[M+H] + 2481.46467, found 2481.13983.

[0329] Example 71. Preparation of the compound represented by formula C-B18

[0330]

[0331] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.96 g (10 mmol) of compound A18, 7.30 g (22 mmol) of compound BB, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.01 g of a pale yellow powder, C-B18, in a 56% yield.

[0332] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 90 B2N 14 Se8[M+H] + 2866.09123, found 2866.07543.

[0333] Example 72. Preparation of compounds represented by formula P-B18 and M-B18

[0334]

[0335] In an ice bath, 28.67 g (10 mmol) of compound C-B18, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 14.76 g of a light yellow powder with a yield of 53%. P-B18 and M-B18 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0336] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 162 H 88 B2N 14 Se8[M+H] + 2865.09654, found 2865.03783.

[0337] Example 73. Preparation of the compound represented by formula C-C01

[0338]

[0339] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 4.14 g (10 mmol) of compound A01, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene, ethanol, and water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 4.74 g of a pale yellow powder, C-C01, in a 53% yield.

[0340] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 64 H 35 B2N5[M+H] + 895.21296, found 895.31125.

[0341] Example 74. Preparation of compounds represented by formula P-C01 and M-C01

[0342]

[0343] In an ice bath, 8.93 g (10 mmol) of compound C-C01, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane to afford 6.34 g of a pale yellow powder in a 71% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-C01 and M-C01.

[0344] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 64 H 33 B2N5[M+H] + 893.29696, found 893.30105.

[0345] Example 75. Preparation of the compound represented by formula C-C02

[0346]

[0347] In a glove box, 4.70 g (10 mmol) of compound A02, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 ml of a mixed solvent of toluene / ethanol / water (2:1:1) were added to a 500 mL double-necked round-bottom flask and reacted at 85°C for 16 hours. After stopping heating and lowering the reaction to room temperature, 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (6:1) as the eluting solvent to obtain 6.31 g of a light yellow powder C-CO2 with a yield of 65%.

[0348] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 51 B2N5[M+H] + 1007.41216, found 1007.41452.

[0349] Example 76. Preparation of compounds represented by formula P-C02 and M-C02

[0350]

[0351] In an ice bath, compound C-CO2 10.06g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.13g of a light yellow powder with a yield of 83%. P-CO2 and M-CO2 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0352] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 49 B2N5[M+H] + 1005.42216, found 1005.40032.

[0353] Example 77, Preparation of the Compound of Formula C-C03

[0354]

[0355] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.38 g (10 mmol) of compound A03, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a mixed solvent of toluene / ethanol / water (2:1:1). The mixture was reacted at 85°C for 16 hours. After heating was stopped and the reaction mixture was cooled to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (6:1) as the eluting solvent to obtain 7.51 g of a light yellow powder C-C03, with a yield of 56%.

[0356] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 99 B2N5[M+H] + 1343.79123, found 1343.61229.

[0357] Example 78, Preparation of compounds represented by formula P-C03 and M-C03

[0358]

[0359] In an ice bath, compound C-CO3 13.43g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.13g of a light yellow powder with a yield of 75%. P-CO3 and M-CO3 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0360] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 97 B2N5[M+H] + 1341.79663, found 1341.60129.

[0361] Example 79, Preparation of the Compound of Formula C-C04

[0362]

[0363] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.34 g (10 mmol) of compound A04, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a toluene / ethanol / water (2:1:1) mixture. The mixture was reacted at 85°C for 16 hours. After heating and cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.15 g of a pale yellow powder, C-C04, in a 63% yield.

[0364] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 51 B2N5O8[M+H]+ 1135.38123, found 1135.02159.

[0365] Example 80, Preparation of compounds represented by formula P-C04 and M-C04

[0366]

[0367] In an ice bath, compound C-CO4 11.35g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.14g of a light yellow powder with a yield of 72%. P-CO4 and M-CO4 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0368] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 51 B2N5O8[M+H] + 1133.38123, found 1133.02159.

[0369] Example 81. Preparation of the compound represented by formula C-C05

[0370]

[0371] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.14 g (10 mmol) of compound A05, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After heating and cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.41 g of a pale yellow powder, C-C05, in a 67% yield.

[0372] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 27 B2N 13 [M+H] + 1095.25895, found 1095.03659.

[0373] Example 82. Preparation of compounds represented by formula P-C05 and M-C05

[0374]

[0375] In an ice bath, compound C-C05 10.95g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography with petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 5.95g of a light yellow powder with a yield of 54%. P-C05 and M-C05 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0376] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 25 B2N 13 [M+H] + 1093.25895, found 1093.03659.

[0377] Example 83. Preparation of the compound represented by formula C-C06

[0378]

[0379] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 6.86 g (10 mmol) of compound A06, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.41 g of a pale yellow powder, C-C06, in a 58% yield.

[0380] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 27 B2F 24 N7[M+H] + 1439.48196, found 1439.01256.

[0381] Example 84. Preparation of compounds of formula P-C06 and M-C06

[0382]

[0383] In an ice bath, 14.39 g (10 mmol) of compound C-C06, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.42 g of a light yellow powder with a yield of 59%. P-C06 and M-C06 were separated by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0384] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 25 B2F 24 N7[M+H] + 1437.48196, found 1437.01256.

[0385] Example 85. Preparation of the compound represented by formula C-C07

[0386]

[0387] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.82 g (10 mmol) of compound A07, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.32 g of a pale yellow powder, C-C07, in a 75% yield.

[0388] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 88 H 83 B2N5[M+H] + 1231.67289, found 1231.40234.

[0389] Example 86. Preparation of compounds represented by formula P-C07 and M-C07

[0390]

[0391] In an ice bath, 12.31 g (10 mmol) of compound C-C07, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 9.33 g of a light yellow powder with a yield of 76%. P-C07 and M-C07 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0392] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 88 H 81 B2N5[M+H] +1229.67289, found 1229.40234.

[0393] Example 87, Preparation of the Compound Represented by Formula C-C08

[0394]

[0395] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 10.82 g (10 mmol) of compound A08, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene, ethanol, and water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.66 g of a pale yellow powder, C-C01, in a 52% yield.

[0396] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 107 B2N 13 [M+H] + 2223.88493, found 2223.90156.

[0397] Example 88. Preparation of compounds represented by formula P-C08 and M-C08

[0398]

[0399] Under an ice bath, 22.23 g (10 mmol) of compound C-C08, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.15 g of a light yellow powder with a yield of 45%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-C08 and M-C08.

[0400] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 105 B2N 13 [M+H] + 2221.88493, found 2221.90156.

[0401] Example 89, Preparation of the Compound of Formula C-C09

[0402]

[0403] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 7.20 g (10 mmol) of compound A09, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.17 g of a pale yellow powder, C-C09, in a 54% yield.

[0404] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 67 B2N5[M+H] + 1505.53489, found 1505.12694.

[0405] Example 90, Preparation of Compounds of Formula P-C09 and M-C09

[0406]

[0407] In an ice bath, 15.05 g (10 mmol) of compound C-C09, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.61 g of a light yellow powder with a yield of 57%. P-C09 and M-C09 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0408] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 65 B2N5[M+H] + 1503.53489, found 1503.12694.

[0409] Example 91. Preparation of the compound represented by formula C-C10

[0410]

[0411] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.78 g (10 mmol) of compound A10, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.06 g of a pale yellow powder, C-C10, in a 68% yield.

[0412] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 110 H 83 B2N5[M+H] + 1617.66457, found 1617.98306.

[0413] Example 92. Preparation of compounds of formula P-C10 and M-C10

[0414]

[0415] In an ice bath, 16.17 g (10 mmol) of compound C-C10, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 10.55 g of a light yellow powder in a 65% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-C10 and M-C10.

[0416] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 110 H 81 B2N5[M+H] + 1615.66457, found 1615.98306.

[0417] Example 93: Preparation of the compound represented by formula C-C11

[0418]

[0419] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.44 g (10 mmol) of compound A11, 7.02 g (22 mmol) of compound B-C, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.58 g of a pale yellow powder, C-C11, in a 57% yield.

[0420] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 144 H 131 B2N5[M+H] + 1952.04278, found 1952.34589.

[0421] Example 94. Preparation of compounds of formula P-C11 and M-C11

[0422]

[0423] In an ice bath, 19.52 g (10 mmol) of compound C-C11, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 14.90 g of a light yellow powder in a yield of 76%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-C11 and M-C11.

[0424] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 144 H 131 B2N5[M+H] + 1950.04278, found 1950.34589.

[0425] Example 95: Preparation of the compound represented by formula C-C12

[0426]

[0427] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.88 g (10 mmol) of compound A12, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.25 g of a pale yellow powder, C-C12, in a 57% yield.

[0428] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 208 H 139 B2N 13[M+H] + 2840.13698, found 2840.09867.

[0429] Example 96. Preparation of compounds of formula P-C12 and M-C12

[0430]

[0431] In an ice bath, 28.40 g (10 mmol) of compound C-C12, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.23 g of a light yellow powder with a yield of 54%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-C12 and M-C12.

[0432] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 208 H 139 B2N 13 [M+H] + 2838.13698, found 2838.09867.

[0433] Example 97: Preparation of the compound represented by formula C-C13

[0434]

[0435] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.32 g (10 mmol) of compound A13, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.11 g of a pale yellow powder, C-C13, in a 54% yield.

[0436] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 59 B2F 23 N5[M+H] + 2047.44644, found 2048.03789.

[0437] Example 98. Preparation of compounds of formula P-C13 and M-A13

[0438]

[0439] In an ice bath, 20.47 g (10 mmol) of compound C-C13, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.44 g of a light yellow powder with a yield of 75%. P-C13 and M-C13 were separated by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0440] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 57 B2F 23 N5[M+H] + 2045.44644, found 2046.03789.

[0441] Example 99, Preparation of the Compound of Formula C-C14

[0442]

[0443] In a glove box, a 500 mL double-necked round-bottom flask was charged with 8.20 g (10 mmol) of compound A14, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.14 g of a pale yellow powder, C-C14, in a 65% yield.

[0444] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 118 H 59 B2N 13 [M+H] + 1703.50935, found 1703.50935.

[0445] Example 100, Preparation of Compounds of Formula P-C14 and M-C14

[0446]

[0447] In an ice bath, 17.03 g (10 mmol) of compound C-C14, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed by adding 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 11.14 g of a light yellow powder in a 65% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-C14 and M-C14.

[0448] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 118 H 57 B2N 13 [M+H] + 1701.50935, found 1701.50935.

[0449] Example 101. Preparation of the compound represented by formula C-C15

[0450]

[0451] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.44 g (10 mmol) of compound A15, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 13.58 g of a pale yellow powder, C-C15, in a 53% yield.

[0452] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H 139 B2N 11 [M+H] + 2552.13515, found 2551.98335.

[0453] Example 102, Preparation of Compounds of Formula P-C15 and M-C15

[0454]

[0455] In an ice bath, 25.52 g (10 mmol) of compound C-C15, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 17.64 g of a light yellow powder with a yield of 69%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-C15 and M-C15.

[0456] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H 137 B2N11 [M+H] + 2550.13515, found 2549.98335.

[0457] Example 103, Preparation of the Compound Represented by Formula C-C16

[0458]

[0459] In a glove box, a 500 mL double-necked round-bottom flask was charged with 11.38 g (10 mmol) of compound A16, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 12.52 g of a pale yellow powder, C-C16, in a 52% yield.

[0460] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 91 B2N 13 O8[M+H] + 2343.17859, found 2343.37489.

[0461] Example 104. Preparation of compounds of formula P-C16 and M-C16

[0462]

[0463] In an ice bath, 23.43 g (10 mmol) of compound C-C16, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 15.23 g of a light yellow powder in a 65% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-C16 and M-C16.

[0464] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 89 B2N 13 O8[M+H] + 2341.17859, found 2341.37489.

[0465] Example 105. Preparation of the compound represented by formula C-C17

[0466]

[0467] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.08 g (10 mmol) of compound A17, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 14.15 g of a pale yellow powder, C-C17, in a 57% yield.

[0468] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 91 B2N 13 S8[M+H] + 2471.46467, found 2471.13983.

[0469] Example 106. Preparation of compounds of formula P-C17 and M-C17

[0470]

[0471] In an ice bath, 24.71 g (10 mmol) of compound C-C17, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.73 g of a light yellow powder with a yield of 66%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-C17 and M-C17.

[0472] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 89 B2N 13 S8[M+H] + 2469.46467, found 2469.13983.

[0473] Example 107, Preparation of Compounds Represented by Formula C-C18

[0474]

[0475] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.96 g (10 mmol) of compound A18, 7.02 g (22 mmol) of compound BC, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.01 g of a pale yellow powder, C-C18, in a 56% yield.

[0476] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 91 B2N 13 Se8[M+H] + 2855.09654, found 2855.03783.

[0477] Example 108. Preparation of compounds of formula P-C18 and M-C18

[0478]

[0479] In an ice bath, 28.55 g (10 mmol) of compound C-C18, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 14.77 g of a light yellow powder in a 53% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-C18 and M-C18.

[0480] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 89 B2N 13 Se8[M+H] + 2853.09654, found 2853.03783.

[0481] Example 109, Preparation of the Compound of Formula C-D01

[0482]

[0483] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 4.14 g (10 mmol) of compound A01, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene, ethanol, and water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 4.74 g of a pale yellow powder, C-D01, in a 53% yield.

[0484] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 64 H 34 B2N4O[M+H]+ 896.21296, found 896.31125.

[0485] Example 110. Preparation of compounds represented by formula P-D01 and M-D01

[0486]

[0487] To a 500mL double-necked round-bottom flask, 8.93g (10mmol) of compound C-D01, 16.2g (0.1mol) of anhydrous ferric chloride, 50ml of nitromethane, and 200ml of dichloromethane were added sequentially under an ice bath and allowed to react at room temperature for 16 hours. Extraction was then performed with 150ml of water and 100ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 10:1 ratio of petroleum ether to dichloromethane to afford 6.34g of a pale yellow powder in a 71% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-D01 and M-D01.

[0488] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 64 H 32 B2N4O[M+H] + 894.29696, found 894.30105.

[0489] Example 111, Preparation of the Compound of Formula C-D02

[0490]

[0491] In a glove box, a 500 mL double-necked round-bottom flask was charged with 4.70 g (10 mmol) of compound A02, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a toluene / ethanol / water (2:1:1) mixture. The mixture was reacted at 85°C for 16 hours. After heating and cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 6.31 g of a pale yellow powder, C-D02, for a yield of 65%.

[0492] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 50 B2N4O[M+H] + 1008.41216, found 1008.41452.

[0493] Example 112, Preparation of Compounds of Formula P-D02 and M-D02

[0494]

[0495] In an ice bath, compound C-D02 10.06g (10mmol), anhydrous ferric chloride 16.2g (0.1mol), nitromethane 50ml and dichloromethane 200ml were added to a 500mL double-necked round-bottom flask in sequence and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added thereto for extraction. The organic phase after extraction was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.13g of a light yellow powder with a yield of 83%. P-D02 and M-D02 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0496] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 48 B2N4O[M+H] + 1006.42216, found 1006.40032.

[0497] Example 113, Preparation of the Compound of Formula C-D03

[0498]

[0499] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.38 g (10 mmol) of compound A03, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.51 g of a pale yellow powder, C-D03, in a 56% yield.

[0500] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 98 B2N4O[M+H] + 1344.79123, found 1344.61229.

[0501] Example 114, Preparation of compounds represented by formula P-D03 and M-D03

[0502]

[0503] In an ice bath, 13.43 g (10 mmol) of compound C-D03, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 10.13 g of a light yellow powder in a 75% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D03 and M-D03.

[0504] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 96 H 96 B2N4O[M+H] + 1342.79663, found 1342.60129.

[0505] Example 115, Preparation of the Compound of Formula C-D04

[0506]

[0507] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.34 g (10 mmol) of compound A04, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.15 g of a pale yellow powder, C-D04, in a 63% yield.

[0508] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 50 B2N4O9[M+H] + 1136.38123, found 1136.02159.

[0509] Example 116, Preparation of compounds represented by formula P-D04 and M-D04

[0510]

[0511] In an ice bath, 11.35 g (10 mmol) of compound C-D04, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.14 g of a light yellow powder with a yield of 72%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D04 and M-D04.

[0512] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 50 B2N4O9[M+H] + 1134.38123, found 1134.02159.

[0513] Example 117, Preparation of the Compound of Formula C-D05

[0514]

[0515] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.14 g (10 mmol) of compound A05, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 7.41 g of a pale yellow powder, C-D05, in a 67% yield.

[0516] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 26 B2N 12 O[M+H] + 1096.25895, found 1096.03659.

[0517] Example 118, Preparation of compounds represented by formula P-D05 and M-D05

[0518]

[0519] In an ice bath, 10.95 g (10 mmol) of compound C-D05, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 5.95 g of a light yellow powder in a 54% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D05 and M-D05.

[0520] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H24 B2N 12 O[M+H] + 1094.25895, found 1094.03659.

[0521] Example 119, Preparation of the Compound of Formula C-D06

[0522]

[0523] In a glove box, a 500 mL double-necked round-bottom flask was charged with 6.86 g (10 mmol) of compound A06, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.41 g of a pale yellow powder, C-D06, in a 58% yield.

[0524] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 26 B2F 24 N6O[M+H] + 1440.48196, found 1440.01256.

[0525] Example 120, Preparation of compounds represented by formula P-D06 and M-D06

[0526]

[0527] In an ice bath, 14.39 g (10 mmol) of compound C-D06, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 8.42 g of a light yellow powder in a 59% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-D06 and M-D06.

[0528] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 72 H 26 B2F 24 N6O[M+H] + 1437.48196, found 1437.01256.

[0529] Example 121, Preparation of the Compound of Formula C-D07

[0530]

[0531] In a glove box, a 500 mL double-necked round-bottom flask was charged with 5.82 g (10 mmol) of compound A07, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 9.32 g of a pale yellow powder, C-D07, in a 75% yield.

[0532] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 88 H 82 B2N4O[M+H] + 1232.67289, found 1232.40234.

[0533] Example 122, Preparation of compounds represented by formula P-D07 and M-D07

[0534]

[0535] In an ice bath, 12.31 g (10 mmol) of compound C-D07, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 9.33 g of a light yellow powder in a yield of 76%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D07 and M-D07.

[0536] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 88 H 80 B2N4O[M+H] + 1229.67289, found 1229.40234.

[0537] Example 123, Preparation of the Compound of Formula C-D08

[0538]

[0539] In a glove box, a 500-mL, double-necked round-bottom flask was charged with 10.82 g (10 mmol) of compound A08, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.66 g of a pale yellow powder, C-D01, in a 52% yield.

[0540] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 106 B2N 12 O[M+H] + 2224.88493, found 2224.90156.

[0541] Example 124. Preparation of compounds represented by formula P-D08 and M-D08

[0542]

[0543] Under an ice bath, 22.23 g (10 mmol) of compound C-D08, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was then performed with 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 10.15 g of a light yellow powder in a 45% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) yielded P-D08 and M-D08.

[0544] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 104 B2N 12 O[M+H] + 2221.88493, found 2221.90156.

[0545] Example 125, Preparation of the Compound of Formula C-D09

[0546]

[0547] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.20 g (10 mmol) of compound A09, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 8.17 g of a pale yellow powder, C-D09, in a 54% yield.

[0548] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 66 B2N4O[M+H] +1506.53489, found 1506.12694.

[0549] Example 126. Preparation of compounds represented by formula P-D09 and M-D09

[0550]

[0551] In an ice bath, 15.05 g (10 mmol) of compound C-D09, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 8.61 g of a light yellow powder with a yield of 57%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D09 and M-D09.

[0552] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 112 H 66 B2N4O[M+H] + 1503.53489, found 1503.12694.

[0553] Example 127, Preparation of the Compound of Formula C-D10

[0554]

[0555] In a glove box, a 500 mL double-necked round-bottom flask was charged with 7.78 g (10 mmol) of compound A10, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.06 g of a pale yellow powder, C-D10, in a 68% yield.

[0556] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 110 H 82 B2N4O[M+H] + 1618.66457, found 1618.98306.

[0557] Example 128. Preparation of compounds represented by formula P-D10 and M-D10

[0558]

[0559] In an ice bath, 16.17 g (10 mmol) of compound C-D10, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 10.55 g of a light yellow powder in a 65% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D10 and M-D10.

[0560] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 110 H 80 B2N4O[M+H] + 1615.66457, found 1615.98306.

[0561] Example 129, Preparation of the Compound of Formula C-D11

[0562]

[0563] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.44 g (10 mmol) of compound A11, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.58 g of a pale yellow powder, C-D11, in a 57% yield.

[0564] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 144 H 130 B2N4O[M+H] + 1953.04278, found 1953.34589.

[0565] Example 130, Preparation of Compounds of Formula P-D11 and M-D11

[0566]

[0567] In an ice bath, 19.52 g (10 mmol) of compound C-D11, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 14.90 g of a light yellow powder with a yield of 76%. P-D11 and M-D11 were obtained by HPLC separation (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0568] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 144 H 130 B2N4O[M+H] + 1950.04278, found 1950.34589.

[0569] Example 131, Preparation of the Compound of Formula C-D12

[0570]

[0571] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.88 g (10 mmol) of compound A12, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.25 g of a pale yellow powder, C-D12, in a 57% yield.

[0572] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 208 H 138 B2N 12 O[M+H] + 2841.13698, found 2841.09867.

[0573] Example 132, Preparation of compounds represented by formula P-D12 and M-D12

[0574]

[0575] In an ice bath, 28.40 g (10 mmol) of compound C-D12, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.23 g of a light yellow powder with a yield of 54%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D12 and M-D12.

[0576] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 208 H 136 B2N 12 O[M+H] +2838.13698, found 2838.09867.

[0577] Example 133. Preparation of the compound represented by formula C-D13

[0578]

[0579] In a glove box, a 500 mL double-necked round-bottom flask was charged with 9.32 g (10 mmol) of compound A13, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.11 g of a pale yellow powder, C-D13, in a 54% yield.

[0580] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 58 B2F 24 N4O[M+H] + 2048.44644, found 2048.03789.

[0581] Example 134. Preparation of compounds of formula P-D13 and M-D13

[0582]

[0583] In an ice bath, 20.47 g (10 mmol) of compound C-D13, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 15.44 g of a light yellow powder with a yield of 75%. P-D13 and M-D13 were separated by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)).

[0584] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 120 H 56 B2F 24 N4O[M+H] + 2045.44644, found 2046.03789.

[0585] Example 135, Preparation of the Compound of Formula C-D14

[0586]

[0587] In a glove box, a 500 mL double-necked round-bottom flask was charged with 8.20 g (10 mmol) of compound A14, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 11.14 g of a pale yellow powder, C-D14, in a 65% yield.

[0588] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 118 H 58 B2N 12 O[M+H] + 1704.50935, found 1704.50935.

[0589] Example 136. Preparation of compounds of formula P-D14 and M-D14

[0590]

[0591] In a 500mL double-necked round-bottom flask, 17.03g (10mmol) of compound C-D14, 16.2g (0.1mol) of anhydrous ferric chloride, 50ml of nitromethane, and 200ml of dichloromethane were added sequentially under an ice bath and reacted at room temperature for 16 hours. 150ml of water and 100ml of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 11.14g of a light yellow powder with a yield of 65%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D14 and M-D14.

[0592] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 118 H 56 B2N 12 O[M+H] + 1701.50935, found 1701.50935.

[0593] Example 137, Preparation of the Compound of Formula C-D15

[0594]

[0595] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.44 g (10 mmol) of compound A15, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 13.58 g of a pale yellow powder, C-D15, in a 53% yield.

[0596] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H 138 B2N 10 O[M+H] + 2553.13515, found 2553.98335.

[0597] Example 138, Preparation of compounds of formula P-D15 and M-D15

[0598]

[0599] In an ice bath, 25.52 g (10 mmol) of compound C-D15, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the product. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 17.64 g of a light yellow powder with a yield of 69%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D15 and M-D15.

[0600] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 84 H 136 B2N 10 O[M+H] + 2550.13515, found 2549.98335.

[0601] Example 139, Preparation of the Compound of Formula C-D16

[0602]

[0603] In a glove box, a 500 mL double-necked round-bottom flask was charged with 11.38 g (10 mmol) of compound A16, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 12.52 g of a pale yellow powder, C-D16, in a 52% yield.

[0604] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 90 B2N12 O9[M+H] + 2344.17859, found 2344.37489.

[0605] Example 140, Preparation of compounds represented by formula P-D16 and M-D16

[0606]

[0607] In an ice bath, 23.43 g (10 mmol) of compound C-D16, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and allowed to react at room temperature for 16 hours. Extraction was performed by adding 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 15.23 g of a light yellow powder in a 65% yield. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D16 and M-D16.

[0608] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 88 B2N 12 O9[M+H] + 2341.17859, found 2341.37489.

[0609] Example 141, Preparation of the Compound of Formula C-D17

[0610]

[0611] In a glove box, a 500 mL double-necked round-bottom flask was charged with 12.08 g (10 mmol) of compound A17, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain the crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 14.15 g of a pale yellow powder, C-D17, in a 57% yield.

[0612] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 90 B2N 12 S8O[M+H] + 2471.46467, found 2471.13983.

[0613] Example 142, Preparation of compounds represented by formula P-D17 and M-D17

[0614]

[0615] Under an ice bath, 24.71 g (10 mmol) of compound C-D17, 16.2 g (0.1 mol) of anhydrous ferric chloride, 50 ml of nitromethane, and 200 ml of dichloromethane were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. 150 ml of water and 100 ml of dichloromethane were added to extract the mixture. The organic phase was dried over anhydrous sodium sulfate, filtered, and then the organic liquid phase was distilled off to obtain a crude product. The crude product was purified by column chromatography using petroleum ether: dichloromethane (10:1) as the eluting solvent to obtain 16.73 g of a light yellow powder with a yield of 66%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D17 and M-D17.

[0616] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 88 B2N 12 S8O[M+H] + 2470.46467, found 2470.13983.

[0617] Example 143, Preparation of the Compound of Formula C-D18

[0618]

[0619] In a glove box, a 500 mL double-necked round-bottom flask was charged with 13.96 g (10 mmol) of compound A18, 7.02 g (22 mmol) of compound BD, 0.51 g (0.44 mmol) of Pd(PPh3)4, 18.24 g (0.132 mol) of potassium carbonate, and 200 mL of a 2:1:1 mixture of toluene / ethanol / water. The mixture was reacted at 85°C for 16 hours. After cooling to room temperature, 150 mL of water and 100 mL of dichloromethane were added for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to obtain a crude product. The crude product was purified by column chromatography using a 6:1 ratio of petroleum ether to dichloromethane to afford 16.01 g of a pale yellow powder, C-D18, in a 56% yield.

[0620] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 88 B2N 12 Se8O[M+H] + 2856.09654, found 2856.03783.

[0621] Example 144. Preparation of compounds of formula P-D18 and M-D18

[0622]

[0623] Under an ice bath, compound C-D18 (28.55 g, 10 mmol), anhydrous ferric chloride (16.2 g, 0.1 mol), nitromethane (50 ml), and dichloromethane (200 ml) were added to a 500 mL double-necked round-bottom flask and reacted at room temperature for 16 hours. Extraction was performed by adding 150 ml of water and 100 ml of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered, and then distilled to remove the organic liquid phase to obtain a crude product. The crude product was purified by column chromatography using petroleum ether:dichloromethane (10:1) as the eluting solvent to obtain 14.77 g of a light yellow powder with a yield of 53%. Separation by HPLC (ID column, mobile phase: n-hexane / dichloromethane = 90 / 10 (v / v)) gave P-D18 and M-D18.

[0624] The structural confirmation data are as follows: HRMS (MALDI TOF) m / z calcd for C 160 H 90 B2N 12 Se8O[M+H] + 2853.09654, found 2853.03783.

[0625] Example 145: Preparation of device

[0626] The circularly polarized organic light emitting diode device was fabricated and its performance was evaluated using the light emitting layer material based on the helical chiral helicene skeleton prepared in Example 2 of the present invention.

[0627] (1) The steps for preparing an organic electroluminescent device using the helical chiral helicene skeleton-based light-emitting layer material P-A01 as the light-emitting layer are as follows:

[0628] 1) Pretreatment of glass substrate: Select a glass substrate with 3×3mm 2 A glass substrate with an indium tin oxide (ITO) film pattern as a transparent electrode is prepared; the glass substrate is cleaned with pure water, placed in ethanol for ultrasonic treatment, and then treated with a plasma cleaning machine to obtain a pretreated glass substrate.

[0629] 2) Vacuum evaporation: Vacuum evaporation of subsequent layers is performed on the pre-treated glass substrate using vacuum evaporation. First, place the glass substrate in a vacuum evaporation chamber and reduce the pressure to 6×10 -4 Pa below; starting from the hole injection layer, followed by the hole transport layer, and then the light-emitting layer, the organic compound is heated by resistance to The film formation rate is vacuum evaporated to form films in sequence (1: electron transport layer; 2: electron injection layer; 3: cathode). Among them, the glass substrate with an ITO transparent electrode is used as the anode; the hole injection layer material HAT-CN with a film thickness of 5nm is the hole injection layer, the hole transport layer material TAPC with a film thickness of 30nm and the hole transport layer material TCTA with a film thickness of 15nm are the hole transport layer; the hole blocking layer material mCBP with a film thickness of 10nm is the hole blocking layer; P-A01 with a film thickness of 20nm doped into DMIC-TRZ is the light-emitting layer; the electron blocking layer material PO-T2T with a film thickness of 20nm is the electron blocking layer; ANT-BIZ with a film thickness of 30nm is used as the electron transport layer; Liq with a film thickness of 2nm is used as the electron injection layer; aluminum with a film thickness of 100nm is arranged with a metal mask in a manner orthogonal to the ITO stripes to form the cathode to obtain an organic light-emitting diode. The film thickness is measured using a stylus film thickness meter. Its structural schematic diagram is shown as follows Figure 1 shown.

[0630] 3) Device packaging: The prepared organic electroluminescent device is sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of less than 0.1 ppm, and then the film-forming substrate is covered with a sealing cover with epoxy-type ultraviolet-curable resin glass and sealed by self-digging curing.

[0631] (II) Performance Evaluation of Organic Light-Emitting Diodes Using P-A01, a Helical Chiral Helicene Framework-Based Light-Emitting Layer Material: A DC current was applied to the fabricated organic circularly polarized light-emitting diodes, and the luminescence performance was evaluated using a Spectrascan PR670 luminance meter. The current-voltage characteristics were measured using a computer-controlled Keithley 2400 Digital SourceMeter. The luminescence properties of the organic light-emitting diodes were measured while varying the applied DC voltage.

[0632] The CIE color coordinates of the fabricated organic electroluminescent device are (0.55, 0.44), the external quantum efficiency is 36.7%, the current efficiency is 95.58 cd / A, the power efficiency is 100.09 lm / W, and the luminescence asymmetry factor is +4.4×10 -3 .

[0633] According to the above method, circularly polarized organic light-emitting diode devices were fabricated and their performance evaluated using the helical chiral helicene skeleton light-emitting layer materials PA-PD and MA-MD in the above embodiments as light-emitting layer materials. The results are shown in Table 1.

[0634] Table 1 Performance of organic light emitting diode devices made with materials prepared in various examples as light emitting layer materials

[0635]

[0636]

[0637]

[0638]

[0639] As can be seen from the data in Table 1, the light-emitting layer material based on the helical chiral helicene skeleton of the present invention has a wide range of applications; the organic film formed by the light-emitting layer material based on the helical chiral helicene skeleton of the present invention has high surface smoothness, anti-oxidation and reduction properties, and high luminous efficiency, and can be used as the light-emitting layer of an organic light-emitting diode; the organic light-emitting diode using the organic thin film layer formed by the light-emitting layer material based on the helical chiral helicene skeleton as the light-emitting layer improves the efficiency of the device and reduces the driving voltage of the device.

Claims

1. A helical chiral multiple resonance thermally activated delayed luminescent material, the structural formulas of which are shown in Formulas P1-P4 and M1-M4: In the formula, the group R represents a C1~C12 alkane group or a C6~C12 aromatic group.

2. A helical chiral multi-resonance thermally activated delayed luminescent material, the structural formula of which is any one of the following: 。 3. The method for preparing the helical chiral multi-resonance thermally activated delayed luminescence material according to claim 1, comprising the following steps: S1. The compound represented by formula A is subjected to a Suzuki coupling reaction with the compound represented by formula B to obtain a compound represented by formula C; S2. Performing a Scholl coupling reaction on the compound represented by formula C to obtain the helical chiral multiple resonance thermally activated delayed luminescent material; In the formula, the group R is defined as described in any one of claim 1.

4. The preparation method according to claim 3, wherein: In step S1, the coupling reaction is carried out in the presence of Pd(PPh3)4 and potassium carbonate; The molar ratio of Pd(PPh3)4 to the compound represented by formula B is 0.02-0.1:1; The molar ratio of potassium carbonate to the compound represented by formula B is 5 to 7:1; The molar ratio of the compound represented by formula B to the compound represented by formula A is 1:2.2-2.4; The solvent used in the Suzuki coupling reaction is a mixed solvent of toluene, ethanol and water in a mixing ratio of 2:1:1; The temperature of the Suzuki coupling reaction is 80-100° C., and the time is 12-24 hours.

5. The preparation method according to any one of claims 3 and 4, characterized in that: In step S2, the Scholl coupling reaction is carried out under the conditions of anhydrous ferric chloride and nitromethane; The molar ratio of the anhydrous ferric chloride to the compound represented by formula C is 10-30:1; The amount of nitromethane used is 5-20 ml per millimole of the compound represented by formula C; The solvent used in the Scholl coupling reaction is anhydrous DCM; The temperature of the Scholl coupling reaction is 0-30° C., and the reaction time is 12-20 hours.

6. The preparation method according to any one of claims 3 and 4, characterized in that: After step S2, the steps of purification and chiral separation are sequentially included; The purification method is column chromatography; The chiral separation method is high performance liquid chromatography separation, which is used to separate P and M Two enantiomers.

7. Use of the helical chiral multiple resonance thermally activated delayed luminescence material according to claim 1 or 2 in the preparation of an organic light emitting diode device.

8. The use according to claim 7, characterized in that: The helical chiral multiple resonance thermally activated delayed luminescence material is used as the light-emitting layer material of the organic light-emitting diode device.

9. An organic light emitting diode device, characterized in that: The light-emitting layer material of the organic light-emitting diode device is the helical chiral multiple resonance thermally activated delayed luminescence material according to claim 1 or 2.

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