A method for constructing isoquinoline compounds based on aryl migration strategy, a hole transport material molecule and a preparation method thereof, and a perovskite solar cell and a preparation method thereof

Abstract

The patent application relates to a kind of catalyst (for example trivalent rhodium catalyst) catalysis, additive (such as N-bromosuccinimide) promotes the tandem reaction of aromatic ring ortho vinyl group-containing imidic acid ester, oxidation C-H bond amination, and the C3 position to C4 position migration of olefin connected aryl group.This patent application discloses a kind of method for constructing isoquinoline compound based on aryl migration strategy, hole transport material molecule and its preparation method, perovskite solar cell and its preparation method.The oxidation amination, aryl migration tandem reaction has good site selectivity, atom economy, step economy, meet the requirements of green and sustainable chemistry, can quickly construct site diversity functional molecule library.The substrate of the method is widely used, and the target product C1-ethoxy isoquinoline can be further converted into isoquinoline ketone and C1 position halogenated isoquinoline derivative.The isoquinoline derivative obtained in the application patent can also be applied to potential perovskite battery hole transport layer material.

Description

Technical Field

[0001] This patent application relates to the field of organic compound synthesis technology, and more specifically, to a method for constructing isoquinoline compounds based on an aryl migration strategy, hole transport material molecules and their preparation methods, and perovskite solar cells and their preparation methods. Background Technology

[0002] Isoquinoline derivatives are not only a very important nitrogen-containing fused heterocyclic skeleton in organic synthesis, widely found in drug molecules such as the anti-inflammatory and antibacterial drug palmatine chloride, the anesthetic quinisocaine, and the anemia treatment roxadustat; in addition, isoquinolines are also found in many natural products and physiologically active alkaloids, such as berberine and corydamine. Isoquinolines can also be used as fused-ring skeletons in the field of organic optoelectronic materials.

[0003] Traditional methods for synthesizing polysubstituted isoquinolines in organic processes are often lengthy, require harsh reaction conditions, and are not very atom- and step-economical. Therefore, green and efficient methods for synthesizing isoquinoline derivatives are still highly anticipated.

[0004] Furthermore, because different reaction sites in (hetero)aromatic hydrocarbons exhibit different propensities for participating in electrophilic, nucleophilic, or radical reactions, controlling the activation of the target site remains challenging for different reaction sites. Through decades of exploration by organic chemists, numerous aromatic rearrangement reactions, such as the Smiles rearrangement, Claisen rearrangement, and Bamberger rearrangement, have been discovered and invented to address this challenge. These rearrangement reactions not only possess high atom economy and step economy but also allow for the rearrangement and recombination of the entire (hetero)aromatic ring skeleton, rapidly constructing a diverse library of functional molecules. However, these rearrangements leave behind some original functional groups on the initially substituted carbon atom, forming several different products, including the target product. Therefore, to obtain the target product at a specific site, organic chemists have invented another more practical solution: functional group migration. This involves completely removing the original functional group from the carbon atom and migrating it to the target carbon atom.

[0005] In recent decades, organic chemists have discovered several phenomena in which functional groups can migrate under specific chemical conditions, particularly in the study of (hetero)aromatic hydrocarbon functional group migration. These include classic alkyl migration phenomena, which occur under the influence of Brønsted or Lewis acids via reversible Friedel-Crafts migration. Crafts-type reactions cause alkyl groups to migrate around the aromatic ring, thereby forming different isomers.

[0006] Furthermore, the migration reaction of halogens, also known as the halogen dance reaction, occurs in the presence of alkali (NaNH2, ...). t BuOK, Grignard reagents and n Under the promotion of BuLi et al., halogen substituents in haloaromatic hydrocarbons move to new substitution positions, resulting in 1,2-substitution reactions of halogen groups.

[0007] Recently, transition metal-catalyzed C-H bond activation has also promoted the migration of certain functional groups. For example, Yamaguchi reported in 2020 that the synergistic effect of divalent palladium and phosphine ligands facilitated the migration of ester groups from the C1 to C2 position on the aromatic ring. Sci. Adv. 2020; 6 (eaba7614). This reaction may have involved activation of the ortho-CH bond and decarbonylation, forming the key intermediate η. 2 -Arylpalladium species, subsequently thermodynamically driven, achieve the migration of the ester group at the C1 to C2 position on the aromatic ring.

[0008] In recent years, transition metal-catalyzed carbon-hydrogen bond activation reactions have also achieved boron-based migration, silicon-based migration, and acyl-based migration. J. Am. Chem. Soc. , 2019, 141 , 12305 12311; Org. Lett. , 2021, 23 , 6714 6718; Chem. Sci. , 2021, 12 , 3216 (3225), thus enriching the functional group migration reaction, a highly valuable type of synthetic transformation.

[0009] Furthermore, tandem reaction strategies involving free radicals can also achieve aryl migration. For example, in 2014, Liang Yongmin and Liu Xueyuan's research group reported a one-pot method for achieving a tandem reaction involving monovalent copper catalysis, Togni trifluoromethyl reagent-induced trifluoromethylation of high propargyl alcohol compounds, 1,4-aryl migration, and carbonyl formation. Angew. Chem. Int. Ed. , 2014, 53 7629 7633). Among them, the 1,4-aryl migration may be achieved by the addition of trifluoromethyl radical to the alkyne to form a radical intermediate, which is then induced by the radical.

[0010] Our research group has always had a strong interest in the site-selective C-H bond activation and its applications promoted by readily available and easily convertible directing groups. ChemCatChem., 2020, 12 , 2358 2384 (Invited Review)), we have also recently achieved imide-directed CH and C-C bond activation, enabling the simple construction of various nitrogen-containing fused rings ( ACS Catal .,2019, 9 8749 8756), and the ordered multiple carbon-hydrogen bond activation reactions of aromatic rings to construct multifunctionalized aromatic heterocycles ( Chem. Commun ., 2021, 57 , 8075 8078).

[0011] In summary, there are few reported methods for constructing isoquinoline compounds based on aryl migration strategies. Therefore, it is necessary to develop methods with good site selectivity, atom economy, and step economy to synthesize C4-aryl or heteroaryl-substituted isoquinolines with high regioselectivity under mild reaction conditions. Summary of the Invention

[0012] To overcome at least one problem with existing technologies, this patent application provides a method for constructing isoquinoline compounds based on an aryl migration strategy. This method can synthesize C4-aryl or heteroaryl-substituted isoquinolines in a one-pot process. This method not only possesses a wide substrate applicability and good atom and step economy, but more importantly, the generated target product, the C1-ethoxy isoquinoline, can be further converted into isoquinolinones and C1-halogenated isoquinoline derivatives.

[0013] To solve the above-mentioned technical problems, the technical solution adopted in this patent application is:

[0014] A method for constructing isoquinoline compounds based on an aryl migration strategy is described. In an inert solvent, under the catalysis of a catalyst and the promotion of additives, 2-styrenebenzylinate ethyl ester (Formula II) undergoes an oxidative CH bond amination and a tandem reaction involving the C3-to-C4 migration of the aryl group attached to the olefin, yielding a C4-aryl or heteroaryl-substituted isoquinoline (Formula I). ​​The reaction is shown below:

[0015] ;

[0016] Where R 1 Substituents include hydrogen, alkyl, halogen, and aryl groups; R 2 It is a saturated or unsaturated straight-chain hydrocarbon group or cyclic hydrocarbon group, or a fused-ring aryl group, containing functional groups such as halogen, ester, nitro, cyano, and acyl groups.

[0017] This patent application also provides a hole transport material molecule, which is prepared from C4-aryl or heteroaryl-substituted isoquinoline (Formula I) obtained by the above method as a raw material.

[0018] This patent application also provides a method for preparing the above-mentioned hole transport material molecules, specifically including the following preparation steps:

[0019] S1. Under an atmospheric pressure and air atmosphere, 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole, HCl, and 1,4-dioxane were added sequentially to a Schlenk reaction tube at a temperature of 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether and ethyl acetate in a volume ratio of 1:1, to obtain product 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a.

[0020] S2. Under an atmospheric pressure, 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a was added sequentially to a Schlenk reaction tube, and phosphorus oxychloride was reacted at room temperature for 12 hours. The crude product was separated by chromatography using a prepared silica gel plate with a petroleum ether to ethyl acetate volume ratio of 50:1 as the developing or eluent to obtain product 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a.

[0021] S3. Under an air atmosphere at one atmosphere, 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a, triphenylamine 4-borate 5a, tetrakis(triphenylphosphine)palladium, sodium carbonate, ethanol:water = 1:1, and toluene were added sequentially to a Schlenk reaction tube. The reaction was carried out under a nitrogen atmosphere at a temperature of 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether to ethyl acetate in a volume ratio of 50:1, to obtain product N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline 6a.

[0022] This patent application also provides a perovskite solar cell, which includes a transparent electrode, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a hole blocking layer, and a metal back electrode stacked sequentially, wherein the hole transport layer is the aforementioned hole transport material molecule.

[0023] This patent application also provides a method for fabricating the aforementioned perovskite solar cell, which specifically includes the following steps:

[0024] Compound 6a was dissolved in 1 mL of chlorobenzene to prepare an organic hole transport material solution with a concentration of 3 mg / mL. This solution was then spin-coated onto conductive glass treated with UV ozone at 3000 rpm. The solution was then subjected to a 110°C test. o Annealing at C for 15 min, and after cooling to room temperature, the perovskite precursor solution was spin-coated onto conductive glass at 5000 rpm. Subsequently, it was annealed at 110 °C. o Annealed at C for 20 min, and after cooling to room temperature, a chlorobenzene solution of [6,6]-phenyl-C61-butyrate isomethyl ester was spin-coated onto the perovskite layer, and then annealed at 70 °C. o Anneal at C for 20 min, cool, then spin-coat the copper bath onto the surface, and heat at 70°C. o Annealing at C for 10 min, and finally, under vacuum, a 15-25 nm electron transport layer and an 85-95 nm top electrode are continuously deposited by thermal evaporation.

[0025] Compared with the prior art, the beneficial effects of this patent application are:

[0026] This patent application describes a method for constructing isoquinoline compounds based on an aryl migration strategy. This method involves a catalyst-catalyzed, additive-promoted tandem reaction of an ortho-vinyl-containing imine ester on an aromatic ring. The reaction proceeds via oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin, achieving the synthesis of C4-aryl or heteroaryl-substituted isoquinolines. This invention exhibits excellent site selectivity, atom economy, and step economy. The resulting C4-aryl or heteroaryl-substituted isoquinolines have significant application value in the fields of pharmaceuticals, materials, and natural products. Attached Figure Description

[0027] Figure 1 Compound 1a prepared for Example 1 of this patent application 1 H NMR spectrum;

[0028] Figure 2 Compound 1a prepared for Example 1 of this patent application 13 C NMR spectrum;

[0029] Figure 3 Compound 1a prepared for Example 1 of this patent application 19 F NMR spectrum;

[0030] Figure 4 Compound 1b prepared for Example 2 of this patent application 1 H NMR spectrum;

[0031] Figure 5 Compound 1b prepared for Example 2 of this patent application 13 C NMR spectrum;

[0032] Figure 6 Compound 1c prepared for Example 3 of this patent application 1 H NMR spectrum;

[0033] Figure 7 Compound 1c prepared for Example 3 of this patent application 13 C NMR spectrum;

[0034] Figure 8 Compound 1d prepared for Example 4 of this patent application 1 H NMR spectrum;

[0035] Figure 9 Compound 1d prepared for Example 4 of this patent application 13 C NMR spectrum;

[0036] Figure 10 Compound 1e prepared for Example 5 of this patent application 1 H NMR spectrum;

[0037] Figure 11 Compound 1e prepared for Example 5 of this patent application 13 C NMR spectrum;

[0038] Figure 12 Compound 1f prepared for Example 6 of this patent application 1 H NMR spectrum;

[0039] Figure 13 Compound 1f prepared for Example 6 of this patent application 13 C NMR spectrum;

[0040] Figure 14 1g of the compound prepared for Example 7 of this patent application 1 H NMR spectrum;

[0041] Figure 15 1g of the compound prepared for Example 7 of this patent application 13 C NMR spectrum;

[0042] Figure 16 Compound 3a prepared for application examples of this patent application 1 H NMR spectrum;

[0043] Figure 17 Compound 3a prepared for application examples of this patent application 13 C NMR spectrum;

[0044] Figure 18Compound 4a prepared for application examples of this patent application 1 H NMR spectrum;

[0045] Figure 19 Compound 4a prepared for application examples of this patent application 13 C NMR spectrum;

[0046] Figure 20 Compound 6a prepared for application examples of this patent application 1 H NMR spectrum;

[0047] Figure 21 Compound 6a prepared for application examples of this patent application 13 C NMR spectrum;

[0048] Figure 22 The current density-voltage characteristic curve of the perovskite solar cell prepared for the test example of this patent application. Detailed Implementation

[0049] The embodiments of this patent application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be construed as limiting the scope of this patent application. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0050] It should be noted that:

[0051] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0052] In this patent application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0053] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this patent application.

[0054] This patent application provides a method for constructing isoquinoline compounds based on an aryl migration strategy. The method involves, in an inert solvent, under the catalysis of a catalyst and the promotion of additives, the addition of a halide ion extractor, an inorganic base, and an organic acid. Ethyl 2-styrenebenzylinate (Formula II) undergoes an oxidative CH bond amination, followed by a tandem reaction in which the aryl group attached to the olefin migrates from the C3 to C4 position, yielding a C4-position aryl or heteroaryl-substituted isoquinoline (Formula I). ​​The reaction is shown below:

[0055] ;

[0056] Where R 1 Substituents include hydrogen, alkyl, halogen, and aryl groups; R 2 It is a saturated or unsaturated straight-chain hydrocarbon group or cyclic hydrocarbon group, or a fused-ring aryl group, containing functional groups such as halogen, ester, nitro, cyano, and acyl groups.

[0057] The principle of this patent application is a tandem reaction involving the oxidative CH bond amination of imine ester compounds of ortho-olefins, catalyzed by a catalyst (e.g., a rhodium-containing catalyst) and promoted by additives (e.g., NBS), and the C3-to-C4 migration of the aryl group attached to the olefin. This process achieves the synthesis of isoquinoline compounds with C4-aryl or heteroaryl substitution. The specific reaction mechanism is as follows:

[0058] First, a trivalent rhodium catalyst (such as dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer [Cp*RhCl2]2) generates an active Rh(III) catalyst A under the action of the halide ion-scavenging agent bis(trifluoromethanesulfonyl)imide silver salt. This catalyst A undergoes electrophilic metallization with (Formula II) to produce intermediate B. Subsequently, an olefin migrates and inserts into the N-Rh bond, forming intermediate C. The entire process from A to C described above is an oxidative CH bond amination. Intermediate C undergoes electrophilic substitution under the action of NBS to generate a C4-brominated intermediate D. Further, intermediate D generates a migration key allyl cation intermediate E under the action of a protic acid. Intermediate E then transitions to intermediate F. Intermediate F undergoes 3,4-aryl migration to form a C3-carbocation intermediate G. Finally, it is deprotonated under the action of acetate to obtain a C4-aryl or heteroaryl-substituted isoquinoline compound (Formula I).

[0059] The possible reaction mechanism flow in the preparation method of this patent application can be represented as follows:

[0060] ;

[0061] In some embodiments, the amount of catalyst used is 1 to 10 mol% of the amount of ethyl 2-styrylbenzylimine (Formula II). This setting ensures that the reaction of the above preparation method can proceed.

[0062] In some preferred embodiments, the inert solvent is any one or more of 1,2-dichloroethane, ethyl acetate, acetone, toluene, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, 1,4-dioxane, N,N-dimethylformamide, N-methylpyrrolidone, ethanol, and water.

[0063] In some preferred embodiments, the catalyst is any one or more of pentamethylcyclopentadienyl rhodium chloride dimer, pentamethylcyclopentadienyl iridium chloride dimer, and triacetonitrile-pentamethylcyclopentadienyl rhodium chloride dimer.

[0064] In some preferred embodiments, the halide ion grabber is any one or more of silver bis(trifluoromethanesulfonyl)imide and silver hexafluoroantimonate.

[0065] In some preferred embodiments, the inorganic base is any one or more of copper acetate monohydrate, sodium carbonate, sodium acetate, and silver carbonate.

[0066] In some embodiments, the organic acid is any one or more of pentanoic acid, glacial acetic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and isobutyric acid.

[0067] In some preferred embodiments, the reaction further requires the addition of an additive, which is any one or more of N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and tetrabromocyclohexadien-1-one.

[0068] In some preferred embodiments, the method for constructing isoquinoline compounds based on the aryl migration strategy specifically includes the following experimental steps:

[0069] In a reaction flask, pentamethylcyclopentadiene rhodium dichloride dimer, bis(trifluoromethanesulfonyl)imide silver, N-bromosuccinimide, copper acetate monohydrate, tervaponic acid, 1,2-dichloroethane, and ethyl 2-styrenebenzylimide were added sequentially to air. The reaction solution was reacted at 80 °C for 12 hours. After the reaction was completed, the mixture was separated by column chromatography to obtain the target compound.

[0070] This patent application also provides a hole transport material molecule, which is prepared by using the above-mentioned C4-position aryl or heteroaryl-substituted isoquinoline (Formula I) as a raw material.

[0071] This patent application also provides a method for preparing the above-mentioned hole transport material molecules, including the following preparation steps:

[0072] S1. Under an atmospheric pressure and air atmosphere, 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole, HCl, and 1,4-dioxane were added sequentially to a Schlenk reaction tube at a temperature of 100°C.o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether and ethyl acetate in a volume ratio of 1:1, to obtain product 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a.

[0073] S2. Under an atmospheric pressure, 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a was added sequentially to a Schlenk reaction tube, and phosphorus oxychloride was reacted at room temperature for 12 hours. The crude product was separated by chromatography using a prepared silica gel plate with a petroleum ether to ethyl acetate volume ratio of 50:1 as the developing or eluent to obtain product 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a.

[0074] S3. Under an air atmosphere at one atmosphere, 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a, triphenylamine 4-borate 5a, tetrakis(triphenylphosphine)palladium, sodium carbonate, ethanol:water = 1:1, and toluene were added sequentially to a Schlenk reaction tube. The reaction was carried out under a nitrogen atmosphere at a temperature of 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether to ethyl acetate in a volume ratio of 50:1, to obtain product N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline 6a.

[0075] This patent application also provides a perovskite solar cell, which includes a transparent electrode, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a hole blocking layer, and a metal back electrode stacked sequentially, wherein the hole transport layer is composed of the aforementioned hole transport material molecules.

[0076] This patent application also provides a method for preparing the above-mentioned perovskite solar cell, characterized by comprising the following steps:

[0077] Compound 6a was dissolved in 1 mL of chlorobenzene to prepare an organic hole transport material solution with a concentration of 3 mg / mL. This solution was then spin-coated onto conductive glass treated with UV ozone at 3000 rpm. The solution was then subjected to a 110°C test. o Annealing at C for 15 min, and after cooling to room temperature, the perovskite precursor solution was spin-coated onto conductive glass at 5000 rpm. Subsequently, it was annealed at 110 °C. o Annealed at C for 20 min, and after cooling to room temperature, a chlorobenzene solution of [6,6]-phenyl-C61-butyrate isomethyl ester was spin-coated onto the perovskite layer, and then annealed at 70 °C. oAnneal at C for 20 min, cool, then spin-coat the copper bath onto the surface, and heat at 70°C. o Annealing at C for 10 min, and finally, under vacuum, a 15-25 nm electron transport layer and an 85-95 nm top electrode are continuously deposited by thermal evaporation.

[0078] Next, specific embodiments will be used to describe in detail the method for constructing isoquinoline compounds based on the aryl migration strategy, the hole transport material molecules and their preparation methods, and the perovskite solar cells and their preparation methods in this patent application.

[0079] 1. Preparation Example

[0080] Example 11 - Ethoxy-4-(4-fluorophenyl)isoquinoline (1a)

[0081] ;

[0082] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E Ethyl 2-(4-fluorostyryl)benzoimide 2a (53.8 mg, 0.20 mmol), trivalent rhodium catalyst [Cp*RhCl2]2 (2.5 mg, 0.004 mmol), silver bis(trifluoromethanesulfonyl)imide (3.9 mg, 0.01 mmol), N-bromosuccinimide (53.4 mg, 0.30 mmol), copper acetate monohydrate (59.7 mg, 0.30 mmol), pentyl acid (10.2 mg, 0.1 mmol), 1,2-dichloroethane (DCE, 1 mL), at 80 o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by chromatography using the prepared silica gel plate with petroleum ether and ethyl acetate in a volume ratio of 55:1 as the developing or eluent, yielding 30.9 mg of 1-ethoxy-4-(4-fluorophenyl)isoquinoline (1a), with a yield of 58%.

[0083] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 1 are shown below. Figure 1 and Figure 2 As shown. From Figure 1 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ8.38-8.35 (m, 1H), 7.91 (s, 1H), 7.74-7.72 (m,1H), 7.65-7.61 (m, 1H), 7.58-7.56 (m, 1H), 7.45-7.41 (m, 2H), 7.21-7.16 (m,2H), 4.61 (q, J = 7.2 Hz, 2H), 1.54 (t, J = 7.2 Hz, 3H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 2 It can be seen that: 13 C NMR (100 MHz, CDCl3): δ 163.6, 161.1, 160.3,139.4, 136.4, 133.5 (d, J CF = 3.0 Hz), 131.7 (d, J CF = 7.0 Hz), 130.5, 126.5 (d, J CF = 10.0 Hz), 124.4 (d, J CF = 18.0 Hz), 119.4, 115.5, 115.3, 62.1, 14.6, the molecular carbon spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 3 It can be seen that, 19 F NMR (125 MHz, CDCl3): δ -115.2, the molecular fluorine spectrum peak energy corresponds one-to-one with the target product, and the number is reasonable. Combining the results of the above analysis of the 1H NMR spectrum, 1C NMR spectrum and fluorine spectrum, it can be seen that the product obtained in Example 1 is 1-ethoxy-4-(4-fluorophenyl)isoquinoline (1a).

[0084] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(4-fluorostyryl)benzoimide 2a was synthesized into 1-ethoxy-4-(4-fluorophenyl)isoquinoline (1a) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 1-ethoxy-4-(4-fluorophenyl)isoquinoline (1a) in a high yield.

[0085] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry, and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 1-ethoxy-4-(4-fluorophenyl)isoquinoline (1a) was synthesized efficiently.

[0086] The chemical transformation described in this application is compatible with fluorine, which is widely used in materials and pharmaceutical fields.

[0087] Example 24: Preparation of 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b)

[0088] ;

[0089] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E Ethyl 2-(4-chlorostyryl)benzoimide 2b (57.0 mg, 0.20 mmol), trivalent rhodium catalyst [Cp*RhCl2]2 (3.7 mg, 0.006 mmol), silver bis(trifluoromethanesulfonyl)imide (2.3 mg, 0.006 mmol), N-bromosuccinimide (39.2 mg, 0.22 mmol), copper acetate monohydrate (47.8 mg, 0.24 mmol), pentyl acid (11.2 mg, 0.11 mmol), 1,2-dichloroethane (DCE, 1 mL), at 80 o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by chromatography using the prepared silica gel plate with petroleum ether and ethyl acetate in a volume ratio of 45:1 as the developing solvent or eluent, yielding 29.4 mg of product 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b), with a yield of 52%.

[0090] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 2 are shown below. Figure 4 and Figure 5 As shown. From Figure 4 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.36 (dd, J = 0.8, 8.4 Hz, 1H), 7.91 (s, 1H), 7.74(d, J = 8.4 Hz, 1H), 7.65-7.61 (m, 1H), 7.56 (t,J = 7.6 Hz, 1H), 7.47 (d, J = 8.4Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 4.61 (q, J = 7.2 Hz, 2H), 1.54 (t, J = 7.2 Hz, 3H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 5 It can be seen 13 C NMR (100 MHz, CDCl3): δ 160.4, 139.4, 136.1, 136.1, 133.4, 131.4, 130.6, 128.7, 126.5, 126.4, 124.5, 124.2, 119.4, 62.1, 14.6. The molecular carbon spectrum peaks correspond one-to-one with the target product, and the number is reasonable. Combining the results of the above 1H and 1C NMR spectrum analysis, it can be concluded that the product obtained in Example 2 is 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b).

[0091] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(4-chlorostyryl)benzoimide 2b was synthesized into 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b) in high yield.

[0092] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 4-(4-chlorophenyl)-1-ethoxyisoquinoline (1b) was synthesized efficiently.

[0093] The chemical transformation in this embodiment can rapidly construct C4-aryl-substituted isoquinoline molecules, and the substituted aryl group contains easily convertible halogen functional groups, thus providing a basis for further functional modification of the molecule.

[0094] Example 34 - Preparation of (1-ethoxyisoquinoline-4-yl)benzonitrile (1c)

[0095] ;

[0096] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E Ethyl 2-(4-cyanostylenyl)benzoimide 2c (55.2 mg, 0.20 mmol), rhodium trivalent catalyst [Cp*RhCl2]2 (6.2 mg, 0.01 mmol), silver bis(trifluoromethanesulfonyl)imide (3.1 mg, 0.008 mmol), N-bromosuccinimide (49.8 mg, 0.28 mmol), copper acetate monohydrate (47.8 mg, 0.24 mmol), pentyl acid (10.2 mg, 0.10 mmol), 1,2-dichloroethane (DCE, 1 mL), at 80 o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by chromatography using the prepared silica gel plate with petroleum ether and ethyl acetate in a volume ratio of 40:1 as the developing solvent or eluent, yielding 30.1 mg of 4-(1-ethoxyisoquinoline-4-yl)benzonitrile (1c), with a yield of 55%.

[0097] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 3 are shown below. Figure 6 and Figure 7 As shown. From Figure 6 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.38 (dd, J = 1.6, 8.4 Hz, 1H), 7.92 (s, 1H),7.80-7.78 (m, 2H), 7.71-7.64 (m, 2H), 7.61-7.58 (m, 3H), 4.62 (q, J = 7.2 Hz, 2H), 1.54 (t, J = 7.2 Hz, 3H). The molecular proton spectrum peak energies correspond one-to-one with the target products, and the number is reasonable. From Figure 7 It can be seen that: 13 C NMR (100 MHz, CDCl3): δ160.9, 142.7, 139.8, 135.6, 132.3, 131.0, 130.8, 126.8, 125.8, 124.7, 123.7, 119.4, 118.8, 111.2, 62.3, 14.6. The molecular carbon spectrum peaks correspond one-to-one with the target product, and the number is reasonable. Therefore, the product obtained in Example 3 is 4-(1-ethoxyisoquinoline-4-yl)benzonitrile (1c).

[0098] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(4-cyanostylenyl)benzoimide 2c was synthesized into 4-(1-ethoxyisoquinoline-4-yl)benzonitrile (1c) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 4-(1-ethoxyisoquinoline-4-yl)benzonitrile (1c) in a high yield.

[0099] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 4-(1-ethoxyisoquinoline-4-yl)benzonitrile (1c) was synthesized efficiently.

[0100] The chemical transformation in this embodiment is compatible with nitrile groups that have strong electron-withdrawing capabilities. These groups can be further functionalized, such as by hydrolysis to generate amides or carboxylic acids, thus providing a platform for the construction of more complex molecules. Furthermore, biaryl nitrile compounds are classic liquid crystal material frameworks.

[0101] Example 4 Preparation of 1-ethoxy-4-(naphth-2-yl)isoquinoline (1d)

[0102] ;

[0103] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. EEthyl 2-(2-(naphthyl)vinyl)benzoimide 2d (60.2 mg, 0.20 mmol), trivalent rhodium catalyst [Cp*RhCl2]2 (3.7 mg, 0.006 mmol), silver bis(trifluoromethanesulfonyl)imide (2.3 mg, 0.006 mmol), N-bromosuccinimide (60.5 mg, 0.34 mmol), copper acetate monohydrate (47.8 mg, 0.24 mmol), terpentine (11.2 mg, 0.11 mmol), 1,2-dichloroethane (DCE, 1 mL), heated to 80°C. o The reaction was continued in C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was then subjected to chromatographic separation using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether to ethyl acetate in a volume ratio of 55:1, yielding 36.0 mg of 1-ethoxy-4-(naphth-2-yl)isoquinoline (1d), with a yield of 60%.

[0104] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 4 are shown below. Figure 8 and Figure 9 As shown. From Figure 8 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.42-8.40 (m, 1H), 8.07 (s, 1H), 7.98-7.90 (m,4H), 7.85 (d, J = 8.0 Hz, 1H), 7.65-7.53 (m, 5H), 4.66 (q, J = 7.2 Hz, 2H), 1.58(t, J = 7.2 Hz, 3H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 9 It can be seen that: 13 CNMR (100 MHz, CDCl3): δ 160.3, 139.7, 136.5, 135.2, 133.5, 132.6, 130.5, 128.8, 128.5, 128.0, 127.9, 127.7, 127.5, 126.4, 126.3, 126.1, 124.6, 124.5, 119.4, 62.1, 14.7. The molecular carbon spectrum peaks correspond one-to-one with the target product, and the number is reasonable. The product obtained in Example 4 is 1-ethoxy-4-(naphth-2-yl)isoquinoline (1d).

[0105] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(2-(naphthyl)vinyl)benzoimide 2d was synthesized into 1-ethoxy-4-(naphthyl-2-yl)isoquinoline (1d) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 1-ethoxy-4-(naphth-2-yl)isoquinoline (1d) in high yield.

[0106] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 1-ethoxy-4-(naphth-2-yl)isoquinoline (1d) was synthesized efficiently.

[0107] The chemical transformation described in this embodiment can be applied to polycyclic aromatic hydrocarbon materials.

[0108] Example 54 - (4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e)

[0109] ;

[0110] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E Ethyl 2-(4-tert-butyl)styryl)-4-chlorobenzoimide 2e (68.2 mg, 0.20 mmol), trivalent rhodium catalyst [Cp*RhCl2]2 (2.5 mg, 0.004 mmol), silver bis(trifluoromethanesulfonyl)imide (3.1 mg, 0.008 mmol), N-bromosuccinimide (71.2 mg, 0.40 mmol), copper acetate monohydrate (39.9 mg, 0.20 mmol), tertivalic acid (10.2 mg, 0.10 mmol), 1,2-dichloroethane (DCE, 1 mL), at 80 o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by silica gel chromatography using a prepared silica gel plate with a volume ratio of petroleum ether to ethyl acetate of 40:1 as the developing or eluent, yielding 46.7 mg of 4-(4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e), with a yield of 69%.

[0111] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 5 are shown below. Figure 10 and Figure 11 As shown. From Figure 10 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.28 (d, J = 8.8 Hz, 1H), 7.96 (s, 1H), 7.81(d, J = 2.0 Hz, 1H), 7.54-7.51 (m, 2H), 7.48 (dd, J = 2.0, 8.8 Hz, 1H), 7.40-7.36(m, 2H), 4.59 (q, J = 7.2 Hz, 2H), 1.53 (t, J = 7.2 Hz, 3H), 1.41 (s, 9H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 11 It can be seen that: 13 C NMR (100 MHz, CDCl3): δ 160.0, 150.6, 140.6, 137.5, 136.9, 133.9, 129.7, 127.1, 126.8, 126.3, 125.6, 123.8, 117.6, 62.2, 34.7, 31.4, 14.6. The molecular carbon spectrum peaks correspond one-to-one with the target product, and the number is reasonable. Based on the above evidence, the product obtained in Example 5 is 4-(4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e).

[0112] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(4-tert-butyl)styryl)-4-chlorobenzoimide (2e) was synthesized into 4-(4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 4-(4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e) in high yield.

[0113] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 4-(4-tert-butyl)phenyl-6-chloro-1-ethoxyisoquinoline (1e) was efficiently synthesized.

[0114] The chemical transformation in this embodiment contains easily convertible halogen functional groups, thus providing a basis for further functional modification of the molecule.

[0115] Example 64: Preparation of (4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f)

[0116] ;

[0117] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E Ethyl 2-(4-(tert-butyl)styryl)-4-methoxybenzoimide 2f (67.4 mg, 0.20 mmol), trivalent rhodium catalyst [Cp*RhCl2]2 (2.5 mg, 0.004 mmol), silver bis(trifluoromethanesulfonyl)imide (2.3 mg, 0.006 mmol), N-bromosuccinimide (64.0 mg, 0.36 mmol), copper acetate monohydrate (59.9 mg, 0.30 mmol), tertivalic acid (10.2 mg, 0.10 mmol), 1,2-dichloroethane (DCE, 1 mL), at 80 o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by silica gel chromatography using a petroleum ether to ethyl acetate in a volume ratio of 60:1 as the developing or eluent, yielding 48.9 mg of 4-(4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f), with a yield of 73%.

[0118] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 6 are shown below. Figure 12 and Figure 13 As shown. From Figure 12 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.26 (dd, J= 0.4, 8.4 Hz 1H), 7.89 (s, 1H),7.52.-7.50 (m, 2H),7.43-7.41(m, 2H), 7.19-7.14 (m, 2H), 4.57 (q, J = 6.8 Hz,2H), 3.82 (s, 3H), 1.52 (t, J = 7.2 Hz, 3H), 1.40 (s, 9H). The molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 13 It can be seen 13 C NMR (100 MHz, CDCl3): δ 160.0, 150.6, 140.6, 137.5, 136.9, 133.8, 129.7, 127.1, 126.8, 126.3, 125.6, 123.8, 117.6, 62.2, 34.6, 31.4, 14.6. The carbon spectral peaks in the molecular spectrum correspond one-to-one with the target product, and the number is reasonable. The product obtained in Example 6 is 4-(4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f).

[0119] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E Ethyl 2-(4-(tert-butyl)styryl)-4-methoxybenzoimide (2f) was synthesized into 4-(4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f) via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80°C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 4-(4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f) in high yield.

[0120] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 4-(4-tert-butyl)phenyl-1-ethoxy-6-methoxyisoquinoline (1f) was synthesized efficiently.

[0121] Example 72: Preparation of 1-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole (1g)

[0122] ;

[0123] Under an atmospheric pressure environment, add ( ) sequentially to a 15 mL Schlenk reaction tube. E 2 g (83.2 mg, 0.20 mmol) of ethyl 2-(2-(9-phenyl-9H-carbazole-3-yl)vinyl)benzoimide, 3.7 mg (0.006 mmol) of trivalent rhodium catalyst [Cp*RhCl2]2, 1.6 mg (0.004 mmol) of silver bis(trifluoromethanesulfonyl)imide, 71.2 mg (0.40 mmol) of N-bromosuccinimide, 19.9 mg (0.20 mmol) of copper acetate monohydrate, 8.2 mg (0.08 mmol) of tertival acid, and 1,2-dichloroethane (DCE, 1 mL) were added at 80 °C. o The reaction was carried out at temperature C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through diatomaceous earth, and concentrated to obtain the crude product. The crude product was separated by silica gel chromatography using a petroleum ether to ethyl acetate in a volume ratio of 50:1 as the developing or eluent, yielding 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole (1 g), 34.8 mg, with a yield of 42%.

[0124] The 1H NMR and 1C NMR spectra of the compounds prepared in Example 7 are shown below. Figure 14 and Figure 15 As shown. From Figure 14 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.40 (dd, J = 0.8, 8.0 Hz, 1H), 8.24 (t, J = 1.2Hz, 1H), 8.17-8.15 (m, 1H), 8.08 (s, 1H), 7.92-7.89 (m, 1H), 7.65-7.63 (m,5H), 7.59-7.55 (m, 1H), 7.52-7.49 (m, 3H), 7.45 (dd, J = 1.2, 5.6 Hz, 3H),7.33-7.29 (m, 1H), 4.65 (q, J = 7.2 Hz, 2H), 1.58 (t, J = 6.8 Hz, 3H), the molecular proton spectrum peak energies correspond one-to-one with the target products, and the number is reasonable. From Figure 15 It can be seen that: 13 C NMR (100 MHz, CDCl3): δ 160.0, 141.3, 140.3, 139.4, 137.6, 137.0, 130.4, 130.0, 129.9, 129.2, 128.3, 128.2, 127.6, 127.1, 127.0, 126.3, 126.2, 124.9, 124.4, 123.6, 123.2, 121.8, 120.4, 120.1, 119.4, 109.9, 109.7. The carbon spectral peaks in the molecular spectrum correspond one-to-one with the target product, and the quantity is reasonable. The product obtained in Example 7 is 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole (1g).

[0125] In this embodiment, a trivalent rhodium catalyst [Cp*RhCl2]2 is used as the catalyst, and N-bromosuccinimide promotes the (… E 2 g of ethyl 2-(2-(9-phenyl-9H-carbazole-3-yl)vinyl)benzoimide was synthesized into 1 g of 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole via a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin. The reaction in this example only required an inert solvent and a relatively mild temperature of 80 °C. o The reaction was carried out at C for 12 hours, then cooled, and then a series of subsequent treatments were performed to obtain the final target product 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole (1g) in a high yield.

[0126] Therefore, the tandem reaction of oxidative amination and aryl migration in this embodiment exhibits good site selectivity, atom economy, and step economy, meeting the requirements of green and sustainable chemistry and enabling the rapid construction of functional molecular libraries with diverse sites. Under mild reaction conditions, 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole (1g) was efficiently synthesized.

[0127] The chemical transformation in this embodiment can serve as a framework for organic optoelectronic materials.

[0128] Application examples

[0129] Preparation and performance characterization of hole transport material molecule: N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline (6a)

[0130] The isoquinoline C4-substituted derivative obtained by the method described in this patent application can be efficiently synthesized into isoquinoline multi-substituted π-unit material molecules through three functionalization modifications. The specific preparation method is as follows:

[0131] ;

[0132] S1. Under an atmospheric pressure and air atmosphere, 1 g (82.0 mg, 0.20 mmol) of 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole, 1.5 mL of HCl (12 M, 1.5 mL), and 1.0 mL of 1,4-dioxane were added sequentially to a 15 mL Schlenk reaction tube at 100 °C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate with petroleum ether and ethyl acetate in a volume ratio of 1:1 as the developing solvent or eluent, yielding product 4-(9-phenyl-9H-carbazol-2-yl)isoquinoline-1(2H)one 3a, a white solid, 64.0 mg, with a yield of 83%.

[0133] The 1H NMR spectrum and 1C NMR spectrum of the compound prepared in step S1 are shown below. Figure 16 and Figure 17 As shown. From Figure 16 It can be seen that: 1 H NMR (400 MHz, d 6-DMSO): δ 11.49 (s, 1H), 8.35-8.27 (m, 3H), 7.70-7.66(m, 5H), 7.59-7.54 (m, 3H), 7.47-7.42 (m, 3H), 7.39 (d, J = 8.0 Hz, 1H), 7.28(t, J = 7.6 Hz, 1H), 7.18 (d, J = 4.0 Hz, 1H), the molecular proton spectrum peak energies correspond one-to-one with the target products, and the number is reasonable. From Figure 17 It can be seen that: 13 C NMR (100 MHz, d 6-DMSO): δThe molecular spectrum peaks correspond one-to-one with the target product, and the number is reasonable. Therefore, the product obtained in step S1 is 4-(9-phenyl-9H-carbazol-2-yl)isoquinoline-1(2H)one 3a.

[0134] S2. Under an atmospheric pressure, 61.7 mg (0.16 mmol) of 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a prepared in step S1 and 1.0 mL of phosphorus oxychloride (POCl3) were added sequentially to a 15 mL Schlenk reaction tube, and the reaction was carried out at room temperature for 12 hours. The crude product was separated by silica gel chromatography using a petroleum ether to ethyl acetate (volume ratio 50:1) as the developing or eluent to obtain 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a, a yellow liquid, 54.9 mg, with a yield of 85%.

[0135] The 1H NMR spectrum and 1C NMR spectrum of the compound prepared in step S2 are shown below. Figure 18 and Figure 19 As shown. From Figure 18 It can be seen that: 1 H NMR (400 MHz, CDCl3): δ 8.47-8.44 (m, 1H), 8.37 (s, 1H), 8.25-8.24(m, 1H), 8.18-8.15 (m, 1H), 8.04-8.02 (m, 1H), 7.72 (dd, J = 3.6, 6.8 Hz, 2H),7.67-7.63 (m, 4H), 7.54-7.51 (m, 3H), 7.46 (dd, J = 1.2, 3.6 Hz, 2H), 7.35-7.31 (m, 1H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 19 It can be seen that: 13 C NMR (100MHz, CDCl3): δThe molecular spectrum peaks 150.4, 141.5, 141.4, 140.7, 137.4, 136.9, 134.4, 132.0, 131.1, 130.0, 128.3, 128.0, 127.7, 127.7, 127.1, 126.6, 126.5, 125.9, 123.7, 123.0, 121.9, 120.4, 120.3, 110.0, 109.9. The peak energies in the molecular spectrum correspond one-to-one with the target product, and the number is reasonable. Therefore, the product obtained in step S2 is 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a.

[0136] S3. Under an atmospheric pressure and air atmosphere, 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a (52.5 mg, 0.13 mmol), triphenylamine 4-borate 5a (56.3 mg, 0.20 mmol), tetra(triphenylphosphine)palladium (7.5 mg, 0.0065 mmol), sodium carbonate (27.5 mg, 0.26 mmol), 0.5 mL each of ethanol and water, and 1.0 mL of toluene were added sequentially to a 15 mL Schlenk reaction tube under a nitrogen atmosphere at 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate with petroleum ether and ethyl acetate in a volume ratio of 50:1 as the developing or eluent, yielding N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline 6a, a yellow solid, 55.7 mg, with a yield of 70%.

[0137] The 1H NMR spectrum and 1C NMR spectrum of the compound prepared in step S3 are shown below. Figure 20 and Figure 21 As shown. From Figure 20 It can be seen 1 H NMR (400 MHz, CDCl3): δ 8.68 (s, 1H), 8.33-8.31 (m, 2H), 8.16 (dd, J =0.8, 7.6 Hz, 1H), 8.10 - 8.06 (m, 1H), 7.71-7.62 (m, 8H), 7.58-7.56 (m, 2H), 7.45-7.43 (m, 2H), 7.31-7.27 (m, 6H), 7.24-7.19 (m, 6H), 7.08-7.03 (m, 2H), the molecular proton spectrum peak energies correspond one-to-one with the target product, and the number is reasonable. From Figure 21 It can be seen that: 13 C NMR (100 MHz, CDCl3): δ 159.3, 148.3, 147.6, 142.4, 141.3, 140.5, 137.5, 135.8, 133.5, 132.8, 131.0, 130.1, 129.9, 129.3, 128.9, 128.2, 127.8, 127.6, 127.1, 126.7, 126.4, 126.3, 125.6, 124.7, 123.6, 123.2, 123.1, 123.0, 122.0, 120.4, 120.2, 110.0, 109.9. The peaks in the molecular spectrum correspond one-to-one with the target product, and the number is reasonable. Therefore, the product obtained in step S3 is N,N-diphenyl-4-(4-(9-phenyl-9H-carbazole-3-yl)isoquinoline-1-yl)aniline 6a.

[0138] Test Example: Fabrication of Perovskite Solar Cells

[0139] The steps for preparing perovskite solar cells from N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline (6a), a material molecule with polysubstituted π-unit isoquinoline, are as follows:

[0140] 3.0 mg of compound 6a was dissolved in 1 mL of chlorobenzene solvent to prepare an organic hole transport material solution with a concentration of 3 mg / mL. This solution was then spin-coated onto conductive glass treated with UV ozone at 3000 rpm. The solution was then subjected to a 110°C test. o Annealing at C for 15 min. After cooling to room temperature, the perovskite precursor solution was spin-coated onto the conductive glass at 5000 rpm. Subsequently, it was annealed at 110 °C. o Annealing at C for 20 min. After cooling to room temperature, a chlorobenzene solution of [6,6]-phenyl-C61-butyrate isomethyl ester (PCBM) was spin-coated onto the perovskite layer and annealed at 70 °C. o Anneal at C for 20 min, cool, and then spin-coat copper bath (BCP) onto the PCBM, then heat at 70°C. o Annealing at C for 10 min. Finally, under vacuum, a 15-25 nm electron transport layer and an 85-95 nm top electrode were continuously deposited using thermal evaporation.

[0141] In this application example, the perovskite solar cell provided was measured under standard AM 1.5 simulated sunlight. The optimal device performance of the perovskite solar cell is: 100 mW / cm² light intensity. 2 Short-circuit photocurrent densityJ sc is 20.54 mA / cm 2 The open-circuit optical voltage (Voc) is 0.68 V, the fill factor (FF) is 0.40, and the power conversion efficiency (PCE) is 9.24%. The device performance test results are shown in Table 1. J -V curve as shown Figure 22 As shown, the photoelectric conversion performance test results indicate that the photoelectric material molecules of isoquinoline multi-substituted π units synthesized based on the aryl migration strategy (such as N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline 6a) have certain photoelectric conversion performance.

[0142] Table 1

[0143] ;

[0144] In summary, this patent application provides a method for constructing isoquinoline compounds based on an aryl migration strategy. Specifically, in an inert solvent, with the aid of a catalyst and additives, a halide ion extractor, an inorganic base, and an organic acid are added. Ethyl 2-styrenebenzylinate (Formula II) undergoes an oxidative CH bond amination and a tandem reaction involving the migration of the aryl group attached to the olefin from the C3 to C4 position, yielding a C4-position aryl or heteroaryl-substituted isoquinoline (Formula I). ​​The reaction is shown below:

[0145] ;

[0146] Where R 1 Substituents include hydrogen, alkyl, halogen, and aryl groups; R 2 It is a saturated or unsaturated straight-chain hydrocarbon group or cyclic hydrocarbon group, or a fused-ring aryl group, containing functional groups such as halogen, ester, nitro, cyano, and acyl groups.

[0147] This patent application provides a method for constructing isoquinoline compounds based on an aryl migration strategy. This method involves a trivalent rhodium-catalyzed, N-bromosuccinimide-promoted reaction of an ortho-vinyl-containing imine ester on an aromatic ring. The reaction proceeds via oxidative CH bond amination and a C3-to-C4 migration of the aryl group attached to the olefin, achieving the synthesis of C4-aryl or heteroaryl-substituted isoquinolines. This synthetic approach allows for the one-pot synthesis of C4-aryl or heteroaryl-substituted isoquinolines. This method not only boasts a wide substrate applicability and good atom and step economy, but more importantly, the resulting C1-ethoxyated isoquinoline can be further converted into isoquinolinones and C1-halogenated isoquinoline derivatives.

Claims

1. A method for constructing isoquinoline compounds based on an aryl migration strategy, characterized in that: In an inert solvent, with the aid of a catalyst and additives, ethyl 2-styrenebenzimidate (Formula II) undergoes a tandem reaction involving oxidative CH bond amination and C3-to-C4 migration of the aryl group attached to the olefin, catalyzed by a catalyst and promoted by additives, after the addition of a halide ion extractant, additive 2, and an organic acid, to yield a C4-aryl or heteroaryl-substituted isoquinoline (Formula I). ​​The reaction is shown below: ； Where R 1 Substituents include hydrogen, alkyl, halogen, and aryl groups; R 2 It is one of the functional groups of fluorine, chlorine, cyano, and tert-butyl; or when the ethyl 2-styrenebenzimidate shown in Formula II is 2d, the aryl or heteroaryl substituted isoquinoline at the C4 position shown in Formula I is 1d, wherein the molecular structural formulas of 2d and 1d are as follows: and ; Alternatively, when the amount of ethyl 2-styrenebenzimidate shown in Formula II is 2g, the amount of C4-aryl or heteroaryl-substituted isoquinoline shown in Formula I is 1g, wherein the molecular structural formulas for 2g and 1g are as follows: and ; The catalyst is selected from either pentamethylcyclopentadienyl rhodium chloride dimer or triacetonitrile-pentamethylcyclopentadienyl rhodium chloride dimer; The additive is selected from any one of N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and tetrabromocyclohexadien-1-one; The halide ion grabber is selected from either silver bis(trifluoromethanesulfonyl)imide or silver hexafluoroantimonate. The organic acid is selected from any one of pentanoic acid, glacial acetic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and isobutyric acid; The additive 2 is either copper acetate monohydrate or sodium acetate.

2. The method for constructing isoquinoline compounds based on the aryl migration strategy according to claim 1, characterized in that: The amount of catalyst used is 1 to 10 mol% of the amount of ethyl 2-styrenebenzimidate (Formula II).

3. The method for constructing isoquinoline compounds based on the aryl migration strategy according to claim 1, characterized in that: The inert solvent is selected from any one of 1,2-dichloroethane, ethyl acetate, acetone, toluene, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, 1,4-dioxane, N,N-dimethylformamide, N-methylpyrrolidone, and ethanol.

4. The method for constructing isoquinoline compounds based on the aryl migration strategy according to claim 1, characterized in that: The specific experimental procedures include the following: In a reaction flask, pentamethylcyclopentadiene rhodium dichloride dimer, bis(trifluoromethanesulfonyl)imide silver, N-bromosuccinimide, copper acetate monohydrate, tervaponic acid, 1,2-dichloroethane, and ethyl 2-styrenebenzylimide were added sequentially to air. The reaction solution was reacted at 80 °C for 12 hours. After the reaction was completed, the mixture was separated by column chromatography to obtain the target compound.

5. A method for preparing hole transport material molecules, characterized in that: The preparation steps include the following: S1. Under an atmospheric pressure, 1 g of 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole as described in claim 1, HCl, and 1,4-dioxane were sequentially added to a Schlenk reaction tube at a temperature of 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether and ethyl acetate, with a volume ratio of 1:1, to obtain product 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a. S2. Under an atmospheric pressure, 4-(9-phenyl-9H-carbazole-2-yl)isoquinoline-1(2H)one 3a was added sequentially to a Schlenk reaction tube, and phosphorus oxychloride was reacted at room temperature for 12 hours. The crude product was separated by chromatography using a prepared silica gel plate. The selected developing solvent or eluent was petroleum ether and ethyl acetate, with a volume ratio of 50:1, to obtain product 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a; S3. Under an atmospheric pressure and air atmosphere, 2-(1-chloroisoquinoline-4-yl)-9-phenyl-9H-carbazole 4a, triphenylamine 4-borate 5a, tetra(triphenylphosphine)palladium, sodium carbonate, ethanol, water, and toluene are added sequentially to a Schlenk reaction tube, wherein the ethanol:water ratio is 1:

1. The reaction is carried out under a nitrogen atmosphere at a temperature of 100°C. o The reaction was carried out in C for 12 hours. The crude product was separated by chromatography using the prepared silica gel plate. The selected developing solvent or eluent was petroleum ether and ethyl acetate, with a volume ratio of 50:1, to obtain product N,N-diphenyl-4-(4-(9-phenyl-9H-carbazol-3-yl)isoquinoline-1-yl)aniline 6a. The preparation method further includes the following steps: preparing 1g of 2-(1-ethoxyisoquinoline-4-yl)-9-phenyl-9H-carbazole by the method for constructing isoquinoline compounds based on the aryl migration strategy according to claim 1.

6. A method for fabricating a perovskite solar cell, characterized in that, Specifically, the following steps are included: Compound 6a of claim 5 was dissolved in 1 mL of chlorobenzene solvent to prepare an organic hole transport material solution with a concentration of 3 mg / mL. This solution was then spin-coated onto conductive glass treated with ultraviolet ozone at 3000 rpm. o Annealing at C for 15 min, and after cooling to room temperature, the perovskite precursor solution was spin-coated onto conductive glass at 5000 rpm. Subsequently, it was annealed at 110 °C. o Annealed at C for 20 min, and after cooling to room temperature, a chlorobenzene solution of [6,6]-phenyl-C61-butyrate isomethyl ester PCBM was spin-coated onto the perovskite layer, and then annealed at 70°C. o Anneal at C for 20 min, cool, then spin-coat the copper bath onto the PCBM, and heat at 70°C. o Annealing at C for 10 min, and finally, under vacuum, continuously depositing an electron transport layer of 15-25 nm and a top electrode of 85-95 nm by thermal evaporation; the preparation method further includes the following step: preparing compound 6a according to the method for preparing hole transport material molecules according to claim 5.

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