Preparation method of fullerene pyrrolidino quinazolinone

Abstract

The invention discloses a preparation method of fullerene pyrrolidino quinazolinone, and belongs to the technical field of organic synthesis, namely the field of fullerene derivative synthesis, and the specific method is as follows: fullerene, a 2-aminobenzamide compound and an aldehyde compound are used as reaction substrates, lead acetate and DMAP are used as accelerators, o-dichlorobenzene is used as a solvent, and the fullerene pyrrolidino quinazolinone is prepared through a one-pot reaction. And carrying out one-step thermal reaction in the air to obtain the target product fullerene pyrrolidine quinazolinone. The method is simple in step, the obtained fullerene pyrrolidino quinazolinone derivatives are novel in structure, the variety of fullerene derivatives is greatly enriched, and meanwhile the fullerene pyrrolidino quinazolinone derivatives have good substrate universality and wide application prospects.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing fullerene pyrrolidine quinazolinone based on lead acetate promotion. Background Technology

[0002] The unique three-dimensional hollow carbon molecular structure and photoelectric properties of fullerenes have attracted great interest in materials science, biomedicine, supramolecular chemistry, organic photovoltaics, and perovskite solar cells. Chemical modification of the fullerene framework and the construction of functional fullerene systems by incorporating diverse functional groups have become one of the core directions of fullerene research.

[0003] As shown in Equation 1, in 2018, Professor Wang Guanwu's research group at the University of Science and Technology of China reported that, under the promotion of Cu(OAc)2·H2O, C 60 A novel fullerene tetrahydropyridazine compound was synthesized by cycloaddition reaction with acylhydrazine compounds. Mechanistic studies showed that the formation of the product was dominated by the heterodiels-Alder process (Organic Chemistry Frontiers, 2018, 5: 1188-1193).

[0004] Formula 1.

[0005] As shown in Equation 2, in 2019, Professor Wang Guanwu's research group also used triethylamine and aromatic aldehydes with C 60 The reaction produced 2-arylene-substituted

[60] fullerene pyrrolidine (European Journal of Organic Chemistry, 2019, 2019: 6504-6509).

[0006] Equation 2.

[0007] As shown in Equation 3, in 2021, Liu Tongxin's research group at Henan Normal University described the first metal-free catalytic multicomponent cyclization reaction of

[60] fullerenes. Using I2 as a catalyst, C... 60 A series of fullerene-1,2-tetrahydrocarbazole derivatives were obtained by cyclization of ketones and indoles via [2+2+2] cyclization reaction (Organic Letters, 2021, 23: 1775-1781).

[0008] Formula 3.

[0009] As shown in Formula 4, in 2023, Professor Li Fabao's research group at Hubei University reported the successful synthesis of ketone-containing

[60] fullerene pyrrolidine dimer derivatives by the aminomethylation reaction of ketone-containing

[60] fullerene pyrrolidine and N-unsubstituted

[60] fullerene pyrrolidine with paraformaldehyde under the promoting effect of TsOH·H2O (Organic & Biomolecular Chemistry, 2023, 21: 4881-4892).

[0010] Formula 4. CN120623098A discloses a fullerene-pyrrolidine derivative as an electron transport layer material, which significantly improves the photoelectric performance and stability of tin-based perovskite solar cells. The device fabricated from the F6 / F12 composite material achieves a PCE as high as 12.0%. Furthermore, these derivatives exhibit excellent chemical stability and environmental adaptability, effectively extending the device's lifespan and providing strong support for the commercialization of tin-based perovskite solar cells.

[0011] Current reports indicate that novel fullerene pyrrolidine derivatives have great potential and prospects in the perovskite field. We urgently need to consider more effective synthesis strategies to prepare different fullerene pyrrolidine derivatives to broaden their application market. Summary of the Invention

[0012] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art, provide a method for the synthesis of fullerene pyrrolidine and quinazolinone based on lead acetate, and verify the universality of the substrate.

[0013] The present invention adopts the following technical solution to achieve the above objectives: a method for preparing fullerene pyrrolidine quinazolinone, which uses fullerene and 2-aminobenzamide compounds and aldehyde compounds as raw materials, lead acetate and DMAP as promoters, and o-dichlorobenzene as solvent, and heats in air to undergo an aldehyde-amine reaction to synthesize fullerene pyrrolidine quinazolinone. The 2-aminobenzamide compounds are 2-aminobenzamide or derivatives thereof whose benzene ring is substituted by a substituent R1, wherein the substituent R1 is one of alkyl, halogroup, or alkoxy group; The aldehyde compounds include The structure, wherein R2 is one of alkyl and benzyl groups; The fullerene is C 60 Fullerenes.

[0014] Furthermore, the synthetic equation for the above aldehyde-amine reaction is as follows: .

[0015] Furthermore, the 2-aminobenzamide compound is 2-aminobenzamide, and the aldehyde compound is n-propanal, n-butyral, n-pentanal, and phenylpropanal.

[0016] Furthermore, the aldehyde compound is n-propionaldehyde, and the 2-aminobenzamide compound is 2-amino-5-methylbenzamide, 2-amino-5-methoxybenzamide, 2-amino-5-fluorobenzamide, 2-amino-5-chlorobenzamide, and 2-amino-5-bromobenzamide.

[0017] This invention also provides specific steps for the preparation of the above-mentioned fullerene pyrrolidine quinazolinone: The raw material fullerene C was added to the reaction vessel. 60 2-Aminobenzamide compounds and aldehyde compounds were added, along with lead acetate and DMAP as promoters, and o-dichlorobenzene as solvent. The mixture was fully dissolved under ultrasound. The reaction vessel was then heated and stirred on a constant temperature heater. After the reaction was completed, the reaction solution was cooled to room temperature and then separated in a silica gel column using carbon disulfide as eluent. Unreacted fullerenes were obtained first, and then further separated using carbon disulfide and dichloromethane as eluents. Finally, a brown solid fullerene pyrrolidine quinazolinone derivative was obtained.

[0018] Furthermore, the constant temperature heating temperature is 170 ℃, and the molar ratio of fullerene, 2-aminobenzamide compounds and aldehyde compounds, lead acetate and DMAP is 1:2~8:2~8:1~8:0.5~2.

[0019] Furthermore, the structural formula of the fullerene pyrrolidine quinazolinone is as follows: R1 is one of alkyl, halogroup, or alkoxy, and R2 is one of alkyl or benzyl; the fullerene is C 60 Fullerenes.

[0020] Furthermore, the fullerene pyrrolidine quinazolinone obtained based on the above preparation method includes one of the following compounds: .

[0021] The present invention also proposes an application of the above-mentioned fullerene pyrrolidine quinazolinone to the preparation of electron transport materials for perovskite solar cells.

[0022] Compared with the prior art, the present invention has the following outstanding advantages: 1. This invention provides a method for preparing fullerene pyrrolidine quinazolinone with high yield and promising application prospects in the field of perovskite solar cells. Specifically, its excellent electron transport capability and stability make it an important electron transport material that plays a key role in perovskite solar cells and improves device efficiency. 2. The fullerene pyrrolidine derivative obtained by this method has a novel structure, enriching the preparation methods of novel fullerene pyrrolidine derivatives. The product, fullerene pyrrolidine quinazolinone, has excellent solubility and selectivity and is easy to separate and purify. 3. The substrates used in this method, such as 2-aminobenzamide compounds and aldehyde compounds, have a wide range of applications and good universality. Most of them are inexpensive and readily available. At the same time, the method for preparing fullerene pyrrolidine and quinazolinone is simple. The product can be obtained by one-step thermal reaction in air. The preparation conditions and process are relatively relaxed compared with other existing technologies, which reduces the difficulty of preparing fullerene pyrrolidine derivatives. 4. Thermogravimetric analysis demonstrates that the product prepared by this method has good overall thermal stability and is suitable for use at 368°C. o C's previous work; 5. The redox potential diagram of the compound obtained by cyclic voltammetry can demonstrate that it has certain redox activity and has certain application potential in the field of solar cells. Attached Figure Description

[0023] Figure 1 This is for Example 1 of the present invention

[60] fullerene pyrrolidine quinazolinone A 1 H NMR spectrum; Figure 2 This is for Example 1 of the present invention

[60] fullerene pyrrolidine quinazolinone A 13 C NMR spectrum; Figure 3 This is for Example 2 of the present invention

[60] fullerene pyrrolidine quinazolinone B. 1 H NMR spectrum; Figure 4 This is for Example 2 of the present invention

[60] fullerene pyrrolidine quinazolinone B. 13 C NMR spectrum; Figure 5 This is for Example 3 of the present invention

[60] fullerene pyrrolidine quinazolinone C 1 H NMR spectrum; Figure 6 This is for Example 3 of the present invention

[60] fullerene pyrrolidine quinazolinone C 13 C NMR spectrum; Figure 7This is for Example 4 of the present invention

[60] fullerene pyrrolidine quinazolinone D. 1 H NMR spectrum; Figure 8 This is for Example 4 of the present invention

[60] fullerene pyrrolidine quinazolinone D. 13 C NMR spectrum; Figure 9 This is for Example 5 of the present invention

[60] fullerene pyrrolidine quinazolinone E 1 H NMR spectrum; Figure 10 This is for Example 5 of the present invention

[60] fullerene pyrrolidine quinazolinone E 13 C NMR spectrum; Figure 11 This is for Example 6 of the present invention

[60] fullerene pyrrolidine quinazolinone F. 1 H NMR spectrum; Figure 12 This is for Example 6 of the present invention

[60] fullerene pyrrolidine quinazolinone F. 13 C NMR spectrum; Figure 13 This is for Example 7 of the present invention

[60] fullerene pyrrolidine quinazolinone G 1 H NMR spectrum; Figure 14 This is for Example 7 of the present invention

[60] fullerene pyrrolidine quinazolinone G 13 C NMR spectrum; Figure 15 This is for Example 8 of the present invention

[60] fullerene pyrrolidine quinazolinone H. 1 H NMR spectrum; Figure 16 This is for Example 8 of the present invention

[60] fullerene pyrrolidine quinazolinone H. 13 C NMR spectrum; Figure 17 This is for Example 9 of the present invention

[60] fullerene pyrrolidine quinazolinone I. 1 H NMR spectrum; Figure 18 This is for Example 9 of the present invention

[60] fullerene pyrrolidine quinazolinone I. 13 C NMR spectrum; Figure 19 This is a thermogravimetric analysis (TGA) diagram of fullerene pyrrolidine quinazolinone A for the implementation of this invention

[60] ; Figure 20 This is the CV curve of fullerene pyrrolidine quinazolinone A for the implementation of this invention

[60] . Detailed Implementation

[0024] The present invention will be further described in detail below through embodiments, but the content of the invention is not limited to these embodiments.

[0025] Example 1 This embodiment describes

[60] fullerene pyrrolidine quinazolinone A Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-aminobenzamide (34.0 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (4-dimethylaminopyridine) (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was dissolved completely by sonication with 6 mL of o-dichlorobenzene. The solution was then incubated at 170 °C under air. o The mixture was heated and stirred in an oil bath for 4.5 h, and then tracked using thin-layer chromatography (TLC) plate spotting.

[0026] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone A. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone A was 33%.

[0027] The reaction synthesis equation is as follows: .

[0028] like Figure 1 As shown,

[60] fullerene pyrrolidine quinazolinone A 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.28-8.25 (m, 1H), 7.83-7.81 (m, 1H), 7.81 (d, J = 1.1 Hz, 1H), 7.51-7.48 (m, 1H), 5.23 (q, J = 7.4 Hz, 1H), 2.28 (d, J = 7.4 Hz, 3H).

[0029] like Figure 2 As shown,

[60] fullerene pyrrolidine quinazolinone A 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 159.56 (C=O), 157.81 (C=N), 154.04,149.50, 147.23, 147.08, 146.65, 146.51, 146.31, 145.49, 145.44, 145.37,145.33, 145.27, 145.17, 145.14, 144.92, 144.89, 144.59, 144.52 (2C), 144.50,144.37, 144.29, 144.26, 144.11, 144.09, 143.91 (2C), 143.55, 143.49, 143.32,143.27, 143.03, 141.88, 141.74, 141.70, 141.64, 141.62, 141.53, 141.07,141.01, 140.94, 140.87, 140.84, 140.80, 140.77, 140.66, 140.45, 140.09,139.53, 139.17, 137.07, 136.81, 136.10 (2C), 135.23, 135.17, 133.79, 132.62,126.53 (2C, aryl C), 126.11 (2C, aryl C), 125.90 (aryl C), 120.73 (aryl C),83.28, 66.99, 49.42, 18.22.

[0030] Example 2 This embodiment describes

[60] fullerene pyrrolidine quinazolinone B Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-aminobenzamide (34.0 mg, 0.25 mmol), n-butyraldehyde (22 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was dissolved completely by sonication with 6 mL of o-dichlorobenzene. The solution was then dissolved in air at 170 °C. o The mixture was heated and stirred in an oil bath for 5 h, and then tracked using thin-layer chromatography (TLC) plate spotting.

[0031] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone B. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone B was 21%.

[0032] The reaction synthesis equation is as follows: .

[0033] like Figure 3 As shown,

[60] fullerene pyrrolidine quinazolinone B 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.29-8.23 (m, 1H), 7.79 (dd, J = 10.5, 3.7 Hz, 2H), 7.52-7.44(m, 1H), 5.09-4.92 (m, 1H), 2.88-2.75 (m, 2H), 1.65 (td, J = 7.3, 3.1 Hz, 3H).

[0034] like Figure 4 As shown,

[60] fullerene pyrrolidine quinazolinone B 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 160.11 (C=O), 157.98 (C=N), 154.99,149.82, 147.71, 147.57, 147.24, 147.17, 146.85, 146.07, 146.01, 145.95,145.91 (2C), 145.81, 145.72 (2C), 145.45 (2C), 145.37, 145.30, 145.12,144.92, 144.82 (2C), 144.69, 144.64, 144.56, 144.45, 144.14, 144.01, 143.95,143.87, 143.52, 142.47, 142.31, 142.29, 142.22 (2C), 142.19, 142.15, 141.67,141.61, 141.52, 141.33 (2C), 141.32, 141.27, 140.91, 140.64, 139.97, 139.32,137.55, 137.34, 136.39, 135.98, 135.95, 134.17 (2C), 133.19, 127.09 (2C, arylC), 126.59 (aryl C), 126.31 (2C, aryl C), 121.25 (aryl C), 83.98, 67.60, 55.24, 26.74, 13.06.

[0035] Example 3 This embodiment describes

[60] fullerene pyrrolidine quinazolinone C Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-aminobenzamide (34.0 mg, 0.25 mmol), n-pentanal (27 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was dissolved completely by sonication with 6 mL of o-dichlorobenzene. Then, the mixture was incubated at 170 °C under air. o The mixture was heated and stirred in an oil bath for 5 h, and then tracked using thin-layer chromatography (TLC) plate spotting.

[0036] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidinequinazolinone C. In this example, the yield of

[60] fullerene pyrrolidinequinazolinone C was 18%.

[0037] The reaction synthesis equation is as follows: .

[0038] like Figure 5 As shown,

[60] fullerene pyrrolidine quinazolinone C 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.26 (d, J = 8.5 Hz, 1H), 7.84-7.78 (m, 2H), 751-7.47 (m,1H), 5.08 (t, J = 6.4 Hz, 1H), 2.83-2.73 (m, 1H), 2.68-2.61 (m, 1H), 2.37-2.25 (m,1H), 2.15-2.02 (m, 1H), 1.15 (t, J = 7.3 Hz, 3H).

[0039] like Figure 6 As shown,

[60] fullerene pyrrolidine quinazolinone C 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 159.83 (C=O), 157.80 (C=N), 154.59,149.50, 147.39, 147.26, 146.87, 146.85, 146.54, 145.76, 145.70, 145.63,145.60, 145.57, 145.49, 145.38, 145.16 (2C), 145.06, 145.00, 144.80 (2C),144.60, 144.50 (2C), 144.36, 144.31, 144.22, 144.14, 143.82, 143.70, 143.62,143.54, 143.20, 142.14 (2C), 141.98 (2C), 141.90, 141.87, 141.82, 141.35,141.28, 141.19, 141.01 (2C), 140.94 (2C), 140.60, 140.31, 139.62, 138.96,137.23, 137.01, 136.12, 135.59 (3C), 133.94, 132.89, 126.80 (2C, aryl C),126.28 (2C, aryl C), 126.05 (aryl C), 120.91 (aryl C), 83.62, 67.37, 53.35,35.25, 21.39, 13.94.

[0040] Example 4 This embodiment describes

[60] fullerene pyrrolidine quinazolinone D Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-aminobenzamide (34.0 mg, 0.25 mmol), phenylpropionaldehyde (33 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. Then, the mixture was heated and stirred in an oil bath at 170 °C for 4.5 h under air. Thin-layer chromatography (TLC) was used for monitoring.

[0041] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone D. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone D was 19%.

[0042] The reaction synthesis equation is as follows: .

[0043] like Figure 7 As shown, it is

[60] fullerene pyrrolidine quinazolinone D. 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.29 (d, J = 8.6 Hz, 1H), 7.87-7.79 (m, 2H), 7.53-7.49 (m,1H), 7.37 (d, J = 7.4 Hz, 2H), 7.11 (t, J = 7.5 Hz, 2H), 7.04 (t, J = 7.3 Hz, 1H), 5.69 (dd, J = 10.2, 3.9 Hz, 1H), 4.41 (dd, J = 15.2, 4.0 Hz, 1H), 3.86 (dd, J = 15.2, 10.2 Hz, 1H).

[0044] like Figure 8 As shown, it is

[60] fullerene pyrrolidine quinazolinone D. 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 160.19 (C=O), 157.75 (C=N), 154.37,149.11, 147.62, 147.39, 147.21, 147.03, 146.74, 146.01, 145.96, 145.92,145.81 (2C), 145.73, 145.67, 145.65, 145.62, 145.41, 145.05 (2C), 144.91,144.83, 144.70 (2C), 144.63, 144.49, 144.45, 144.38, 143.96, 143.89, 143.81,143.78, 143.39, 142.28 (2C), 142.22, 142.12 (2C), 142.06, 142.01, 141.62,141.57, 141.28, 141.25, 141.18, 141.10, 141.07, 140.89, 140.76, 140.55,139.24, 137.92, 137.51, 137.35, 137.24, 136.33, 135.95, 135.53, 134.29,133.097 (aryl C), 128.97 (3C, aryl C), 128.09 (3C, aryl C), 127.007 (aryl C),126.627 (aryl C), 126.477 (aryl C), 126.447 (aryl C), 121.277 (aryl C),84.14, 67.36, 54.09, 39.10.

[0045] Example 5 This embodiment describes

[60] fullerene pyrrolidine quinazolinone E Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-amino-5-methylbenzamide (37.5 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. The mixture was then heated and stirred in an oil bath at 170 °C for 4.5 h under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0046] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone E. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone E was 41%.

[0047] The reaction synthesis equation is as follows: .

[0048] like Figure 9 As shown,

[60] fullerene pyrrolidine quinazolinone E 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.05 (s, 1H), 7.69 (d, J = 8.3 Hz, 1H), 7.61 (dd, J = 8.3, 2.1Hz, 1H), 5.18 (q, J = 7.3 Hz, 1H), 2.54 (s, 3H), 2.25 (d, J = 7.4 Hz, 3H).

[0049] like Figure 10 As shown,

[60] fullerene pyrrolidine quinazolinone E 13 C NMR spectrum 13C NMR (150MHz, CS2 / CDCl3) (all 1C unless indicated) δ 159.32 (C=O), 156.66 (C=N),153.85, 149.33, 146.84, 146.37, 146.27, 146.02, 145.21, 145.15, 145.12,145.08, 145.05, 145.01, 144.98, 144.88, 144.83, 144.63, 144.61, 144.35,144.25, 144.23, 144.08, 144.00, 143.97, 143.83, 143.80, 143.74, 143.62,143.27, 143.21, 143.04, 142.99, 142.78, 141.60, 141.45, 141.41, 141.36,141.33, 141.25, 140.79, 140.73, 140.66, 140.60, 140.56, 140.51, 140.48,140.37, 140.18, 139.82, 139.24, 138.87, 136.75, 136.49, 135.83 (3C), 135.45,134.95, 134.90, 132.34 (2C, aryl C), 126.14 (aryl C), 125.33 (2C, aryl C), 120.21 (aryl C), 82.93, 66.78, 48.48, 20.37, 16.92.

[0050] Example 6 This embodiment describes

[60] fullerene pyrrolidine quinazolinone F Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-amino-5-methoxybenzamide (41.6 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. The mixture was then heated and stirred in an oil bath at 170 °C for 4.5 h under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0051] After the reaction was completed, the reaction solution was first cooled with room temperature water, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, followed by further separation using a mixed solution of carbon disulfide and dichloromethane as the eluent, ultimately yielding a brown solid,

[60] fullerene pyrrolidine quinazolinone F. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone F was 36%. The reaction synthesis equation is as follows: .

[0052] like Figure 11 As shown,

[60] fullerene pyrrolidine quinazolinone F 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 7.72 (d, J = 8.9 Hz, 1H), 7.63 (d, J = 3.0 Hz, 1H), 7.38 (dd, J= 8.9, 3.0 Hz, 1H), 5.19 (q, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.26 (d, J = 7.3Hz, 3H).

[0053] like Figure 12 As shown,

[60] fullerene pyrrolidine quinazolinone F 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 159.70 (C=O), 157.61 (C=N), 155.64,154.40, 149.88, 147.37, 146.91, 146.78, 146.55, 145.74, 145.69, 145.65,145.63, 145.58, 145.52, 145.42, 145.37, 145.18, 145.15, 144.87 (2C), 144.77,144.61, 144.54, 144.51, 144.37, 144.34, 144.26, 144.17, 143.80, 143.75,143.57, 143.54, 143.31, 142.14, 142.06, 141.99, 141.96, 141.90, 141.87,141.78, 141.33, 141.28, 141.21, 141.15, 141.10, 141.03, 140.89, 140.73,140.36, 139.79, 139.42, 137.29, 137.02 (2C), 136.37, 135.48, 135.42 (2C),132.85, 128.18 (2C, aryl C), 124.26 (aryl C), 121.72 (2C, aryl C), 105.48(aryl C), 83.43, 67.39, 54.80, 48.90, 17.46.

[0054] Example 7 This embodiment describes

[60] fullerene pyrrolidine quinazolinone G Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-amino-5-fluoro-benzamide (38.5 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. The mixture was then heated and stirred in an oil bath at 170 °C for 5.5 h under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0055] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone G. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone G was 24%.

[0056] The reaction synthesis equation is as follows: .

[0057] like Figure 13 As shown,

[60] fullerene pyrrolidine quinazolinone G 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 7.91-7.82 (m, 2H), 7.60-7.55 (m, 1H), 5.23 (q, J = 7.3 Hz, 1H), 2.26 (d, J = 7.4 Hz, 3H).

[0058] like Figure 14 It is

[60] fullerene pyrrolidine quinazolinone G 13 C NMR spectrum 13 C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 159.96 (d, J C-F=247.9Hz, aryl C), 158.92 (C=O), 157.44 (C=N), 154.04, 149.49, 147.16, 146.82, 146.59, 146.48, 145.66,145.61 (2C), 145.55, 145.50, 145.44, 145.34, 145.09, 145.07, 144.69, 144.63(2C), 144.54, 144.46, 144.43, 144.40, 144.27 (2C), 144.07, 144.00, 143.78,143.70, 143.64, 143.46, 143.43, 143.12, 142.06, 141.91, 141.88, 141.80 (2C),141.69, 141.23, 141.17, 141.09, 141.02, 141.00, 140.97, 140.92, 140.83,140.57, 140.20, 139.70, 139.34, 137.26, 136.99 (2C), 136.30, 135.42, 135.28(2C), 132.72, 128.96 (d, J C-F =6.9 Hz, aryl C), 122.41 (aryl C), 122.25 (2C,aryl C), 111.11 (d, J C-F =23.1Hz, aryl C), 83.43, 67.13, 48.93, 17.28.

[0059] Example 8 This embodiment describes

[60] fullerene pyrrolidine quinazolinone H Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-amino-5-chloro-benzamide (42.7 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. The mixture was then heated and stirred in an oil bath at 170 °C for 5.5 h under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0060] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone H. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone H was 22%.

[0061] The reaction synthesis equation is as follows: .

[0062] like Figure 15 As shown,

[60] fullerene pyrrolidine quinazolinone H 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.22-8.20 (m, 1H), 7.80 (d, J = 8.6 Hz, 1H), 7.76 (dd, J = 8.7,2.4 Hz, 1H), 5.24 (q, J = 7.4 Hz, 1H), 2.27 (dd, J = 7.4, 2.7 Hz, 3H).

[0063] like Figure 16 It is

[60] fullerene pyrrolidine quinazolinone H 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 158.53 (C=O), 158.31 (C=N), 153.88,149.33, 147.05, 146.73, 146.48, 146.38, 145.76, 145.57, 145.52 (2C), 145.46,145.41, 145.35, 145.25 (2C), 145.00, 144.97, 144.57, 144.54, 144.52, 144.45,144.37, 144.34, 144.21, 144.18, 143.98, 143.60 (2C), 143.54, 143.36, 143.33,143.01, 141.96, 141.82, 141.79, 141.70 (3C), 141.59, 141.13, 141.07, 140.99,140.92, 140.87, 140.83, 140.73, 140.47, 140.09, 139.61, 139.25, 137.17 (2C),136.91, 136.21, 135.33, 135.18, 134.21, 132.64, 132.03 (aryl C), 128.17 (2C, aryl C), 125.47, (2C, aryl C), 121.91 (aryl C), 83.44, 66.98, 48.96, 17.17.

[0064] Example 9 This embodiment describes

[60] fullerene pyrrolidine quinazolinone I Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), 2-amino-5-bromo-benzamide (53.8 mg, 0.25 mmol), n-propionaldehyde (18 μL, 0.25 mmol), lead acetate (32.4 mg, 0.10 mmol), and DMAP (6.1 mg, 0.05 mmol) were added to a 100 mL round-bottom flask. The mixture was completely dissolved by sonication with 6 mL of o-dichlorobenzene. The mixture was then heated and stirred in an oil bath at 170 °C for 5 h under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0065] After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene was first obtained using carbon disulfide as the eluent, and then further separation was carried out using a mixed solution of carbon disulfide and dichloromethane as the eluent, finally yielding brown solid

[60] fullerene pyrrolidine quinazolinone H. In this example, the yield of

[60] fullerene pyrrolidine quinazolinone H was 18%.

[0066] The reaction synthesis equation is as follows: .

[0067] like Figure 17 As shown, it is

[60] fullerene pyrrolidine quinazolinone I. 1 H NMR spectrum 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.38 (d, J = 2.4 Hz, 1H), 7.90 (dd, J = 8.7, 2.4 Hz, 1H), 7.73(d, J = 8.6 Hz, 1H), 5.22 (q, J = 7.4 Hz, 1H), 2.26 (d, J = 7.4 Hz, 3H).

[0068] like Figure 18 As shown, it is

[60] fullerene pyrrolidine quinazolinone I. 13 C NMR spectrum 13C NMR (150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 158.53 (C=O), 158.43 (C=N), 153.96,149.40, 147.14, 146.81, 146.57, 146.47, 146.18, 145.65, 145.60 (2C), 145.54,145.49, 145.43, 145.33 (2C), 145.08 (2C), 144.65, 144.61 (2C), 144.53,144.45, 144.42, 144.28, 144.26 (2C), 144.06, 143.67, 143.62, 143.45, 143.41,143.09, 142.04, 141.90, 141.87, 141.78 (2C), 141.67, 141.21, 141.15, 141.07,141.00 (2C), 140.95, 140.91, 140.82, 140.55, 140.17, 139.69, 139.33, 137.25,137.04, 136.99, 136.29 (2C), 135.40, 135.27, 132.72, 128.75 (2C, aryl C),128.38 (aryl C), 122.32 (2C, aryl C), 120.05 (aryl C), 83.54, 67.04, 49.09,17.22.

[0069] This invention relates to compounds comprising one or more of the fullerenes described above, pyrrolidine, and quinazolinones, and methods for their preparation, but does not limit the scope of the invention. The above examples use fullerenes and 2-aminobenzamide compounds. Aldehyde compounds Using lead acetate and DMAP as raw materials, and o-dichlorobenzene as a solvent, fullerene pyrrolidine-quinazolinone was synthesized by heating in air. R1 is one of alkyl, halogroup, or alkoxy, and R2 is one of alkyl or benzyl.

[0070] Pyrrolidines, due to their unique chemical structure and properties, have broad application prospects in medicine, pesticides, and materials science. The pyrrolidine skeleton is not only the core structure of many natural products and bioactive molecules, but it also plays a crucial role in the synthesis of complex organic molecules and the development of novel drugs. Quinazolinones (fused benzene and six-membered pyrimidine rings) are core structural units in many natural products and drugs, playing a vital role in expressing their biological activities. Their skeleton structures frequently appear in natural products, and they are widely used in antimalarial drugs, antitumor drugs, anticonvulsants, antifungal drugs, antibacterial agents, and anti-inflammatory drugs. Therefore, the study of quinazolinone compounds is of great significance; however, no reaction has yet been found in fullerene derivatization that links pyrrolidine and quinazolinone structural fragments.

[0071] Therefore, the synthesis of this novel fullerene derivative is of great significance. Deng Linlong et al., in their paper "Application of Fullerene Pyrrolidine Derivative Interface Modification Materials in Perovskite Solar Cells," described the application of fullerene pyrrolidine derivatives in perovskite solar cells. These derivatives were used as interface modification layers between SnO2 and the perovskite light-absorbing layer to fabricate nip-type perovskite solar cells. This effectively passivates oxygen vacancies and incompletely coordinated Sn in SnO2. 4+ The defects can be improved by increasing the electron mobility of the SnO2 electron transport layer, allowing charge carriers to be transported more effectively at the interface, thereby improving the photoelectric conversion efficiency of perovskite solar cells. The modified device achieved an optimal photoelectric conversion efficiency of 22.79%, and its stability was also improved.

[0072] Application Example 1 Thermogravimetric analysis (TGA) is a technique used to determine the change in mass of a substance with temperature. It is primarily used to study the thermal stability and decomposition behavior of materials. By heating a sample and accurately recording its mass change, the physical and chemical properties of the material can be analyzed. A TGA analyzer can provide data on the mass loss or gain of a sample during heating or cooling, thus helping to determine key information such as the material's composition, purity, thermal decomposition temperature, and oxidative stability. TGA technology is widely used for the rapid assessment of the thermal stability of various substances.

[0073] like Figure 19 Thermogravimetric analysis results of

[60] fullerene pyrrolidine quinazolinone A are presented. Below 368 °C, substrate A obtained in Example 1 exhibits good thermal stability with negligible mass loss. When the temperature rises to 368 °C, substrate A begins to decompose significantly, a process that results in a mass reduction of approximately 13% at 462 °C. Subsequently, the decomposition rate gradually slows down until it accelerates again at 564 °C.

[0074] Application Example 2 Cyclic voltammetry (CV) is a commonly used testing method in electrochemistry. Its measurement principle involves simultaneously scanning the potential across the working electrode using a triangular wave, i.e., scanning the potential at a given rate v from the initial potential E0 to the final potential E0. λ Then, the current-potential (IE) curve is recorded in reverse at the same rate to E0, also known as the volt-ampere curve.

[0075] like Figure 20 As shown, we used cyclic voltammetry to test the redox potential of

[60] fullerene pyrrolidine quinazolinone D. We found that the oxidation potential peak of this compound appeared at around 0.82 V, and the reduction potential peak appeared at around -1.71 V. These two peaks indicate that it has a certain redox potential, suggesting that this type of compound may have certain application potential in the field of solar cells. In addition, the symmetrical peak shape and repeatable scanning indicate that the compound is structurally stable and not easily decomposed during the redox process, which is the basis for the long-term device stability. Related research indicates that perovskite solar cells (PSCs) have attracted widespread attention; however, traditional materials used in related devices have inherent limitations. (1) Low-temperature treated TiO2 is one of the commonly used ETL materials, but low-temperature treated TiO2 has two key defects: the energy barrier of charge injection is not ideal and the inherent low charge mobility.

[0076] (2) This results in a low charge transfer rate and a high charge recombination rate in the device, which leads to low electron injection efficiency from the perovskite layer to TiO2, resulting in charge accumulation at the relevant interface and hysteresis behavior when measuring PSCs.

[0077] Therefore, due to the excellent electron transport capability and stability of fullerene derivatives, they play a key role in perovskite solar cells as an important type of electron transport material. The fullerene pyrrolidine quinazolinone proposed in this invention

[60] can be combined with low-temperature treated TiO2 to play a role. That is, the fullerene derivative acts as an interface layer and works synergistically with TiO2. It reduces defects through interface passivation and improves stability with hydrophobic structures such as alkyl groups. This can balance the performance and process stability of perovskite solar cells (PSCs).

[0078] (3) The known fullerene dimer NMBF-Cl offers excellent stability and efficiency improvements; however, the preparation of NMBF-Cl is cumbersome, its identification is complex, and its cost is high. In contrast, the method of preparing fullerene pyrrolidine quinazolinone in this invention is simple, and the product can be obtained by a one-step thermal reaction in air, and most of the substrates are inexpensive and readily available.

[0079] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0080] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing fullerene pyrrolidine quinazolinone, characterized in that: Using fullerenes, 2-aminobenzamide compounds, and aldehydes as raw materials, lead acetate and DMAP as promoters, and o-dichlorobenzene as solvent, an aldehyde-amine reaction was carried out by heating in air to synthesize fullerene pyrrolidine quinazolinone. ; The 2-aminobenzamide compounds are 2-aminobenzamide or derivatives thereof whose benzene ring is substituted by a substituent R1, wherein the substituent R1 is one of alkyl, halogroup, or alkoxy group; The aldehyde compounds include The structure, wherein R2 is one of alkyl and benzyl groups; The fullerene is C 60 Fullerenes.

2. The method for preparing fullerene pyrrolidine quinazolinone according to claim 1, characterized in that: The synthesis equation is: 。 3. The method for preparing fullerene pyrrolidine quinazolinone according to claim 2, characterized in that: The 2-aminobenzamide compound is 2-aminobenzamide, and the aldehyde compound is n-propanal, n-butyral, n-pentanal, and phenylpropanal.

4. The method for preparing fullerene pyrrolidine quinazolinone according to claim 2, characterized in that: The aldehyde compound is n-propionaldehyde, and the 2-aminobenzamide compound is 2-amino-5-methylbenzamide, 2-amino-5-methoxybenzamide, 2-amino-5-fluorobenzamide, 2-amino-5-chlorobenzamide, and 2-amino-5-bromobenzamide.

5. The method for preparing fullerene pyrrolidine quinazolinone according to any one of claims 1 to 4, characterized in that, Includes the following steps: The raw material fullerene C was added to the reaction vessel. 60 2-Aminobenzamide compounds and aldehyde compounds were added, along with lead acetate and DMAP as promoters, and o-dichlorobenzene as solvent. The mixture was fully dissolved under ultrasound. The reaction vessel was then heated and stirred on a constant temperature heater. After the reaction was completed, the reaction solution was cooled to room temperature and then separated in a silica gel column using carbon disulfide as eluent. Unreacted fullerenes were obtained first, and then further separated using carbon disulfide and dichloromethane as eluents. Finally, a brown solid fullerene pyrrolidine quinazolinone derivative was obtained.

6. The preparation method according to claim 5, characterized in that, The constant temperature heating temperature is 170 ℃, and the molar ratio of fullerene, 2-aminobenzamide compounds and aldehyde compounds, lead acetate and DMAP is 1:2~8:2~8:1~8:0.5~2.

7. The fullerene pyrrolidine quinazolinone prepared according to the method of claim 6, characterized in that: The structural formula of fullerene pyrrolidine quinazolinone is: R1 is one of alkyl, halogroup, or alkoxy, and R2 is one of alkyl or benzyl; the fullerene is C 60 Fullerenes.

8. The fullerene pyrrolidine quinazolinone prepared according to the method of claim 7, characterized in that: Fullerene pyrrolidine quinazolinones include one of the following compounds: 。 9. An application of the fullerene-pyrrolidine-quinazolinone of claim 8 to the preparation of electron transport materials for perovskite solar cells.

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