A method for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline

Abstract

This invention discloses a method for preparing cis-fullerene pyrrolidinetetrahydroisoquinoline, belonging to the field of fullerene derivative synthesis. Using fullerene, arylmethylamine, and o-(2-haloethyl)benzaldehyde as raw materials, Lewis acids as promoters, and organic solvents as the reaction medium, cis-fullerene pyrrolidinetetrahydroisoquinoline was successfully isolated through a one-step thermal reaction in air. This method offers high yield and novel product structure. It significantly enriches the variety of fullerene derivatives and possesses good substrate versatility and broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology and relates to a method for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline. Background Technology

[0002] Fullerenes have attracted significant attention from the scientific community since their discovery and are widely used in fields such as biomedical molecules, materials chemistry, and perovskite solar cells. However, due to their perfect symmetry... ]][][][][ The limited solubility, or even insolubility, of fullerenes in most organic solvents directly restricts their application and development in various fields. Therefore, functionalizing fullerenes to significantly improve their solubility in water or polar organic solvents is of paramount importance. In recent years, nitrogen-containing heterocyclic fullerene derivatives have been widely used as interface modification materials in perovskite solar cell research. The introduction of nitrogen-containing heterocyclic segments onto the carbon cage of fullerenes through chemical modification has gained increasing attention; for example, fullerene pyrrolidine, fullerene pyrrololine, and fullerene indoline have been successively synthesized and reported.

[0003] Pyrrolidines are an important class of five-membered nitrogen-containing heterocyclic compounds with unique chemical structures and properties, and have a wide range of applications. Tetrahydroisoquinolines are important intermediates in organic synthesis, not only used to synthesize a variety of biologically active compounds, but also widely used in the dye and pesticide industries. Their significant application value indicates the importance of related research.

[0004] However, in the field of fullerene derivatization, there are currently no reports of reactions linking pyrrolidine structural fragments with tetrahydroisoquinoline structural fragments. Therefore, the synthesis of such structurally complex fullerene derivatives is of great significance. Dai et al., in their paper "Synthesis of Fullerene Pyrrolidine Derivatives and Their Application in Inverted Perovskite Solar Cells," described the application of fullerene pyrrolidine derivatives in perovskite solar cells, synthesizing two fullerene pyrrolidine derivatives, F1 and F2, in a one-step Prato reaction.

[0005] The study found that F2 containing benzoic acid ester side chains has higher electron mobility, and the highest photoelectric conversion efficiency of its assembled inverse perovskite solar cells reached 19.86%, which is comparable to the performance of PCBM devices, providing a new idea for the design of low-cost fullerene-based electron transport materials.

[0006] In 2016, relevant literature reported a one-step reaction between fullerene and aromatic aldehydes and methylamines under the promotion of Mg(ClO4)3·H2O

[60] to generate a series of cis-2,5-diarylfullerene pyrrolidine derivatives. The cis isomers obtained by this method are a mixture, and the proportions of the two are close, making separation and purification difficult.

[0007] In 2019, a related literature group reported a method for synthesizing fullerene-fused tetrahydroquinoline derivatives by synergistic free radical N-heterocyclization of fullerene and N-sulfonated o-aminoaryl malonate under the promotion of Cu(II) / Mn(III),

[60] but this method mainly yields tetrahydroline structure derivatives and it is difficult to directly construct tetrahydroisoquinoline skeletons by this method.

[0008] In 2020, relevant literature reported palladium-catalyzed C 60 A series of novel

[60] fullerene fused dihydrobenzoxazazole derivatives were synthesized by cycloaddition reactions with oximes. In addition, the generated fullerene fused dihydrobenzoxazazole derivatives can be further functionalized into multiple addition products by electrochemical methods. The main structure constructed is the benzoxazazole skeleton, which cannot be directly applied to the construction of the tetrahydroisoquinoline fullerene pyrrolidine skeleton. Moreover, the starting materials require the use of specific oxime compounds as substrates, which has a narrow range of applications.

[0009] In 2023, relevant literature reported that

[60] fullerenes and readily available β-substituted ethylamines can undergo a simple one-step reaction with Cu(OAc)2 in the absence or presence of aryl acetaldehyde, thereby obtaining a series of previously unreported

[60] fullerene dihydropyridine-3-ones. Due to the large π-conjugated system on the

[60] fullerene dihydropyridine-3-one ring, these derivatives may have broad application prospects in perovskite solar cells, thereby improving the performance of photovoltaic devices.

[0010] CN120623098A discloses a fullerene pyrrolidine derivative, its preparation method, and its applications, and uses it as an electron transport layer material for tin-based perovskite solar cells. This material can effectively improve the open-circuit voltage, short-circuit current, fill factor, and photoelectric conversion efficiency of the cell, with the photoelectric conversion efficiency of the device based on the F6 / F12 composite system reaching 12.0%.

[0011] Meanwhile, these derivatives exhibit good chemical stability and environmental adaptability, significantly extending device lifespan. Furthermore, their fabrication process is simple and low-cost, making them of significant value for the application of tin-based perovskite solar cells.

[0012] The structures of nitrogen-substituted fullerene pyrrolidines reported so far are relatively simple. We are considering whether we can find a new synthetic strategy to prepare complex bicyclic fullerene pyrrolidine derivatives. Summary of the Invention

[0013] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a method for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline. The method utilizes the aldehyde-amine reaction of fullerene with o-(2-haloethyl)benzaldehyde and arylamine to prepare fullerene pyrrolidine tetrahydroisoquinoline, thereby improving the yield of the target derivative and verifying the universality of the substrate.

[0014] The present invention discloses a method for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline, which uses fullerene, arylmethylamine, and o-(2-haloethyl)benzaldehyde as raw materials, Lewis acid as a promoter, and an organic solvent as a reaction medium. The reaction is carried out in air via a one-step thermal reaction, and finally, cis-fullerene pyrrolidine tetrahydroisoquinoline is obtained by separation. The fullerene is selected from C164-C ... 60 To C 84 One of the fullerenes; The arylmethylamine is R1-CH2-NH2, where R1 is... R2 is one of alkyl, halogroup, alkoxy, or phenyl groups; The Lewis acid accelerator is one of a metal halide, a metal trifluoromethanesulfonate, or a metal acetate. In the structure of the cis-fullerene-pyrrolidine-tetrahydroisoquinoline, the fullerene cage is fused with the tetrahydroisoquinoline ring through the pyrrolidine ring, and the fusion of the pyrrolidine ring and the tetrahydroisoquinoline ring is in the cis configuration.

[0015] Furthermore, the fullerene is C 60 ; The aryl methylamine is one of benzylamine, 3-methoxybenzylamine, 3-methylbenzylamine, 4-phenylbenzylamine, 3,4-dichlorobenzylamine, 4-trifluoromethylbenzylamine, 4-chlorobenzylamine, and 4-bromobenzylamine; The Lewis acid accelerator is anhydrous ferric chloride FeCl3; The o-(2-haloethyl)benzaldehyde is o-(2-bromoethyl)benzaldehyde; The organic solvent is one of o-dichlorobenzene and chlorobenzene, preferably o-dichlorobenzene; The cis-fullerenepyrrolidine tetrahydroisoquinoline is R1 is R2 is one of alkyl, halogroup, alkoxy, or phenyl.

[0016] The specific steps for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline provided by this invention are as follows: (1) Add the raw materials fullerene, o-(2-haloethyl)benzaldehyde, arylamine and Lewis acid to the reaction vessel, add organic solvent, and dissolve them completely under ultrasonic treatment. Then place the reaction vessel on a constant temperature heater and heat and stir. (2) After the reaction was completed, the reaction solution was first cooled with water at room temperature, and then the reaction solution was directly added to a silica gel column for separation. Unreacted fullerene was first obtained by using carbon disulfide as the eluent. Then, carbon disulfide was used as the eluent for further separation, and finally brown solid main product cis-fullerene pyrrolidine tetrahydroisoquinoline and trace by-product trans-fullerene pyrrolidine tetrahydroisoquinoline were obtained.

[0017] Furthermore, the molar ratio of fullerene, o-(2-haloethyl)benzaldehyde, aryl methylamine, and Lewis acid accelerator is 1:7~13:7~13:2~4, the reaction temperature is 110-130 ℃, and the reaction time ranges from 5 to 45 min.

[0018] Preferably, the molar ratio of fullerene, o-(2-haloethyl)benzaldehyde, arylamine, and Lewis acid is 1:10:10:3, the reaction temperature is 120 °C, and the reaction time is 30-40 min.

[0019] Furthermore, the separation and purification were performed using column chromatography; the purity of the cis-fullerene pyrrolidine tetrahydroisoquinoline isomer in the obtained product was greater than 95%, and the content of the trans isomer was less than 5%.

[0020] Furthermore, the cis-fullerenepyrrolidinetetrahydroisoquinoline comprises one of the following compounds: .

[0021] Compared with the prior art, the present invention has the following outstanding advantages: (1) This invention provides a method for preparing cis-fullerene pyrrolidine and tetrahydroisoquinoline with high yield and has great application prospects in the field of perovskite solar cells.

[0022] (2) The fullerene pyrrolidine derivative obtained by this invention has a novel structure, the product has excellent solubility and selectivity, and is easy to separate and purify. The substrates used have a wide range of applications and good universality, and most of them are inexpensive and readily available. At the same time, the promoter used, anhydrous ferric chloride FeCl3, has low toxicity, low cost, and high yield and good selectivity of the target product. Finally, the method for preparing cis-fullerene pyrrolidine and tetrahydroisoquinoline 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.

[0023] (3) Thermogravimetric analysis proves that the product prepared by this method has good overall thermal stability and is suitable for use at 252°C. o Previous work by C; the redox potential diagram of the compound obtained by cyclic voltammetry can show that it has certain redox activity and has certain application potential in the field of perovskite solar cells. Attached Figure Description

[0024] Figure 1 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-A of Example 1 of the present invention

[60] . 1 H NMR spectrum; Figure 2 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-A of Example 1 of the present invention

[60] . 13 C NMR spectrum; Figure 3 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-B of Example 2 of the present invention

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

[60] . 13 C NMR spectrum; Figure 5 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-C of Example 3 of the present invention

[60] . 1 H NMR spectrum; Figure 6 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-C of Example 3 of the present invention

[60] . 13 C NMR spectrum; Figure 7 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-D of Example 4 of the present invention

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

[60] . 13 C NMR spectrum; Figure 9 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-E of Example 5 of the present invention

[60] . 1 H NMR spectrum; Figure 10 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-E of Example 5 of the present invention

[60] . 13 C NMR spectrum; Figure 11 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-F of Example 6 of the present invention

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

[60] . 13 C NMR spectrum; Figure 13 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-G of Example 7 of the present invention

[60] . 1 H NMR spectrum; Figure 14 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-G of Example 7 of the present invention

[60] . 13 C NMR spectrum; Figure 15 This is the fullerene-pyrrolidine-tetrahydroisoquinoline cis-H of Example 8 of the present invention

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

[60] . 13 C NMR spectrum; Figure 17 This is the thermogravimetric analysis (TGA) diagram of fullerene pyrrolidine tetrahydroisoquinoline cis-A for the implementation of this invention

[60] ; Figure 18 This is the CV curve of fullerene pyrrolidine tetrahydroisoquinoline cis-A for the implementation of this invention

[60] . Detailed Implementation

[0025] The present invention will be further described in detail below through embodiments, but the content of the invention is not limited to these embodiments. Example 1

[0026] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), benzylamine (55 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 dissolved in air at 120 °C. o Heating and stirring in an oil bath for 30 minutes, followed by thin-layer chromatography (TLC) spotting.

[0027] 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 carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-A (< 5%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A was 53%.

[0028] The reaction synthesis equation is as follows: like Figure 1 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.15 (d, J= 7.8 Hz, 1H), 7.74 (d, J= 6.9 Hz,2H), 7.37 (t,J= 7.4 Hz, 2H), 7.28 (t,J= 7.4 Hz, 2H), 7.17 (t, J= 6.3 Hz, 1H), 7.11 (t,J=7.6Hz, 1H), 5.50 (s,1H),5.28 (s,1H),3.70-3.59 (m, 2H), 3.01-2.94 (m, 1H),2.88-2.81 (m, 1H).

[0029] like Figure 2 As shown, this is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A 13 C NMR spectrum 13C NMR(150 MHz,CS2 / DMSO-d6) (all 1C unless indicated) δ 152.60, 152.34, 151.57,151.52, 146.10, 145.62, 145.51, 145.40, 144.74, 144.73, 144.64 (2C), 144.54,144.43, 144.32, 144.28, 144.23, 144.11, 144.04, 144.02, 143.90, 143.86,143.65, 143.63, 143.51, 143.29, 143.16, 142.94, 142.82, 142.77, 141.51,141.47, 141.41, 141.13, 141.07, 141.06, 140.75, 140.64, 140.61, 140.50(2C),140.45, 140.42, 140.31, 140.11, 139.99, 139.76, 138.53, 137.85, 137.77,137.23, 136.49, 135.21, 135.02, 134.96, 134.70, 134.62, 132.82, 128.51 (arylC), 128.13 (2C, aryl C). 127.57 (3C, aryl C), 127.40 (aryl C), 126.24 (2C, aryl C), 126.07 (2C, aryl C), 124.79 (aryl C). 78.53, 76.09, 73.72, 72.45, 45.08, 29.98. Example 2

[0030] This embodiment introduces

[60] fullerene pyrrolidine and tetrahydroisoquinoline cis-B Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 3-methoxybenzamide (64 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C. o The mixture was heated and stirred in an oil bath for 40 minutes, and then tracked using thin-layer chromatography (TLC) on a plate.

[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 separated using carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-B and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-B (< 2%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-B was 53%.

[0032] The reaction synthesis equation is as follows: like Figure 3 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-B 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.14 (d, J = 7.8 Hz, 1H), 7.30 (d, J = 7.6 Hz, 1H), 7.28-7.23 (m, 3H), 7.18 (t, J = 7.4 Hz, 1H), 7.10 (t, J = 7.4 Hz, 1H), 6.78 (m,1H), 5.48 (s, 1H), 5.23 (s, 1H), 3.73 (s, 3H), 3.71-3.67 (m, 1H), 3.65-3.57(m, 1H), 2.97 (d, J = 17.2 Hz, 1H), 2.88-2.80 (m, 1H).

[0033] like Figure 4 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-B 13 C NMR spectrum 13C NMR(150 MHz, CS2 / DMSO-d6) (all 1C unless indicated) δ 158.43 (aryl C), 152.94,152.57, 151.79, 151.62, 146.30, 145.80, 145.71 (2C), 145.67, 144.93, 144.91,144.81, 144.72, 144.61, 144.51, 144.48, 144.42, 144.23, 144.20, 144.10,144.04, 143.83 (2C), 143.78, 143.70, 143.50, 143.38, 143.13, 143.01, 142.94,141.70, 141.67, 141.59,141.32, 141.28, 141.25 (2C), 140.94, 140.84, 140.80,140.77, 140.71, 140.66, 140.62, 140.51, 140.29, 140.22, 139.94, 138.66,138.04, 137.38, 136.71, 136.29, 135.38, 135.20, 134.94, 134.83, 133.03,128.69 (aryl C), 128.65 (aryl C), 126.41 (2C, aryl C), 126.20 (2C, aryl C), 124.92 (2C, aryl C), 120.58 (aryl C), 114.04 (aryl C), 112.81 (aryl C), 78.60, 76.14, 73.86, 72.64, 53.93, 45.30, 30.12. Example 3

[0034] This embodiment describes

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-C Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 3-methylbenzylamine (63 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 dissolved in air at 120 °C. oThe mixture was heated and stirred in an oil bath for 40 minutes, and then tracked using thin-layer chromatography (TLC) on a plate.

[0035] 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 separated using carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-C and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-C (< 2%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-C was 47%.

[0036] The reaction synthesis equation is as follows: like Figure 5 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-C 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.14 (d, J = 7.8 Hz, 1H), 7.55 (d, J = 7.7 Hz, 1H), 7.51(s, 1H), 7.25 (t, J = 7.7 Hz, 2H), 7.18 (t, J = 7.3 Hz, 1H), 7.13-7.06 (m, 2H), 5.48 (s, 1H), 5.23 (s, 1H), 3.69-3.57 (m, 2H), 3.01-2.92 (m, 1H), 2.87-2.78 (m, 1H), 2.36 (s, 3H).

[0037] like Figure 6 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-C 13 C NMR spectrum 13C NMR(150 MHz, CS2 / DMSO-d6) (all 1C unless indicated) δ 152.65, 152.32, 151.62,151.48, 146.03, 145.53, 145.43 (2C), 145.35, 144.65, 144.63, 144.54, 144.44,144.34, 144.23, 144.20, 144.14, 144.06, 143.96, 143.93, 143.81, 143.76,143.56, 143.52, 143.42, 143.18, 143.08, 142.86, 142.74, 142.67, 141.42 (2C),141.39, 141.32, 141.05, 140.98, 140.66, 140.56, 140.52, 140.42, 140.38,140.33, 140.23, 140.03, 139.92, 139.67, 138.44, 137.76, 137.70, 137.12,136.43, 136.40, 135.12, 134.95, 134.78, 134.57, 134.44, 132.76, 128.87 (arylC), 128.44 (2C, aryl C), 128.04 (2C, aryl C), 127.50 (aryl C), 126.15 (arylC), 126.00 (aryl C), 125.17 (aryl C), 124.71 (2C, aryl C), 78.53, 76.01,73.65, 72.39, 45.02, 29.91, 20.46. Example 4

[0038] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-D Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 4-phenylbenzylamine (87 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C for 40 minutes under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0039] 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 carbon disulfide as the eluent, ultimately yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-D and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-D (< 2%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-D was 44%. The reaction synthesis equation is as follows: like Figure 7 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-D 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.16 (d, J = 7.8 Hz, 1H), 7.82 (d, J = 7.9 Hz, 2H), 7.60 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 7.1 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.26(m, 2H), 7.19 (t, J = 7.5 Hz, 1H), 7.11 (t, J = 9.2 Hz, 1H), 5.52 (s, 1H),5.34 (s, 1H), 3.73-3.60 (m, 2H), 3.02-2.95 (m, 1H), 2.92-2.84 (m, 1H).

[0040] like Figure 8 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-D 13 C NMR spectrum 13C NMR(150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 152.75, 152.64, 151.92,151.73, 146.46, 146.07, 145.98, 145.86, 145.74, 145.19, 145.17, 145.10,145.00, 144.90, 144.77, 144.69, 144.53, 144.48, 144.44, 144.37, 144.31,144.10, 144.08, 143.98, 143.81, 143.59, 143.39, 143.26, 143.20, 141.93 (2C),141.86, 141.59, 141.52 (2C), 141.18, 141.06, 141.02, 140.96, 140.94, 140.87,140.82, 140.54, 140.46, 140.26, 140.19, 139.16, 139.08, 138.38, 138.30,137.72, 136.91, 135.56, 135.49, 135.33, 135.06, 134.08, 133.25, 129.00 (3C,aryl C), 128.74 (aryl C), 127.91 (3C, aryl C), 126.68 (aryl C), 126.58 (arylC), 126.37 (5C, aryl C), 126.04 (3C, aryl C), 125.14 (aryl C), 78.94, 76.50,74.31, 72.89, 45.56, 30.33. Example 5

[0041] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-E Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 3,4-dichlorobenzylamine (67 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C for 40 minutes under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0042] 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 separated using carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-E and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-E (< 5%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-E was 34%.

[0043] The reaction synthesis equation is as follows: like Figure 9 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-E 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.15 (d, J = 7.8 Hz, 1H), 7.86 (s, 1H), 7.68 (d, J = 8.2Hz, 1H), 7.49 (dd, J = 8.2, 3.5 Hz, 1H), 7.27 (d, J = 7.5 Hz, 1H), 7.20 (t, J= 7.4 Hz, 1H), 7.12 (t, J = 7.6 Hz, 1H), 5.52 (s, 1H), 5.28 (d, J = 13.7 Hz,1H), 3.66-3.58 (m, 2H), 3.00 (d, J = 15.6 Hz, 1H), 2.93-2.86 (m, 1H).

[0044] like Figure 10 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-E 13 C NMR spectrum 13C NMR(150 MHz, CS2 / CDCl3) (all 1C unless indicated) δ 151.69, 151.11, 150.73,150.62, 145.78, 145.57, 145.49, 145.13, 144.72, 144.68, 144.65, 144.61,144.57, 144.50, 144.40, 144.27, 144.19, 144.08, 143.95 (2C), 143.83, 143.78,143.58 (2C), 143.50, 143.36 (2C), 143.02, 142.85, 142.68 (2C), 141.42,141.39, 141.36, 141.10, 141.04, 141.02 (2C), 140.65, 140.53, 140.43, 140.39,140.34, 140.24, 139.99, 139.90, 139.66,138.67, 137.97, 137.80, 137.26,136.19, 135.15, 135.08, 134.89, 134.65, 134.51, 132.34, 131.70 (aryl C),131.46 (aryl C), 129.70 (aryl C), 129.29 (aryl C), 128.29 (2C, aryl C),127.04 (aryl C), 126.09 (2C, aryl C), 126.02 (aryl C), 124.75 (2C, aryl C),75.43, 73.68, 72.15, 45.12, 29.72. Example 6

[0045] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-F Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 4-trifluoromethylbenzamide (63 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C for 40 minutes 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 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 carbon disulfide as the eluent, ultimately yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-F and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-F (< 5%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-F was 37%. The reaction synthesis equation is as follows: like Figure 11 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-F 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.16 (d, J = 7.8 Hz, 1H), 7.95 (d, J = 7.9 Hz, 2H), 7.66(d, J = 8.1 Hz, 2H), 7.28 (d, J = 7.6 Hz, 1H), 7.20 (t, J = 7.0 Hz, 1H), 7.12(t, J = 7.6 Hz, 1H), 5.55 (s, 1H), 5.40 (s, 1H), 3.69-3.56 (m, 2H), 3.01-2.96(m, 1H), 2.94-2.85 (m, 1H).

[0047] like Figure 12 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-F 13 C NMR spectrum 13C NMR(150 MHz, CS2 / DMSO-d6) (all 1C unless indicated) δ 152.13, 151.80, 151.28,151.09, 146.08, 145.69, 145.62, 145.43, 145.10, 144.82, 144.80, 144.73,144.63, 144.52, 144.41, 144.33, 144.27, 144.10, 144.06, 144.03, 143.93,143.73, 143.68 (2C), 143.61, 143.46, 143.16, 143.02, 142.85 (2C), 141.56(4C), 141.51, 141.24, 141.18, 141.14, 140.82, 140.69, 140.64, 140.53, 140.46,140.42, 140.11, 140.07, 139.85, 139.23, 138.70, 137.95 (2C), 137.37, 136.40,135.25, 135.20, 134.94 (2C), 132.64, 128.78 (2C, aryl C), 128.60 (2C, arylC), 126.27 (2C, aryl C), 126.22 (2C, aryl C), 124.90 (2C, aryl C), 124.39 (2C, aryl C), 122.34 (q, J C-F = 273.3 Hz), 77.80, 75.71, 73.69, 72.51, 45.19, 29.98. Example 7

[0048] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-G Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 4-chlorobenzylamine (61 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C for 40 minutes under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0049] 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 separated using carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-G and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-G (< 2%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-G was 47%.

[0050] The reaction synthesis equation is as follows: like Figure 13 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-G 1 H NMR spectrum 1 H NMR (400MHz, CS2 / DMSO-d6) δ 8.14 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 7.6 Hz, 1H), 7.19 (t, J = 7.4 Hz, 1H), 7.11(t, J = 7.5 Hz, 1H), 5.51 (s, 1H), 5.29 (s, 1H), 3.65-3.58 (m, 2H), 3.00-2.96(m, 1H), 2.90-2.82 (m, 1H).

[0051] like Figure 14 It is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-G 13 C NMR spectrum 13C NMR (150MHz, CS2 / DMSO-d6) (all 1C unless indicated) δ 152.34, 152.28, 151.55, 151.46,146.24, 145.83, 145.74, 145.63, 145.36, 144.95, 144.87, 144.84, 144.76,144.65, 144.53, 144.45, 144.43, 144.23, 144.20, 144.14, 144.07 (2C), 143.86(2C), 143.83, 143.74, 143.57, 143.35, 143.15, 143.01, 142.98, 141.70 (2C),141.63, 141.36, 141.31, 141.28 (2C), 140.95, 140.83, 140.78, 140.69, 140.61,140.57, 140.25, 139.97, 138.83, 138.12, 138.07, 137.46, 136.58, 135.37,135.28, 135.10, 134.99, 133.56, 133.35, 132.86, 129.68 (2C, aryl C), 128.67(2C, aryl C), 127.86 (2C, aryl C), 126.41 (2C, aryl C), 126.28 (2C, aryl C),124.99 (2C, aryl C), 77.88, 76.07, 73.85, 72.57, 45.26, 30.11. Example 8

[0052] This embodiment introduces

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-H Preparation method:

[60] Fullerene (36.0 mg, 0.05 mmol), o-(2-bromoethyl)benzaldehyde (74 μL, 0.50 mmol), 4-bromobenzamide (63 μL, 0.50 mmol), and anhydrous ferric chloride (24.3 mg, 0.15 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 120 °C for 30 minutes under air conditions. Thin-layer chromatography (TLC) was used to track the reaction.

[0053] 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 separated using carbon disulfide as the eluent, finally yielding brown solids

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-H and

[60] fullerene pyrrolidine tetrahydroisoquinoline trans-H (< 2%). In this example, the yield of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-H was 46%.

[0054] The reaction synthesis equation is as follows: like Figure 15 As shown, it is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-H. 1 H NMR (400 MHz, CS2 / DMSO-d6) δ 8.14 (d, J = 6.6 Hz, 1H), 7.67 (d, J = 8.3 Hz, 2H), 7.50 (d, J =8.4 Hz, 2H), 7.27 (d, J = 7.6 Hz, 1H), 7.19 (t, J = 7.4 Hz, 1H), 7.11 (t, J =7.9 Hz, 1H), 5.51 (s, 1H), 5.29-5.24 (m, 1H), 3.66-3.58 (m, 2H), 2.98 (d, J =16.3 Hz, 1H), 2.90-0.82 (m, 1H).

[0055] like Figure 16 It is

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-H 13 C NMR spectrum 13C NMR (150MHz, CS2 / DMSO-d6) (all 1C unless indicated) δ 152.46, 152.37, 151.65, 151.56,146.36, 145.97, 145.88, 145.75, 145.48, 145.09, 145.06, 145.00, 144.98,144.90, 144.79, 144.67, 144.59, 144.56, 144.36, 144.33, 144.28, 144.20 (2C),143.99, 143.97, 143.88, 143.72, 143.48, 143.28, 143.15, 143.11, 141.83 (2C),141.77, 141.49, 141.44, 141.41, 141.09, 140.96, 140.91, 140.84, 140.82,140.74, 140.71, 140.38 (2C), 140.11, 138.97, 138.29, 138.21, 137.61, 136.71,135.50, 135.43, 135.22, 135.12, 134.20, 132.99, 130.91 (2C, aryl C), 130.09(2C, aryl C), 128.77 (aryl C), 126.54 (2C, aryl C), 126.38 (2C, aryl C),125.10 (2C, aryl C), 122.01 (aryl C), 78.08, 76.14, 73.98, 72.70, 45.38,30.21.

[0056] Performance testing: The present invention performed thermogravimetric analysis and cyclic voltammetry on the substrate

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A obtained in Example 1, and the results are as follows: Figure 17 and Figure 18 As shown.

[0057] 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.

[0058] 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.

[0059] Figure 17 Thermogravimetric analysis results of

[60] fullerene pyrrolidine tetrahydroisoquinoline cis-A are presented. Below 252 °C, the substrate cis-A obtained in Example 1 exhibits good thermal stability, with no significant mass loss observed in this temperature range. When the temperature rises to 252 °C, the sample enters a rapid decomposition stage, with a cumulative mass loss of 12% when the temperature continues to rise to 329 °C. In the temperature range of 329-644 °C, the decomposition rate slows down significantly, followed by a secondary violent decomposition near 644 °C until the sample is completely pyrolyzed.

[0060] like Figure 18 As shown, an oxidation potential peak of the compound was found at around 0.76 V, and a reduction potential peak was found at around -1.13 V. These two peaks indicate that the compound has certain redox potentials, suggesting that this type of compound may have certain application potential in the field of solar cells.

[0061] Furthermore, related studies have shown that TiO2, the electron transport layer widely used in perovskite solar cells, is one of the main reasons for the poor stability of the devices. The low electron mobility of TiO2 and its photocatalytic effect lead to hysteresis and degradation of part of the perovskite layer at the interface.

[0062] Currently, the solution-processable fullerene electron transport layer is mainly C. 60 Derivative [6,6]-phenyl-C 611,4-methyl butyrate (PCBM), is synthesized through multiple steps, resulting in low yields and difficulties in separation and purification, leading to high costs. In contrast, the synthesis of fullerene pyrrolidine derivatives is simpler and easier to chemically modify. The present invention provides a simple method for preparing cis-fullerene pyrrolidine and tetrahydroisoquinoline, which can be obtained through a one-step thermal reaction in air, and most of the substrates are inexpensive and readily available.

[0063] As shown in Table 1, the Lewis acids described in the embodiments of the present invention were screened.

[0064] Table 1 Lewis Acid Screening Note: a Unless otherwise stated, all experiments were conducted in air using 6 mL of o-dichlorobenzene (ODCB) as the reaction solvent. b The molar ratio is C 60 / o-(2-bromoethyl)benzaldehyde / 3-methoxybenzamide / accelerator c Separation yield.

[0065] As can be seen from the table, anhydrous ferric chloride (FeCl3) showed the best performance among all the Lewis acids tested. Furthermore, the promoter used was anhydrous ferric chloride (FeCl3), which is low in toxicity, inexpensive, and yielded a high and selective product. The trans-yield of the obtained product was <2%, exhibiting excellent solubility and selectivity, and was easily separated and purified.

[0066] 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.

[0067] 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 cis-fullerenepyrrolidinetetrahydroisoquinoline, characterized in that, Using fullerene, arylmethylamine, and o-(2-haloethyl)benzaldehyde as raw materials, Lewis acid as a promoter, and organic solvent as the reaction medium, a one-step thermal reaction was carried out in air, and finally, cis-fullerenepyrrolidinetetrahydroisoquinoline was obtained by separation. The fullerene is selected from C 60 To C 84 One of the fullerenes; The aryl methylamine is R1-CH2-NH 2， R1 is R2 is one of alkyl, halogroup, alkoxy, or phenyl groups; The Lewis acid accelerator is one of a metal halide, a metal trifluoromethanesulfonate, or a metal acetate. In the structure of the cis-fullerene-pyrrolidine-tetrahydroisoquinoline, the fullerene cage is fused with the tetrahydroisoquinoline ring through the pyrrolidine ring, and the fusion of the pyrrolidine ring and the tetrahydroisoquinoline ring is in the cis configuration.

2. The method for preparing fullerene pyrrolidine tetrahydroisoquinoline according to claim 1, characterized in that, The fullerene is C 60 Fullerenes; The aryl methylamine is one of benzylamine, 3-methoxybenzylamine, 3-methylbenzylamine, 4-phenylbenzylamine, 3,4-dichlorobenzylamine, 4-trifluoromethylbenzylamine, 4-chlorobenzylamine, and 4-bromobenzylamine; The Lewis acid accelerator is anhydrous ferric chloride FeCl3; The o-(2-haloethyl)benzaldehyde is o-(2-bromoethyl)benzaldehyde; The organic solvent is one of o-dichlorobenzene and chlorobenzene; The cis-fullerenepyrrolidinetetrahydroisoquinoline is R1 is R2 is one of alkyl, halogroup, alkoxy, or phenyl.

3. A method for preparing cis-fullerene pyrrolidine tetrahydroisoquinoline according to any one of claims 1-2, characterized in that, Includes the following steps, (1) Add the raw materials fullerene, o-(2-haloethyl)benzaldehyde and arylamine to the reaction vessel, then add Lewis acid as a promoter, add organic solvent, and dissolve them fully under ultrasonic treatment. Then place the reaction vessel on a constant temperature heater for heating and stirring. (2) 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 fullerene was first obtained by using carbon disulfide as the eluent, and then further separation was carried out by using carbon disulfide as the eluent. Finally, brown solid cis-fullerene pyrrolidine tetrahydroisoquinoline and trace amount of byproduct trans-fullerene pyrrolidine tetrahydroisoquinoline were obtained. .

4. The preparation method according to claim 1, characterized in that, The molar ratio of fullerene, o-(2-haloethyl)benzaldehyde, arylamine, and Lewis acid is 1:7~13:7~13:2~4, the reaction temperature is 110-130 ℃, and the reaction time ranges from 5 to 45 min.

5. The preparation method according to claim 1, characterized in that, The molar ratio of fullerene, o-(2-haloethyl)benzaldehyde, arylamine, and Lewis acid is 1:10:10:3, the reaction temperature is 120 °C, and the reaction time is 30-40 min.

6. The cis-fullerene pyrrolidine tetrahydroisoquinoline prepared according to the method of claim 1, characterized in that, The purity of the cis-fullerene pyrrolidine tetrahydroisoquinoline isomer in the obtained product is greater than 95%, and the content of the trans isomer is less than 5%.

7. The cis-fullerene pyrrolidine tetrahydroisoquinoline prepared based on the method of claim 1, characterized in that, The cis-fullerenepyrrolidinetetrahydroisoquinoline includes one of the following compounds: 。

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