Synthesis method of boron-nitrogen heterocyclic aromatic hydrocarbon

Abstract

The invention discloses a synthesis method of boron-nitrogen heterocyclic aromatic hydrocarbon, which specifically comprises the following steps: taking boron-nitrogen heterocyclic aromatic hydrocarbon borane as a boron source, and carrying out C-H bond boronation reaction on the boron source and simple aromatic hydrocarbon under the condition of transition metal iridium catalysis to synthesize substituted boron-nitrogen heterocyclic aromatic hydrocarbon. The synthesis method disclosed by the invention is simple to operate, and the substituted boron-nitrogen heterocyclic aromatic hydrocarbon can be obtained in one step. The method can expand the pi conjugated system of the boron-nitrogen heterocyclic polycyclic aromatic hydrocarbon, and has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing boron-nitrogen polycyclic aromatic hydrocarbons. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs), as π-conjugated molecules, exhibit unique optoelectronic properties and have broad application prospects in fields such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic photovoltaics (OPVs). The introduction of heteroatoms into PAH structures is an effective strategy to improve material performance. Introducing boron-nitrogen (BN) bonds as isosteres of carbon-carbon double bonds (C=C) into PAHs has been shown to significantly improve the optoelectronic properties of organic conjugated molecules. However, the synthesis of conventional BN-PAHs typically requires pre-functionalized reagents and is often carried out at high temperatures, making the conditions relatively harsh.

[0003] Therefore, it is particularly important to develop a method for synthesizing boron-nitrogen polycyclic aromatic hydrocarbons with relatively mild conditions and readily available raw materials. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a method for synthesizing boron-nitrogen polycyclic aromatic hydrocarbons.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows: A method for synthesizing boron-nitrogen polycyclic aromatic hydrocarbons comprises the following steps: (1) Add iridium catalyst, ligand, boron nitrogen heteroaromatic hydrocarbon borane, solvent and aromatic hydrocarbon into a pressure-resistant sealed reaction tube and heat at 100~140 o C reaction 10-72h; (2) The product obtained in step (1) was taken out and cooled to room temperature, and ethyl acetate was added and mixed thoroughly; (3) The organic solvent in the organic phase obtained in step (2) is dried by spin drying, purified by using a silica gel column, and then eluted with an eluent to obtain the boron nitrogen heteropolycyclic aromatic hydrocarbon compound.

[0006] Furthermore, in step (1), the ratio of the amount of iridium catalyst, aromatic hydrocarbon, ligand, boron nitrogen heteroaromatic hydrocarbon borane and solvent is 0.001 mmol-0.012:0-2 mmol: 0.001-0.0012 mmol:0.2 mmol:0.2-1 mL.

[0007] Furthermore, in step (1), the iridium catalyst, the ligand and the boron nitrogen heteroaromatic hydrocarbon borane are stirred in a solvent at room temperature for 5-10 minutes, and then the aromatic hydrocarbon is added to react for 10-24 hours.

[0008] In a preferred embodiment of the present invention, the ligand is one of 1,2-bis(diphenylphosphino)ethane, 3,4,7,8-tetramethyl-1,10-phenanthroline, and 1,2-bis((2R,5R)-2,5-diisopropylphosphacyclopentane-1-yl)benzene (CAS: 136705-65-2).

[0009] In a preferred embodiment of the present invention, the iridium catalyst is one of (1,5-cyclooctadiene)-η5-indene)iridium and methoxy(cyclooctadiene)iridium dimer.

[0010] In a preferred embodiment of the present invention, the solvent in step (1) is one of ultra-dry 1,4-dioxane, ultra-dry tetrahydrofuran, and ultra-dry mesitylene.

[0011] In a preferred embodiment of the present invention, the borazine aromatic borane may be 2,1-borazanaphthylborane or other 2,1-borazaaromatic boranes.

[0012] In a preferred embodiment of the present invention, the aromatic hydrocarbon may be one of benzene aromatic hydrocarbons, thiophene, pyrrole, indole, benzofuran, benzothiophene, and pyridine.

[0013] In a preferred embodiment of the present invention, the eluent is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate in the eluent is 5:1-200:1.

[0014] The beneficial effects of the present invention are: 1. The present invention can achieve C-H bond borylation of aromatic hydrocarbons using easily prepared 2,1-borane arenes under iridium catalysis conditions, thereby improving the harsh reaction conditions.

[0015] 2. Complying with the concept of green chemistry: The synthesis method of the present invention uses simple aromatic hydrocarbons and does not require pre-functionalization reagents.

[0016] 3. Good substrate universality: The present invention has good substrate compatibility.

[0017] 4. The present invention can effectively expand the π-conjugated system of organic conjugated molecules and improve the photoelectric physical properties of organic conjugated molecules. DETAILED DESCRIPTION

[0018] To make the above features and advantages of the present invention more clearly understood, the following embodiments are given for detailed description. The methods of the present invention are all conventional methods in the art unless otherwise specified.

[0019] Example 1:

[0020] In a glove box filled with Ar gas, 0.012 mmol (1,5-cyclooctadiene)-η5-indene) iridium, 0.012 mmol 1,2-bis(diphenylphosphine)ethane and 0.2 mmol 2,1-borazine naphthalene (1a) were weighed into a pressure-resistant sealed reaction tube, 0.2 mL 1,4-dioxane was added and stirred at room temperature for 5 min, then 1.0 mmol 1,2-dichlorobenzene was added, and the reaction mixture was removed from the glove box and heated at 110 o The reaction was continued for 10 h under TLC monitoring. The product was removed from the pressure-sealed reaction vessel, cooled to room temperature, and 15 mL of ethyl acetate was added and mixed thoroughly. An appropriate amount of silica gel was added, and the organic solvent was removed. The product was separated by column chromatography using petroleum ether:ethyl acetate in a volume ratio of 100:1 to obtain the corresponding product in a yield of 68%.

[0021] The substrate 2,1-boranenaphthalene (1a) was obtained from Nat. Chem. 2024, 16, 1312-1319; ACS Catal. 2024, 14, 16996−17003; Org. Lett. 2007, 9, 7, 1395-1398.

[0022] The universality of the substrates was studied under the standard conditions of the present invention to illustrate that the technical solution of the present invention has good functional group compatibility. The substrate range is as follows:

[0023] The corresponding products are as follows:

[0024] For example, compound 1a reacts with compound 2a to form compound 1, and compound 2a reacts with compound 2b to form compound 2.

[0025] Example 2:

[0026] In a glove box filled with Ar gas, 0.001 mmol of methoxy(cyclooctadiene)iridium dimer, 0.002 mmol of 3,4,7,8-tetramethyl-1,10-phenanthroline and 0.2 mmol of 2,1-boranenaphthalene (1o) were weighed into a pressure-resistant sealed reaction tube, 1 mL of THF was added and the glove box was removed and heated at 100 o The reaction was continued for 12 h and monitored by TLC. The mixture was taken out from the pressure-sealed reaction vessel, cooled to room temperature, and 15 mL of ethyl acetate was added and mixed thoroughly. An appropriate amount of silica gel was added, and the organic solvent was removed. The corresponding product (29) was separated by column chromatography using petroleum ether:ethyl acetate in a volume ratio of 200:1 to obtain the product in a yield of 90%.

[0027] Example 3:

[0028] In a glove box filled with Ar gas, 0.009 mmol of methoxy(cyclooctadiene)iridium dimer, 0.018 mmol of 1,2-bis((2R,5R)-2,5-diisopropylphosphacyclopentane-1-yl)benzene and 0.2 mmol of 2,1-borazine were weighed into a pressure-sealed reaction tube. 0.2 mL of mesitylene was added and the tube was removed from the glove box and heated at 120 o The reaction was continued for 24 h under TLC monitoring. The product was removed from the pressure-sealed reaction vessel, cooled to room temperature, and 15 mL of ethyl acetate was added and mixed thoroughly. An appropriate amount of silica gel was added, and the organic solvent was removed. The product was separated by column chromatography using petroleum ether:ethyl acetate in a volume ratio of 200:1 to obtain the corresponding product in a yield of 68%.

[0029] The substrate range is as follows:

[0030] The preparation method of substrates 1p and 1r is as follows: (1) The synthesis methods of 1p' and 1r' are as follows:

[0031] Weigh 0.3 mmol of Pd2(dba)3, 0.7 mmol of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 15 mmol of sodium tert-butoxide into a 100 ml reaction flask. Evacuate the flask with argon three times. Add 10 mmol of 2-bromostyrene, 15 mmol of phenylethylamine (or n-propylamine), and 30 mL of 1,4-dioxane under argon. Incubate at 105°C for 18 hours and monitor the reaction by TLC. After the reaction is complete, filter the reaction mixture, collect the organic phase, and remove the organic solvent from the resulting phase by spin drying. Purify the product using a silica gel column with a mixture of petroleum ether and ethyl acetate (200:1) as the eluent to obtain 1p' or 1r'.

[0032] (2) Synthesis methods of 1p and 1r:

[0033] The argon atmosphere in a dry 100 mL reaction flask was replaced three times, and 30 mL of toluene, 5 mmol of 1p' or 1r', and 10 mmol of BCl3 (1.0 M in toluene) were added under argon atmosphere. Stir at room temperature for 10 min and then heated at 110 oThe reaction was carried out at 4 °C for 4 h and the reaction was monitored by TLC. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under vacuum to obtain the corresponding intermediate product (the intermediate was sensitive to air and water) without further purification. 10 mL of THF was added to the bottle in the above step and the mixture was heated to -30 °C. o C. Stir for 10 minutes, then add 10 mL of LiAlH₄ (1.0 M in THF). Stir at room temperature for 1 hour and monitor the reaction by TLC. After completion, quench the reaction with 2.5 mL of 4 M aqueous hydrochloric acid. Filter the reaction mixture, dry the filtrate over anhydrous sodium sulfate, spin-dry the organic solvent, and purify on a silica gel column to obtain product 1p or 1r.

[0034] Preparation of substrate 1q (1q' is a known compound):

[0035] The argon atmosphere in the dry 100 mL reaction flask was replaced three times, and 30 mL of toluene, 5 mmol of 1q', and 10 mmol of BCl3 (1.0 M in toluene) were added under argon atmosphere. Stir at room temperature for 10 min and then heated at 110 o The reaction was carried out at 4 °C for 4 h and the reaction was monitored by TLC. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under vacuum to obtain the corresponding intermediate product (the intermediate was sensitive to air and water) without further purification. 10 mL of THF was added to the bottle in the above step and the mixture was heated to -30 °C. o C. Stir for 10 minutes, then add 10 mL of LiAlH₄ (1.0 M in THF). Stir at room temperature for 1 hour after addition. Monitor the reaction by TLC. After completion, quench the reaction by adding 2.5 mL of 4 M aqueous hydrochloric acid. Filter the reaction solution, dry the filtrate over anhydrous sodium sulfate, spin-dry the organic solvent, and purify on a silica gel column to obtain product 1q.

[0036] The corresponding products are as follows (substrate 1p corresponds to product 30, substrate 1q corresponds to product 31, substrate 1r corresponds to product 32):

[0037] Example 4:

[0038] In a glove box filled with Ar gas, 0.012 mmol (1,5-cyclooctadiene)-η5-indene) iridium, 0.012 mmol 1,2-bis(diphenylphosphine)ethane and 0.2 mmol 2,1-borazine naphthalene were weighed into a pressure-resistant sealed reaction tube, 0.2 mL 1,4-dioxane was added and the glove box was removed and heated at 120o The reaction was continued for 48 h under TLC monitoring. The product was removed from the pressure-sealed reaction vessel, cooled to room temperature, and 15 mL of ethyl acetate was added and mixed thoroughly. An appropriate amount of silica gel was added, and the organic solvent was removed. The product was separated by column chromatography using petroleum ether:ethyl acetate in a volume ratio of 200:1 to obtain the corresponding product in a yield of 43%.

[0039] The substrate range is as follows:

[0040] Preparation of substrates 1s and 1t: (1) The synthesis methods of 1s' and 1t' are as follows:

[0041] Weigh 0.3 mmol of Pd2(dba)3, 0.7 mmol of 1,1'-binaphthyl-2,2'-bis(diphenylphosphine), and 15 mmol of sodium tert-butoxide into a 100 ml reaction flask. Evacuate the flask with argon three times. Add 10 mmol of 2-bromostyrene, 15 mmol of o-aminobiphenyl or 2-(thiophen-3-yl)aniline, and 30 mL of 1,4-dioxane under argon. Incubate at 105°C for 18 hours and monitor the reaction by TLC. After completion of the reaction, filter the reaction mixture, collect the organic phase, and spin-dry the organic solvent. Purify the resulting organic phase using a silica gel column eluent (petroleum ether:ethyl acetate = 200:1) to obtain 1s' or 1t'.

[0042] (2) Synthesis methods of 1s and 1t:

[0043] A dry 100 mL reaction flask was evacuated and replaced with argon three times. 30 mL of toluene, 5 mmol of 1s' or 1t', and 10 mmol of BCl3 (1.0 M in toluene) were added under argon atmosphere. Stir at room temperature for 10 min and then heated at 110 o The reaction was carried out at 4 °C for 4 h and the reaction was monitored by TLC. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under vacuum to obtain the corresponding intermediate product (the intermediate was sensitive to air and water) without further purification. 10 mL of THF was added to the bottle in the above step and the mixture was heated to -30 °C. o C. Stir for 10 minutes, then add 10 mL of LiAlH₄ (1.0 M in THF). Stir at room temperature for 1 hour after addition. Monitor the reaction by TLC. After completion, quench the reaction with 2.5 mL of 4 M aqueous hydrochloric acid. Filter the reaction mixture, dry the filtrate over anhydrous sodium sulfate, spin-dry the organic solvent, and purify on a silica gel column to obtain product 1s or 1t.

[0044] Preparation of substrate 1u: (1) The synthesis method of 1u' is as follows:

[0045] Weigh 0.1 mmol Pd(OAc)3, 0.8 mmol P( o -Tol)3, evacuate the argon atmosphere three times in a 100 ml reaction flask, and under argon, add 10 mmol of 2-bromoaniline, 12 mmol of 2-vinyl-1,1'-biphenyl (Org. Lett. 2023, 25, 5, 800-804), and 30 mL of triethylamine. The reaction is incubated at 120°C for 48 hours and monitored by TLC. After the reaction is complete, filter the reaction, collect the organic phase, and spin-dry the organic solvent. Purify the resulting phase using a silica gel column and elute with petroleum ether:ethyl acetate = 200:1 to obtain 1u'.

[0046] (2) Synthesis method of 1u:

[0047] The argon atmosphere in the dry 100 mL reaction flask was replaced three times, and 30 mL of toluene, 5 mmol of 1u', and 10 mmol of BCl3 (1.0 M in toluene) were added under argon atmosphere. Stir at room temperature for 10 min and then heated at 110 o The reaction was carried out at 4 °C for 4 h and the reaction was monitored by TLC. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under vacuum to obtain the corresponding intermediate product (the intermediate was sensitive to air and water) without further purification. 10 mL of THF was added to the bottle in the above step and the mixture was stirred for 1 h. o C. Stir for 10 minutes, then add 10 mL of LiAlH₄ (1.0 M in THF). Stir at room temperature for 1 hour after addition. Monitor the reaction by TLC. After completion, quench the reaction with 2.5 mL of 4 M aqueous hydrochloric acid. Filter the reaction solution, dry the filtrate over anhydrous sodium sulfate, spin-dry the organic solvent, and purify on a silica gel column to obtain product 1u.

[0048] The corresponding products are as follows (substrate 1s corresponds to product 33, substrate 1t corresponds to product 34, substrate 1u corresponds to product 35):

[0049] Example 5:

[0050] In a glove box filled with Ar gas, 0.006 mmol of methoxy(cyclooctadiene)iridium dimer, 0.012 mmol of 3,4,7,8-tetramethyl-1,10-phenanthroline and 0.2 mmol of 2,1-boranenaphthalene (1v) were weighed into a pressure-resistant sealed reaction tube. 0.2 mL of dioxane was added and the glove box was removed and heated at 140 o C was reacted for 72 h and the reaction was monitored by TLC. The product was taken out from the pressure-sealed reaction vessel, cooled to room temperature, and 15 mL of ethyl acetate was added and mixed thoroughly. An appropriate amount of silica gel was added, the organic solvent was removed, and the corresponding product (36) was separated by column chromatography using petroleum ether:ethyl acetate in a volume ratio of 200:1 to obtain the product in a yield of 17%. The NMR data of the above products are as follows: 1: 1 H NMR (500 MHz, Chloroform- d ) d 8.16 (d, J = 11.5 Hz, 1H), 8.09 (s, 1H), 7.93 (d, J = 1.6 Hz, 1H), 7.71 – 7.65 (m, 2H), 7.53 (d, J = 7.9 Hz, 1H), 7.50 –7.44 (m, 1H), 7.35 (d, J = 8.2 Hz, 1H), 7.25 – 7.21 (m, 1H), 7.19 (dd, J = 11.5,2.1 Hz, 1H).

[0051] 13 C NMR (126 MHz, Chloroform- d ) d 146.2, 139.8, 134.4, 133.6, 132.6,131.8, 130.3, 129.6, 128.7, 125.7, 121.5,118.3.

[0052] 11 B NMR (160 MHz, Chloroform- d ) d 32.03. 2: 1 H NMR (400 MHz, Chloroform- d ) d8.18 (d, J = 11.5 Hz, 1H), 8.11 (s, 1H),7.96 (s, 1H), 7.71 (d, J = 7.8 Hz, 2H), 7.56 (d, J = 7.9 Hz, 1H), 7.50 (t, J = 7.6Hz, 1H), 7.37 (d, J = 8.1 Hz, 1H), 7.31 – 7.16 (m, 2H)。

[0054] 13 C NMR (101 MHz, Chloroform- d ) d 146.2, 139.8, 134.4, 133.7, 132.6,131.8, 130.3, 129.6, 128.7, 125.7, 121.5,118.3。 3: 1 H NMR (500 MHz, Chloroform- d ) δ 8.16 (d, J = 11.5 Hz, 1H), 8.07 (s,1H), 7.94 (d, J = 1.5 Hz, 1H), 7.69 (dd, J = 7.9, 1.6 Hz, 1H), 7.65 (d, J = 2.1 Hz,1H), 7.55 (dd, J = 8.5, 2.2 Hz, 1H), 7.53 (d, J = 7.9 Hz, 1H), 7.31 (d, J = 8.5 Hz,1H), 7.18 (dd, J = 11.5, 2.0 Hz, 1H), 1.41 (s, 9H)。

[0056] 13 C NMR (126 MHz, Chloroform- d ) δ 146.5, 144.3, 137.8, 134.4, 133.5,132.6, 131.7, 130.3, 126.7, 125.5, 125.3, 118.0, 34.4,31.5。

[0057] 11 B NMR (160 MHz, Chloroform- d ) δ 31.74。 4: 1 H NMR (400 MHz, Acetone- d 6) δ 9.89 (s, 1H), 8.23 – 8.10 (m, 2H), 7.93(d, J = 8.0 Hz, 1H), 7.60 (d, J = 8.7 Hz, 2H), 7.24 (d, J = 12.2 Hz, 2H), 7.13 (dd, J = 8.9, 2.4 Hz, 1H), 3.86 (s, 3H)。

[0059] 13 C NMR (101 MHz, Acetone- d 6) δ 154.4, 145.6, 135.5, 134.6, 132.9,132.6, 131.8, 130.2, 126.3, 119.8, 118.1,110.3, 55.0。

[0060] 11 B NMR (160 MHz, Acetone- d 6) δ 31.29。 5: 1 H NMR (500 MHz, Chloroform- d ) δ 8.13 (s, 1H), 8.10 (d, J = 11.6 Hz,1H), 7.92 (d, J = 1.5 Hz, 1H), 7.67 (dd, J = 7.9, 1.6 Hz, 1H), 7.53 (d, J = 7.9 Hz,2H), 7.38 – 7.31 (m, 2H),7.26 (dd, J = 11.6, 2.0 Hz, 1H)。

[0062] 13 C NMR (126 MHz, Chloroform-d ) δ 145.4, 143.2, 138.2, 134.5, 134.0,132.8, 131.8, 130.5, 126.0, 122.2, 121.2, 120.6 (q, J = 256.2 Hz), 119.4。

[0063] 19 F NMR (471 MHz, Chloroform- d ) δ -58.02。

[0064] 11 B NMR (160 MHz, Chloroform- d ) δ 32.35。 6: 1 H NMR (500 MHz, Chloroform- d ) δ 8.11 (d, J = 11.5 Hz, 1H), 8.06 (s,1H), 7.91 (d, J = 1.6 Hz, 1H), 7.67 (dd, J = 7.9, 1.6 Hz, 1H), 7.62 (dd, J = 8.7,6.1 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.12 (dd, J = 11.5, 2.0 Hz, 1H), 7.04 (dd, J = 9.9, 2.4 Hz, 1H), 6.97 (td, J = 8.5, 2.4 Hz, 1H)。

[0066] 13 C NMR (101 MHz, Chloroform- d ) δ 162.8 (d, J = 248.0 Hz), 145.7, 141.0(d, J = 10.6 Hz), 134.5, 134.0, 132.8, 131.7, 131.3 (d, J = 9.9 Hz), 130.4,122.5, 110.0 (d, J= 23.1 Hz), 104.2 (d, J = 24.2 Hz)。

[0067] 19 F NMR (471 MHz, Chloroform- d ) δ -111.11。

[0068] 11 B NMR (160 MHz, Chloroform- d ) δ 32.54。 7: 1 H NMR (500 MHz, Chloroform- d ) δ 8.14 (s, 1H), 7.98 (s, 1H), 7.72 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.56 – 7.43 (m, 7H), 7.41 (d, J = 8.2Hz, 1H), 7.16 (t, J = 7.6 Hz, 1H), 7.10 (s, 1H)。

[0070] 13 C NMR (126 MHz, Chloroform- d ) δ 157.5, 142.4, 140.4, 134.5, 133.7,132.6, 131.8, 130.4, 128.9, 128.7, 128.4, 128.2, 127.6,124.8, 121.4, 118.8。

[0071] 11 B NMR (160 MHz, Chloroform- d ) δ 31.98。 8: 1 H NMR (500 MHz, Chloroform- d ) δ 7.94 (s, 1H), 7.92 (d, J = 1.6 Hz,1H), 7.86 (d, J = 8.2 Hz, 1H), 7.67 (dd, J= 8.0, 1.6 Hz, 1H), 7.52 (d, J = 7.9 Hz,1H), 7.50 – 7.45 (m, 1H), 7.33 (dd, J = 8.1, 1.2 Hz, 1H), 7.29 – 7.24 (m, 1H),7.00 (dd, J = 1.9, 0.9 Hz, 1H), 2.66 (d, J = 1.1 Hz, 3H)。

[0073] 13 C NMR (126 MHz, Chloroform- d ) δ 152.5, 140.0, 134.4, 133.5, 132.5,131.7, 130.3, 128.4, 125.8, 125.7, 121.4, 118.8, 77.3,77.0, 76.7, 23.0。

[0074] 11 B NMR (160 MHz, Chloroform- d ) δ 31.56。 9: 1 H NMR (500 MHz, Chloroform- d ) δ 8.08 (d, J = 11.2 Hz, 1H), 7.73 (dd, J =7.7, 1.5 Hz, 1H), 7.67 (d, J = 1.5 Hz, 1H), 7.65 – 7.58 (m, 2H), 7.52 (d, J = 7.9Hz, 1H), 7.41 (dd, J = 7.9, 1.6 Hz, 1H), 7.33 – 7.29 (m, 1H), 6.89 (d, J = 11.3Hz, 1H), 3.70 (s, 3H). 13 C NMR (126 MHz, Chloroform- d) δ 145.3, 142.0, 134.8, 132.3, 132.0,131.9, 130.3, 129.9, 129.0, 126.8, 121.3, 115.1, 36.7。

[0076] 11 B NMR (160 MHz, Chloroform- d ) δ 34.68。 10: 1 H NMR (400 MHz, Chloroform- d ) δ 8.52 (d, J = 8.2 Hz, 1H), 8.47 (d, J =8.1 Hz, 1H), 8.12 (d, J = 7.6 Hz, 1H), 7.84 (s, 1H), 7.80 (t, J = 7.7 Hz, 1H),7.68 (s, 1H), 7.59 (s, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.5 Hz, 1H),7.32 (dd, J = 17.8, 8.0 Hz, 2H)。

[0078] 13 C NMR (126 MHz, Chloroform- d ) δ 139.1, 138.2, 135.7, 134.8, 132.9,132.4, 132.4, 131.3, 130.2, 128.2, 126.3, 124.0, 123.5,122.4, 122.1, 119.2。

[0079] 11 B NMR (160 MHz, Chloroform- d ) δ 36.18。 11: 1 H NMR (400 MHz, Chloroform- d ) δ 9.02 (s, 1H), 8.22 (dd, J= 12.6, 10.2Hz, 2H), 7.93 (s, 1H), 7.89 (d, J = 7.9 Hz, 1H), 7.68 (d, J = 7.9 Hz, 1H), 7.65 –7.46 (m, 7H), 7.25 (d, J = 11.4 Hz, 2H)。

[0081] 13 C NMR (101 MHz, Chloroform- d ) δ 146.9, 135.7, 134.3, 133.6, 133.6,132.7, 131.7, 130.4, 129.0, 127.4, 126.8, 126.1, 123.8,121.7, 121.7, 119.4。

[0082] 11 B NMR (160 MHz, Acetone- d 6) δ 32.50。 12: 1 H NMR (400 MHz, Chloroform- d ) δ 8.24 (d, J = 11.5 Hz, 1H), 8.20 (s,1H), 7.97 (s, 2H), 7.79 (d, J = 7.4 Hz, 1H), 7.71 (d, J = 7.9 Hz, 1H), 7.54 (d, J =7.9 Hz, 1H), 7.47 (d, J = 7.2 Hz, 1H), 7.44 – 7.31 (m, 3H), 7.17 (d, J = 11.5 Hz,1H), 1.58 (s, 6H)。

[0084] 13 C NMR (101 MHz, Chloroform- d) δ 155.2, 153.1, 146.5, 139.9, 138.7,134.4, 133.7, 133.6, 132.6, 131.7, 130.4, 127.2, 127.1,125.2, 122.6, 120.2,119.8, 112.4, 46.8, 27.8。

[0085] 11 B NMR (160 MHz, Chloroform- d ) δ 31.83。 13: 1 H NMR (400 MHz, Chloroform- d ) δ 7.95 (s, 1H), 7.82 – 7.75 (m, 1H),7.71 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.24 – 7.15 (m, 3H), 7.14 (d, J = 3.4 Hz, 1H), 7.01 (s, 1H), 6.76 (s, 1H)。

[0087] 13 C NMR (101 MHz, Chloroform- d ) δ 134.6, 133.8, 132.6, 132.1, 131.2,130.3, 127.4, 124.4, 122.6, 119.4, 118.6, 118.0, 115.5,112.8。

[0088] 11 B NMR (160 MHz, Chloroform- d ) δ 31.33。 14: 1 H NMR (400 MHz, THF- d 8) δ 10.19 (s, 2H), 8.33 (d, J = 11.5 Hz, 2H),7.92 (s, 4H), 7.89 (s, 2H), 7.32 (d, J = 11.5 Hz, 2H)。

[0090] 13 C NMR (101 MHz, THF- d 8) δ 150.2, 145.9, 135.6, 127.6, 125.9, 117.3。

[0091] 11 B NMR (160 MHz, ) δ 29.89。 15: 1 H NMR (400 MHz, Chloroform- d ) δ 8.20 (d, J = 11.5 Hz, 1H), 8.12 (s,1H), 7.94 (s, 2H), 7.77 (s, 1H), 7.72 (d, J = 7.7 Hz, 1H), 7.52 (t, J = 7.3 Hz,1H), 7.39 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 7.6 Hz, 1H), 7.19 (d, J = 11.5 Hz, 1H)。

[0093] 13 C NMR (101 MHz, Chloroform- d ) δ 146.4, 139.7, 134.6, 134.0, 129.6,128.8, 125.8, 123.4, 121.7, 118.4。

[0094] 11 B NMR (160 MHz, Chloroform- d ) δ 31.77。 16: 1 H NMR (400 MHz, Chloroform- d ) δ 8.78 (s, 1H), 8.16 (d, J = 11.6 Hz,1H), 7.66 (d, J = 7.8 Hz, 1H), 7.63 – 7.56 (m, 1H), 7.45 (t, J = 7.6 Hz, 1H),7.34 (d, J= 8.2 Hz, 1H), 7.26 – 7.17 (m, 2H), 7.08 – 7.04 (m, 2H)。

[0096] 13 C NMR (101 MHz, Chloroform- d ) δ 162.8 (d, J = 237.3 Hz), 159.2 (d, J =240.6 Hz), 146.0, 139.8, 129.5, 128.6, 125.6, 121.8 (dd, J = 22.0, 10.3 Hz),121.5, 118.7, 117.8 (dd, J = 24.2, 10.3 Hz), 116.4 (dd, J = 29.5, 8.3 Hz)。

[0097] 19 F NMR (376 MHz, Chloroform- d ) δ -113.55, -120.05。

[0098] 11 B NMR (160 MHz, Chloroform- d ) δ 31.20。 17: 1 H NMR (500 MHz, Chloroform- d ) δ 8.24 – 8.13 (m, 3H), 8.03 (s, 1H),7.83 (s, 1H), 7.70 (d, J = 7.9 Hz, 1H), 7.53 – 7.47 (m, 1H), 7.39 (d, J = 8.1 Hz,1H), 7.28 – 7.24 (m, 1H), 7.21 (dd, J = 11.5, 2.0 Hz, 1H)。

[0100] 13 C NMR (126 MHz, Chloroform- d) δ 146.6, 139.7, 138.8, 132.6, 132.3, 132.1, 131.8, 129.6, 129.0, 129.0, 129.0, 128.9, 128.9, 127.7, 127.7, 127.7, 127.6, 126.7, 125.8, 124.6, 123.1, 122.4, 121.8, 120.2, 118.4。

[0101] 19 F NMR (376 MHz, Chloroform- d ) δ -62.62。

[0102] 18 (Known compound): 1 H NMR (500 MHz, Chloroform- d ) δ 8.25 – 8.09 (m, 1H), 7.99 – 7.92 (m, 2H), 7.69 (d, J = 7.6 Hz, 1H), 7.55 – 7.44 (m, 4H), 7.36 (d, J = 8.1 Hz, 1H), 7.31 (dd, J = 11.5, 2.0 Hz, 1H), 7.25 – 7.19 (m, 1H)。

[0103] 13 C NMR (126 MHz, Chloroform- d ) δ 145.5, 140.1, 132.7, 129.6, 129.5, 128.4, 128.2, 125.7, 121.1, 118.2。 19 1 H NMR (500 MHz, Chloroform- d ) δ 8.16 – 8.02 (m, 2H), 7.65 (d, J = 7.8Hz, 1H), 7.57 (dd, J = 1.8, 0.9 Hz, 1H), 7.47 – 7.43 (m, 1H), 7.35 – 7.29 (m, 2H), 7.24 – 7.15 (m, 2H), 7.12 (t, J= 2.1 Hz, 1H), 3.85 (s, 3H)。

[0105] 13 C NMR (126 MHz, Chloroform- d ) δ 160.3, 146.0, 139.8, 129.5, 128.6,127.6, 125.8, 123.3, 121.4, 118.3, 117.7, 117.3, 55.5。

[0106] 11 B NMR (160 MHz, Chloroform- d ) δ 32.25。 20: 1 H NMR (500 MHz, Chloroform- d ) δ 8.23 – 8.11 (m, 2H), 7.71 (s, 1H),7.69 (d, J = 7.9 Hz, 1H), 7.58 (d, J = 2.6 Hz, 1H), 7.51 – 7.46 (m, 1H), 7.38 (d, J = 8.1 Hz, 1H), 7.26 – 7.21 (m, 2H), 7.20 (s, 1H), 3.93 (s,3H)。

[0108] 13 C NMR (126 MHz, Chloroform- d ) δ 159.6, 146.2, 139.8, 131.7 (q, J =31.9 Hz), 129.6, 128.7, 125.8, 124.3 (q, J = 273.0 Hz), 121.9, 121.5, 121.2 (q, J = 3.9 Hz), 118.4, 111.1 (q, J = 3.7 Hz), 55.5。

[0109] 19 F NMR (471 MHz, Chloroform- d ) δ -62.31。

[0110] 11B NMR (160 MHz, Chloroform- d ) δ 32.45。 21: 1 H NMR (400 MHz, Chloroform- d ) δ 8.29 (s, 1H), 8.21 (d, J = 11.6 Hz,1H), 7.69 (d, J = 7.9 Hz, 1H), 7.61 (s, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.39 (d, J =8.4 Hz, 1H), 7.27 (t, J = 7.3 Hz, 1H), 7.11 (d, J = 11.4 Hz, 1H)。

[0112] 13 C NMR (101 MHz, CDCl3) δ 150.5, 147.2, 139.4, 129.7, 129.1, 126.0,122.2, 118.6。

[0113] 11 B NMR (160 MHz, Chloroform- d ) δ 31.17。 22: 1 H NMR (500 MHz, Acetone- d 6) δ 10.27 (s, 1H), 8.29 (d, J = 11.5 Hz, 1H),8.11 (s, 2H), 7.76 (d, J = 7.9 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 7.52 (ddd, J =8.4, 7.2, 1.4 Hz, 1H), 7.30 – 7.23 (m, 2H)。

[0115] 13 C NMR (126 MHz, ACETONE- D6) δ 147.8, 141.4, 141.3, 131.6, 130.3,129.8, 127.0, 122.7, 119.8。

[0116] 11 B NMR (160 MHz, Acetone- d 6) δ 30.73。 23: 1 H NMR (500 MHz, Chloroform- d ) δ 8.48 (d, J = 0.8 Hz, 1H), 8.45 (s,1H), 8.25 (d, J = 11.4 Hz, 1H), 7.95 (d, J = 0.9 Hz, 1H), 7.72 (d, J = 7.7 Hz, 1H),7.55 – 7.49 (m, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.31 – 7.27 (m, 1H), 7.22 (dd, J =11.4, 2.1 Hz, 1H), 4.03 (s, 2H)。

[0118] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 165.2, 151.8, 147.5, 147.3, 139.5,131.7, 129.7, 129.1, 126.8, 126.1, 122.2, 118.7, 53.1。

[0119] 11 B NMR (160 MHz, Chloroform- d ) δ 36.44。 24: 1 H NMR (500 MHz, Chloroform- d ) δ 8.27 (s, 1H), 8.08 (d, J = 11.5 Hz,1H), 7.72 (d, J = 1.7 Hz, 1H), 7.63 (d, J= 8.0 Hz, 1H), 7.46 – 7.40 (m, 1H),7.32 (d, J = 8.1 Hz, 1H), 7.20 – 7.14 (m, 2H), 7.11 (dd, J = 11.5, 1.8 Hz, 1H),6.54 (dd, J = 3.3, 1.6 Hz, 1H)。

[0121] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 146.1, 145.5, 139.9, 129.5, 128.5,125.6, 120.9, 120.7, 118.1, 110.9。

[0122] 11 B NMR (160 MHz, Chloroform- d ) δ 27.92。 25: 1 H NMR (500 MHz, Chloroform- d ) δ 8.54 (s, 1H), 8.14 (d, J = 11.5 Hz,1H), 7.67 (t, J = 7.2 Hz, 2H), 7.59 (d, J = 7.4 Hz, 1H), 7.50 – 7.44 (m, 2H),7.41 – 7.33 (m, 2H), 7.28 – 7.18 (m, 3H)。

[0124] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 157.3, 145.8, 139.8, 129.6, 128.7,128.7, 125.9, 125.3, 122.6, 121.6, 121.3, 118.3, 117.0,111.4。

[0125] 11 B NMR (160 MHz, Chloroform- d ) δ 28.30。 26: 1H NMR (400 MHz, Chloroform- d ) δ 8.06 (d, J = 11.5 Hz, 1H), 7.89 (s,1H), 7.63 (d, J = 7.8 Hz, 1H), 7.55 (d, J = 2.7 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H),7.29 (d, J = 8.1 Hz, 1H), 7.22 – 7.11 (m, 2H), 6.95 (s, 1H), 2.62 (s, 3H)。

[0127] 13 C NMR (101 MHz, CDCl3) δ 145.8, 145.2, 140.1, 134.2, 129.4, 128.4,127.5, 125.6, 120.9, 118.0, 15.5。

[0128] 11 B NMR (160 MHz, Chloroform- d ) δ 29.92。 27: 1 H NMR (500 MHz, Chloroform- d ) δ 8.18 – 8.09 (m, 2H), 7.98 – 7.93 (m,2H), 7.93 – 7.88 (m, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.50 – 7.44 (m, 1H), 7.42 –7.34 (m, 3H), 7.28 (dd, J = 11.5, 2.0 Hz, 1H), 7.25 – 7.19 (m, 1H)。

[0130] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 145.8, 143.0, 141.4, 139.9, 131.0,129.6, 128.7, 125.9, 124.8, 124.2, 124.0, 122.5, 121.4,118.3。

[0131] 11 B NMR (160 MHz, Chloroform- d ) δ 30.35。 28: 1 H NMR (500 MHz, Acetone- d 6) δ 10.53 (s, 1H), 9.79 (s, 1H), 8.13 (d, J =11.5 Hz, 1H), 7.68 – 7.63 (m, 2H),7.63 – 7.59 (m, 1H), 7.53 (d, J = 8.2 Hz,1H), 7.47 – 7.40 (m, 2H), 7.33 (dd, J = 11.5, 1.9 Hz, 1H), 7.26 (dd, J = 2.1, 0.9Hz, 1H), 7.18 – 7.09 (m, 2H), 7.02 – 6.97 (m, 1H)。

[0133] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 150.4, 146.2, 144.6, 134.6, 134.6,133.7, 131.0, 127.7, 126.0, 124.4, 123.6, 116.6, 116.4。

[0134] 11 B NMR (160 MHz, Chloroform- d ) δ 34.79。 29: 1 H NMR (500 MHz, Chloroform- d ) d 8.19 (d, J = 11.6 Hz, 1H), 8.02 (d, J= 6.9 Hz, 1H), 7.76 (m, J = 7.8, 1.3 Hz, 1H), 7.67 – 7.52(m, 2H), 7.52 – 7.42(m, 3H), 7.29 (d, J = 11.6 Hz, 1H), 7.27 – 7.19 (m, 1H), 5.00 (s, 2H)。

[0136] 13 C NMR (126 MHz, Chloroform- d ) d 149.1, 146.2, 140.8, 130.8, 130.6,129.3, 129.0, 127.0, 126.6, 122.5, 120.6,114.3, 54.6。

[0137] 11 B NMR (128 MHz, Chloroform-d) d 35.6。 30: 1 H NMR (500 MHz, Chloroform-d) d 8.08 (d, J = 11.4 Hz, 1H), 7.97 (dd, J =7.1, 1.6 Hz, 1H), 7.68 (dd, J = 7.7, 1.7 Hz, 1H), 7.65 (d, J = 8.6 Hz, 1H), 7.52(m, J = 8.7, 7.1, 1.6 Hz, 1H), 7.38 (m, J = 7.4, 1.6 Hz, 1H), 7.34 (m, J = 7.3, 1.4Hz, 1H), 7.32 (d, J = 11.5 Hz, 2H), 7.29 – 7.23 (m, 1H),7.21 (m, J = 7.8, 7.0,1.0 Hz, 1H), 4.20 (t, J = 6.7 Hz, 2H), 3.18 (t, J = 6.7 Hz, 2H)。

[0139] 13 C NMR (126 MHz, Chloroform-d) d 145.5, 142.1, 142.0, 133.5, 130.7,130.3, 128.7, 127.1, 126.7, 126.5, 120.6, 113.9, 43.8,32.5。

[0140] 11B NMR (160 MHz, Chloroform-d) d 32.7. 31: 1 H NMR (500 MHz, Chloroform- d ) δ 8.05 (s, 1H), 7.81 (d, J = 7.0 Hz,1H), 7.76 (s, 1H), 7.61 (d, J = 7.7 Hz, 1H), 7.45 – 7.36 (m, 2H), 7.36 – 7.29(m, 3H), 7.18 (t, J = 7.4 Hz, 1H), 3.02 (t, J = 5.8 Hz, 2H), 2.94 (t, J = 5.9 Hz,2H).

[0142] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 148.8, 139.5, 137.9, 130.2, 129.9,128.8, 128.6, 127.1, 126.2, 125.8, 121.0, 118.0, 77.3,77.0, 76.7, 33.2, 31.3.

[0143] 11 B NMR (160 MHz, Chloroform- d ) δ 31.50.

[0144] 32 (known compounds): 1 H NMR (500 MHz, Chloroform- d) δ 8.01 (d, J = 11.5 Hz, 1H), 7.68 (dd,J = 7.8, 1.6 Hz, 1H), 7.50 (m, J = 8.5, 7.1, 1.5 Hz, 1H), 7.35 (d, J = 8.3Hz, 1H), 7.21–7.15 (m, 1H), 6.88 (d, J = 11.5 Hz, 1H), 4.29–3.74 (m, 2H), 2.19 (m, J = 14.5, 7.4 Hz, 2H), 1.63–1.56 (m, 2H).

[0145] 33 (known compound): 1 H NMR (400 MHz, Chloroform- d ) d 8.47 (d, J = 7.5 Hz, 1H), 8.44 – 8.31(m, 4H), 8.14 (d, J = 11.4 Hz, 1H), 7.81 – 7.71 (m, 2H), 7.65 (d, J = 11.4 Hz,1H), 7.59 (t, J = 7.3 Hz, 1H), 7.46 – 7.36 (m, 3H), 7.30 (t, J = 7.4 Hz, 1H).

[0146] 13 C NMR (101 MHz, Chloroform- d ) d 144.5, 138.9, 137.5, 137.4, 133.5,131.1, 129.8, 129.0, 128.1, 126.7, 126.6, 126.0, 125.6, 123.6, 122.4, 122.3,122.0, 120.6.

[0147] 34 (known compounds): 1 H NMR (400 MHz, Chloroform- d ) δ 8.97 (s, 1H), 8.67 (s, 1H), 8.55 –8.42 (m, 3H), 8.23 ​​(d, J= 7.2 Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.70 (t, J = 7.1Hz, 1H), 7.60 – 7.45 (m, 5H), 7.37 – 7.29 (m, 1H)。

[0148] 13 C NMR (126 MHz, Chloroform- d ) δ 141.3, 139.5, 136.9, 133.9, 133.4,130.6, 130.3, 129.8, 128.6, 127.1, 127.1, 126.1, 125.5,125.0, 124.1, 123.0,121.2, 118.2, 77.3, 77.0, 76.7。 35: 1 H NMR (500 MHz, Chloroform- d ) δ 8.50 – 8.45 (m, 1H), 8.43 (d, J = 8.6Hz, 1H), 8.25 – 8.20 (m, 1H), 8.07 (d, J = 11.2 Hz, 1H), 7.96 (d, J = 4.9 Hz,1H), 7.91 (d, J = 4.9 Hz, 1H), 7.76 (dd, J = 7.7, 1.5 Hz, 1H), 7.47 – 7.36 (m,4H), 7.33 – 7.28 (m, 1H)。

[0150] 13 C NMR (126 MHz, CHLOROFORM- D ) δ 144.9, 144.2, 139.2, 137.5, 133.5,129.9, 129.2, 126.7, 125.8, 125.6, 125.1, 123.5, 123.2,122.5, 122.3, 121.0。

[0151] 11 B NMR (160 MHz, Chloroform- d ) δ 28.55。 36: 1 H NMR (400 MHz, Chloroform- d ) d 8.51 (d, J = 8.6 Hz, 1H), 8.26 – 8.12(m, 3H), 7.99 (d, J = 8.2 Hz, 1H), 7.80 (d, J = 7.7 Hz, 1H), 7.75 – 7.68 (m, 2H), 7.67 – 7.55 (m, 2H), 7.39 (d, J = 11.5 Hz, 1H), 7.29 (t, J = 7.5 Hz, 1H).

[0153] 13 C NMR (101 MHz, Chloroform- d ) d 147.9, 145.4, 139.9, 133.9, 131.7,131.3, 130.3, 129.5, 129.2, 128.1, 127.8,127.0, 123.2, 121.2, 116.3, 113.1.

[0154] 11 B NMR (160 MHz, Chloroform- d ) d 36.06.

[0155] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made within the scope of the present invention and the contents of the specification should still be covered by the present invention.

Claims

1. A method for synthesizing boron-nitrogen polycyclic aromatic hydrocarbons, characterized in that: The following steps are involved: (1) Add iridium catalyst, ligand, boron nitrogen heteroaromatic hydrocarbon borane, solvent and aromatic hydrocarbon into a pressure-resistant sealed reaction tube and heat at 100~140 o C reaction 10-72h; (2) The product obtained in step (1) was taken out and cooled to room temperature, and ethyl acetate was added and mixed; (3) The organic solvent in the organic phase obtained in step (2) is dried by spin drying, purified by using a silica gel column, and then eluted with an eluent to obtain the boron nitrogen heteropolycyclic aromatic hydrocarbon compound.

2. The synthesis method according to claim 1, wherein: In step (1), the ratio of the iridium catalyst, aromatic hydrocarbon, ligand, boron nitrogen heteroaromatic hydrocarbon borane and solvent is 0.001 mmol-0.012:0-2 mmol: 0.001-0.0012 mmol:0.2mmol:0.2-1 mL.

3. The synthesis method according to claim 1, wherein: In step (1), the iridium catalyst, the ligand and the boron nitrogen heteroaromatic hydrocarbon borane are stirred in a solvent at room temperature for 5-10 minutes, and then the aromatic hydrocarbon is added to react for 10-24 hours.

4. The synthesis method according to claim 1, characterized in that The ligand is one of 1,2-bis(diphenylphosphino)ethane, 3,4,7,8-tetramethyl-1,10-phenanthroline, and 1,2-bis((2R,5R)-2,5-diisopropylphosphacyclopentane-1-yl)benzene.

5. The synthesis method according to claim 1, wherein: The iridium catalyst is one of (1,5-cyclooctadiene)-η5-indene)iridium and methoxy (cyclooctadiene) iridium dimer.

6. The synthesis method according to claim 1, wherein: The solvent in step (1) is one of super-dry 1,4-dioxane, super-dry tetrahydrofuran, and super-dry mesitylene.

7. The synthesis method according to claim 1, wherein: The boro-azaaromatic hydrocarbon borane is one of 2,1-borazanaphthalene and 2,1-borazaphenanthrene.

8. The synthesis method according to claim 1, wherein: The aromatic hydrocarbon is a simple aromatic hydrocarbon, including one of benzene aromatic hydrocarbons, thiophene, pyrrole, indole, benzofuran, benzothiophene, and pyridine.

9. The synthesis method according to claim 1, wherein: The eluent in step (4) is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate in the eluent is 5:1-200:1.

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