Method for preparing fullerene pyrrolidino-isoindolinone based on participation of carboxybenzaldehyde

Abstract

The invention discloses a method for preparing fullerene pyrrolidino-isoindolinone based on participation of carboxybenzaldehyde, and belongs to the field of fullerene derivative synthesis. Fullerene, aromatic alkylamine and carboxybenzaldehyde are used as raw materials, basic lead acetate is used as an accelerant, o-dichlorobenzene is used as a solvent, and the fullerene pyrrolidino-isoindolinone is prepared through a one-step reaction. And carrying out one-step thermal reaction in air to obtain the target product fullerene pyrrolidine isoindolinone. The method is simple in step, high in yield, novel in product structure and high in product stability at normal temperature, the variety of fullerene derivatives is greatly enriched, and meanwhile the method has good substrate universality and wide application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to a method for preparing fullerene pyrrolidinoisoindolinone based on the participation of o-carboxybenzaldehyde. Background Art

[0002] Since its discovery, fullerene has attracted great attention from the scientific community and has been widely used in the fields of biomedical molecules, material chemistry, and perovskite solar cells. However, due to its perfect symmetry, its solubility in most organic solvents is very limited, or even insoluble, which limits its application and development in various fields. It is particularly important to greatly improve its solubility in water or organic polar solvents through the functionalization of fullerenes. In recent years, nitrogen-containing heterocyclic fullerene derivatives have been widely used in the study of perovskite solar cells as interface modification materials. The introduction of nitrogen-containing heterocyclic fragments into fullerene carbon cages through chemical modification has received increasing attention, such as fullerene pyrrolidine, fullerene pyrroline, fullerene indoline, etc., which have been synthesized and reported one after another.

[0003] As shown in Formula 1, in 2017, Li Fabao's research group at Hubei University reported a DMAP-promoted reaction in which

[60] fullerene reacted with aromatic aldehydes and aromatic methylamines in one step in the presence or absence of manganese (III) acetate to produce a series of scarce

[60] fullerene pyrroline derivatives (The Journal of Organic Chemistry, 2017, 82: 9751-9764).

[0004]

[0005] As shown in Formula 2, in 2019, Professor Wang Guanwu's research group at the University of Science and Technology of China used triethylamine and aromatic aldehydes to react with C 60 The reaction produces 2-arylvinyl-substituted

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

[0006]

[0007] As shown in Formula 3, in 2020, Liu Tongxin's research group at Henan Normal University reported a reaction strategy through iron (II)-catalyzed redox. Through this method, a class of unexplored

[60] fullerene-based nanostructures can be obtained, and this method is suitable for scale-up synthesis (Organic Letters, 2020, 22: 7327-7332).

[0008]

[0009] As shown in Formula 4, in 2023, Li Fabao's research group at Hubei University reported that

[60] fullerenes reacted with cheap and readily available β-substituted ethylamines in the absence or presence of aromatic acetaldehydes via Cu(OAc) 2 The promotion of can result in a simple one-step reaction, thus obtaining a series of unreported

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

[60] fullerene dihydropyridine-3-one ring, this type of derivative may have broad application prospects in perovskite solar cells, thereby improving the performance of photovoltaic devices. (Chinese Journal of Chemistry, 2023, 41: 1557-1565).

[0010]

[0011] CN116322090A discloses a perovskite solar cell based on a fullerene pyrrolidine electron transport layer. Fullerene pyrrolidine (FMG) is used as a functionalized electron transport layer material to form a gradient heterojunction structure with a perovskite film photosensitive layer, thereby achieving efficient electron extraction and grain boundary passivation, improving the energy conversion efficiency and light stability of the solar cell device, and the energy conversion efficiency can reach 23.8%.

[0012] The structures of the nitrogen-substituted fullerene pyrrolidines reported so far are relatively simple. We wondered whether we could find a new synthetic strategy to prepare complex bicyclic fullerene pyrrolidines in one step. 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 fullerene pyrrolidinoisoindolinone based on the participation of o-carboxybenzaldehyde, utilize fullerene and o-carboxybenzaldehyde and aromatic alkylamine to react with aldehyde amine to prepare fullerene pyrrolidinoisoindolinone, improve the yield of target derivatives, and verify the universality of the product.

[0014] The method for preparing fullerene pyrrolidinoisoindolinone based on the participation of o-carboxybenzaldehyde of the present invention uses fullerene, aromatic alkylamine and o-carboxybenzaldehyde as raw materials, basic lead acetate as a promoter, and o-dichlorobenzene as a solvent, and heats the reaction in air to synthesize fullerene pyrrolidinoisoindolinone Aromatic alkyl amine is R 1 -CH 2 -NH 2 , R 1 for R 2 is one of an alkyl group, a halo group, and an alkoxy group, wherein C n It is C 60 To C 84of fullerenes.

[0015] Preferably, the molar ratio of the fullerene, o-carboxybenzaldehyde, aromatic alkylamine and basic lead acetate is 1:7-20:11-22:3-6, and the heating reaction temperature is 170°C.

[0016] Preferably, the synthesis equation is:

[0017]

[0018] Preferably, the aromatic alkylamine is aromatic methylamine, and the synthesis equation is:

[0019]

[0020] Preferably, the molar ratio of the lene, o-carboxybenzaldehyde, aromatic methylamine and basic lead acetate is 1:7:11:3, and the temperature of the heating reaction is 170°C.

[0021] Preferably, the aromatic alkylamine is aromatic ethylamine, and the synthesis equation is:

[0022]

[0023] Preferably, the molar ratio of fullerene, o-carboxybenzaldehyde, aromatic ethylamine and basic lead acetate is 1:20:22:6, and the heating reaction temperature is 170°C.

[0024] Preferably, the specific steps for preparing fullerene pyrrolidine and isoindolinone are as follows: adding raw materials fullerene, o-carboxybenzaldehyde and aromatic alkylamine into a reaction container, adding solvent o-dichlorobenzene, and fully dissolving it under an ultrasonic instrument, then placing the reaction container on a constant temperature heater for heating and stirring, and after the reaction is completed, first cooling the reaction solution with room temperature water, and then directly adding the reaction solution to a silica gel column for separation, using carbon disulfide as an eluent to first obtain unreacted fullerene, and then using carbon disulfide and dichloromethane as eluents to continue separation, and finally obtaining brown solid fullerene pyrrolidine and isoindolinone. The fullerene pyrrolidine and isoindolinone prepared based on the method described is R 1 for R 2 is one of an alkyl group, a halo group, and an alkoxy group, wherein C n It is C 60 To C 84 of fullerenes.

[0025] Based on the fullerene pyrrolidinoisoindolinone prepared by the method, the C n It is C 60 Fullerenes. Fullerene pyrrolidinoisoindolinones include one of the following compounds

[0026]

[0027] Compared with the prior art, the present invention has the following outstanding advantages:

[0028] 1. The present invention provides a method for preparing fullerene pyrrolidinoisoindolinone, which has a high yield and has great application prospects in the field of perovskite solar cells. Specifically, due to its higher electron mobility, conductivity and more suitable lowest unoccupied molecular orbital energy level, it can be used as an interface modification material for an electron transport layer and a perovskite light absorption layer to improve the efficiency of the device;

[0029] 2. The fullerene pyrrolidine derivative obtained by this method has a novel structure, enriching the preparation method of new fullerene pyrrolidine derivatives. The product has excellent solubility and selectivity and is easy to separate and purify;

[0030] 3. The substrates used in this method have a wide range of applications and good universality, and most of them are cheap and easy to obtain. At the same time, the method for preparing fullerene pyrrolidine and isoindolinone is simple, and the product can be obtained after a one-step thermal reaction in the air. The preparation conditions and process are relatively loose compared with the conditions and requirements of other existing technologies, which reduces the difficulty of preparing fullerene pyrrolidine derivatives;

[0031] 4. Thermogravimetric analysis can prove that the product prepared by this method has good overall thermal stability and is suitable for working before 338°C;

[0032] 5. The redox potential diagram of the compound obtained by cyclic voltammetry test can show that it has certain redox activity and has certain application potential in the field of solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is the present invention Example 1

[60] fullerene pyrrolidinoisoindolinone A 1 H NMR spectrum;

[0034] Figure 2 is the present invention Example 1

[60] fullerene pyrrolidinoisoindolinone A 13 C NMR spectrum;

[0035] Figure 3 is the present invention Example 2

[60] fullerene pyrrolidinoisoindolinone B 1 H NMR spectrum;

[0036] Figure 4 is the present invention Example 2

[60] fullerene pyrrolidinoisoindolinone B 13 C NMR spectrum;

[0037] Figure 5 is the present invention Example 3

[60] fullerene pyrrolidinoisoindolinone C 1 H NMR spectrum;

[0038] Figure 6 is the present invention Example 3

[60] fullerene pyrrolidinoisoindolinone C 13 C NMR spectrum;

[0039] Figure 7 is the compound of Example 4

[60] fullerene pyrrolidinoisoindolinone D of the present invention 1 H NMR spectrum;

[0040] Figure 8 is the compound of Example 4

[60] fullerene pyrrolidinoisoindolinone D of the present invention 13 C NMR spectrum;

[0041] Fig. 9 is the compound of Example 5

[60] fullerene pyrrolidinoisoindolinone E of the present invention 1 H NMR spectrum;

[0042] Fig.10 is the compound of Example 5

[60] fullerene pyrrolidinoisoindolinone E of the present invention 13 C NMR spectrum;

[0043] Fig.11 is the present invention Example 6

[60] fullerene pyrrolidinoisoindolinone F 1 H NMR spectrum;

[0044] Fig.12 is the present invention Example 6

[60] fullerene pyrrolidinoisoindolinone F 13 C NMR spectrum;

[0045] Fig.13 is the present invention Example 7

[60] fullerene pyrrolidinoisoindolinone G 1 H NMR spectrum;

[0046] Fig.14 is the present invention Example 7

[60] fullerene pyrrolidinoisoindolinone G 13 C NMR spectrum;

[0047] Fig.15 is the present invention Example 8

[60] fullerene pyrrolidinoisoindolinone H 1 H NMR spectrum;

[0048] Fig.16 is the present invention Example 8

[60] fullerene pyrrolidinoisoindolinone H 13C NMR spectrum;

[0049] Fig.17 is a thermogravimetric analysis (TGA) diagram of

[60] fullerene pyrrolidinoisoindolinone for the implementation of the present invention;

[0050] Fig.18 This is a CV curve diagram of

[60] fullerene pyrrolidinoisoindolinone in the present invention. Specific implementation plan

[0051] The above contents of the present invention are further described in detail below through examples, but the contents of the present invention are not limited by these examples.

[0052] Example 1

[0053] This example introduces

[60] fullerene pyrrolidinoisoindolinone A Preparation method:

[0054]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 4-methoxybenzylamine (72 μL, 0.55 mmol), basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was used to completely dissolve the mixture by ultrasonication in an ultrasonicator. Then, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidine isoindolinone A was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone A was 54%.

[0055] The reaction synthesis equation is:

[0056]

[0057] like Figure 1 As shown,

[60] fullerene pyrrolidinoisoindolinone A 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6)δ7.89(t,J=6.9Hz,2H),7.84(d,J=8.6Hz,2H),7.65-7.55(m,2H),7.15(s,1H),7.04(s,1H),6.96(d,J=8.7Hz,2H),3.79(s,3H).

[0058] like Figure 2 As shown,

[60] fullerene pyrrolidinoisoindolinone A 13 C NMR spectrum 13 C NMR (100MHz, CS 2 / DMSO-d 6 )(all 1C unless indicated)δ156.75,155.71,154.68,154.15,153.74,146.60,146.33,145.58,145.53,145.45,145.42,145.34,145.31, 145.28,145.25,145.15,144.93,144.84,144.79,144.66,144.57,144.54,144.50,144.46,144.43,144.37,144.04,144.0 0,143.82,143.68,142.82,142.47,142.23,141.97,141.78,141.72,141.63,141.37,141.31,141.28,141.14,141.10,14 1.06,140.94,140.86,140.81,140.60,139.46,139.40,139.21,136.77,136.45,135.33,135.03,134.98,129.52(2C,aryl C),127.71(2C,arylC),127.45(4C,aryl C),127.33(2C,aryl C),126.98(aryl C),126.92(4C,aryl C),126.86(aryl C),126.79(aryl C),126.27(aryl C),122.29(2C,aryl C),119.99(2C,arylC),109.65(2C,aryl C),72.04,69.01,65.90,64.67,55.82,54.21,49.81.

[0059] Example 2

[0060] This example introduces

[60] fullerene pyrrolidinoisoindolinone B Preparation method:

[0061]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 4-methylbenzylamine (70 μL, 0.55 mmol), and basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL of o-dichlorobenzene was used to completely dissolve the mixture by ultrasonication in an ultrasonicator. Then, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone B was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone B was 57%.

[0062] The reaction synthesis equation is:

[0063]

[0064] like Figure 3 As shown,

[60] fullerene pyrrolidinoisoindolinone B 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ8.03(d,J=6.6Hz,1H),7.90(d,J=7.2Hz,1H),7.80(d,J=8.1Hz,2H),7.67 -7.59(m,2H),7.30(d,J=8.0Hz,2H),7.13(s,1H),7.03(s,1H),2.41(s,3H).

[0065] like Figure 4 As shown,

[60] fullerene pyrrolidinoisoindolinone B 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ166.91(C=O),154.95,152.67,150.18,148.95,146.05,146.00,145.06,145.04,144.99,144.89(3C),144.77 ,144.75,144.64(2C),144.37,144.25,144.18,144.13,144.11,143.99(3C),143.96(2C),143.92,143.44,143.09,142.98, 142.95,142.32,141.82,141.79,141.46,141.40,141.36,141.09,140.98,140.89,140.86(2C),140.84,140.74,140.51,1 40.39,139.11,139.07,138.58,138.48,136.61,135.92,135.48,134.98,134.62,132.27,131.79,131.71,128.94(4C,aryl C),128.79(aryl C),126.80(4C,aryl C),123.94(2C,aryl C)),123.87(aryl C),79.98,72.84,70.98,66.45,20.52.

[0066] Example 3

[0067] This example introduces

[60] fullerene pyrrolidinoisoindolinone C Preparation method:

[0068]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 3-methylbenzylamine (70 μL, 0.55 mmol), and basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL of o-dichlorobenzene was used to completely dissolve the mixture by ultrasonication. Then, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone C was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone C was 55%.

[0069] The reaction synthesis equation is:

[0070]

[0071] like Figure 5 As shown, the

[60] fullerene pyrrolidinoisoindolinone C 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ8.05(d,J=6.9Hz,1H),7.91(d,J=7.2Hz,1H),7.74(d,J=8.1Hz,1H),7.70(s,1H),7.68-7.5 9(m,2H),7.39(t,J=7.7Hz,1H),7.19(d,J=7.5Hz,1H),7.13(s,1H),7.04(s,1H),2.46(s,3H).

[0072] like Figure 6 As shown, the

[60] fullerene pyrrolidinoisoindolinone C 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated) δ167.56(C=O),154.88,152.52,150.19,148.75,146.45,146.38,145.41,145.38,145.25(2C),145.16,145.13,145. 02,144.75,144.65,144.65(2C),144.56,144.49,144.46,144.40(2C),144.37,144.27,144.04,143.80,143.39,143.31,143.28, 142.84,142.29,142.23,142.16,141.86,141.79,141.76,141.43,141.30,141.26,141.23,141.21,141.18,141.13,141.09,140 .88,140.70,139.60,139.49,138.94,138.86,138.71,137.97,135.74,135.37,135.14,132.72,132.14,132.04,129.08(2C,aryl C),128.51(2C,aryl C),128.38(aryl C),127.55(2C,aryl C),124.49(2C,arylC),124.05(2C,aryl C),123.75(aryl C),80.15,73.41,71.23,66.97,21.15.

[0073] Example 4

[0074] This example introduces

[60] fullerene pyrrolidinoisoindolinone D Preparation method:

[0075]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 4-bromobenzylamine (69 μL, 0.55 mmol), and basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was used to completely dissolve the mixture by sonication in an ultrasonicator. Then, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone D was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone D is 47%. The reaction synthesis equation is:

[0076]

[0077] like Figure 7 As shown, the

[60] fullerene pyrrolidinoisoindolinone D 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ8.07-8.04(m,1H),7.91(d,J=7.3Hz,1H),7.82(d,J=8.4Hz,2H),7.70-7.61(m,4H),7.15(s,1H),7.00(s,1H).

[0078] like Figure 8 As shown, the

[60] fullerene pyrrolidinoisoindolinone D 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated) δ167.58(C=O),153.87,152.28,149.20,148.94,146.67,146.59,145.68,145.62,145.56(2C),145.53,145.49,145. 35,145.23(2C),145.04,144.89,144.84,144.79,144.71,144.68(2C),144.64(3C),144.58,143.96,143.61,143.55(2C),142.47 ,142.10,142.05,142.03,141.97,141.63(2C),141.49,141.46,141.43,141.41,141.32,141.29,140.98,140.88,139.86,139.79 ,139.57,138.99,136.27,135.61,134.96,134.69,133.47,133.40,133.13,132.31,132.12,131.00(2C,arylC),129.23(2C,aryl C),128.92(2C,aryl C),127.01(2C,aryl C),124.53(2C,aryl C),123.97(2C,aryl C),78.40,71.94,70.79,62.57.

[0079] Example 5

[0080] This example introduces

[60] fullerene pyrrolidinoisoindolinone E Preparation method:

[0081]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 4-chlorobenzylamine (67 μL, 0.55 mmol), basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was added. After the mixture was completely dissolved by sonication with an ultrasonicator, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone E was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone E was 45%.

[0082] The reaction synthesis equation is:

[0083]

[0084] like Fig. 9 As shown, the

[60] fullerene pyrrolidinoisoindolinone E 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ8.05(dd,J=6.7,1.2Hz,1H),7.91(d,J=7.1Hz,1H),7.87(d,J=8.5Hz,2H),7.70-7.60(m,2H),7.51-7.46(m,2H),7.16(s,1H),7.00(s,1H).

[0085] like Fig.10 As shown, the

[60] fullerene pyrrolidinoisoindolinone E 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated)δ167.96(C=O),167.96,154.70,152.54,149.82,148.70,146.67,146.62,145.64,145.59,145.49(2C),145.48,14 5.39,145.36,145.25,145.12,144.87,144.82(2C),144.78,144.71(2C),144.63,144.58,144.52,144.11,143.98,143.59,14 3.49(2C),142.83,142.45(2C),142.07,142.03,142.00,141.62,141.47,141.44,141.39(3C),141.36,141.32,141.29,141.0 8,140.91,139.82,139.75,139.27,139.10,137.53,135.99,135.37,135.29,134.05,133.03,132.39,132.05,129.35(2C,aryl C),128.88(3C,aryl C),128.41(3C,aryl C),124.74(2C,aryl C),123.99(2C,aryl C),80.20,73.62,71.41,66.67.

[0086] Example 6

[0087] This example describes

[60] fullerene pyrrolidinoisoindolinone F Preparation method:

[0088]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (52.5 mg, 0.35 mmol), 4-fluorobenzylamine (63 μL, 0.55 mmol), and basic lead acetate (85.0 mg, 0.15 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was used to completely dissolve the mixture by sonication in an ultrasonicator. Then, the mixture was heated and stirred in an oil bath at 170°C for 60 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone F was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone F is 46%. The reaction synthesis equation is:

[0089]

[0090] like Fig.11 As shown, the

[60] fullerene pyrrolidinoisoindolinone F 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ8.02(dd,J=6.5,1.3Hz,1H),7.91-7.85(m,3H),7.66-7.57(m,2H),7.19-7.14(m,2H),7.13(s,1H),6.98(s,1H).

[0091] like Fig.12 As shown, the

[60] fullerene pyrrolidinoisoindolinone F 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3 )(all 1C unless indicated)δ168.12(C=O),161.90(d,J C-F=247.2Hz,arylC),154.90,152.73,150.15,148.88,146.81,146.75,145.77,145.73,145.6 3(2C),145.53,145.49,145.38,145.29,145.01,144.98,144.96,144.91,144.84,144.79,14 4.77,144.72,144.69,144.65,144.27,144.12,143.73,143.62,143.02,142.59,142.53,142 .21,142.16,142.13,141.75,141.60(3C),141.57,141.53(2C),141.49(2C),141.45,141.43 141.20,141.04,139.95,139.88,139.39,139.23,136.08,135.53,135.44,135.05,133.14,132.47,132.24,129.44(2C,aryl C),128.97(2C,aryl C),128.92(aryl C),124.85(2C,aryl C),124.12(2C,aryl C),115.85(aryl C),115.71(aryl C),80.43,73.67,71.51,66.76.

[0092] Example 7

[0093] This example introduces

[60] fullerene pyrrolidinoisoindolinone G Preparation method:

[0094]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (150.1 mg, 1.00 mmol), 4-methylphenylethylamine (160 μL, 1.10 mmol), and basic lead acetate (170.0 mg, 0.30 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was used to completely dissolve the mixture by ultrasonication in an ultrasonicator. Then, the mixture was heated and stirred in an oil bath at 170°C for 180 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone G was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone G was 31%.

[0095] The reaction synthesis equation is:

[0096]

[0097] like Fig.13 As shown,

[60] fullerene pyrrolidinoisoindolinone G 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ7.90(d,J=6.9Hz,1H),7.82(d,J=7.2Hz,1H),7.60-7.52(m,2H),7.44(d,J=7.9Hz,2H),7.1 6(d,J=7.8Hz,2H),6.61(s,1H),6.32(dd,J=9.9,6.5Hz,1H),3.99-3.87(m,2H),2.35(s,3H).

[0098] like Fig.14

[60] Fullerene pyrrolidinoisoindolinone G 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated)δ167.44(C=O),154.27,152.51,149.61(2C),146.74,146.65,145.77,145.68,145.66,145.64,145.61,145.56,145.48,1 45.45,145.32,145.14,144.99,144.96,144.90,144.86,144.80,144.78,144.77,144.74,144.69(2C),144.65,144.07,143.72,143. 69(2C),143.65,142.57,142.19,142.12,142.11,142.09,142.05,141.73,141.69,141.62(2C),141.51,141.41,141.39,141.04,140 .99,139.93,139.83,139.49,139.05,136.21,135.89,135.06,133.57,133.31,132.78,131.99,129.20(2C,arylC),129.01(3C,aryl C),128.60(3C,aryl C),124.54(2C,aryl C),123.99(2C,aryl C),78.69,72.19,70.54,63.35,41.61 20.91.

[0099] Example 8

[0100] This example introduces

[60] fullerene pyrrolidinoisoindolinone H Preparation method:

[0101]

[60] fullerene (36.0 mg, 0.05 mmol), o-carboxybenzaldehyde (150.1 mg, 1.00 mmol), 4-bromophenethylamine (171 μL, 1.10 mmol), and basic lead acetate (170.0 mg, 0.30 mmol) were added to a 100 mL round-bottom flask, and 4 mL o-dichlorobenzene was used to completely dissolve the mixture by sonication in an ultrasonicator. The mixture was then heated and stirred in an oil bath at 170°C for 180 minutes under air conditions, and tracked by thin layer chromatography (TLC) spot plate. 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, and then a mixed solution of carbon disulfide and dichloromethane was used as the eluent to continue separation, and finally a brown solid

[60] fullerene pyrrolidinoisoindolinone H was obtained. In this example, the yield of

[60] fullerene pyrrolidinoisoindolinone H was 30%.

[0102] The reaction synthesis equation is:

[0103]

[0104] like Fig.15 As shown,

[60] fullerene pyrrolidinoisoindolinone G 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / CDCl 3 )δ7.92(d,J=7.0Hz,1H),7.83(d,J=7.1Hz,1H),7.62-7.53(m,2H),7.50(d,J=8.7Hz,2 H),7.47(d,J=8.7Hz,2H),6.61(s,1H),6.32(dd,J=9.6,6.8Hz,1H),3.98-3.87(m,2H).

[0105] like Fig.16

[60] Fullerene pyrrolidinoisoindolinone G 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated)δ167.31(C=O),153.80,152.19,149.19,149.05,146.53,146.45,145.56,145.49,145.44(2C),145.41,145.36,145.23 ,145.12,145.11,144.93,144.74(2C),144.67,144.63,144.57,144.53,144.51,144.49,144.45,144.39,143.83,143.47,143.44, 143.36,142.37,142.34,141.98,141.93,141.90,141.81,141.50(2C),141.37(3C),141.31,141.30,141.24,141.18,140.82,140. 77,139.75,139.63,139.33,138.88,136.02,135.51,135.19,134.81,133.38,132.31,131.97,131.21(3C,arylC),130.08(3C,aryl C),129.16(aryl C),124.45(2C,aryl C),123.82(2C,aryl C),120.92(aryl C),78.34,71.94,70.41,62.77,41.10.

[0106] The present invention relates to a method for preparing pyrrolidine isoindolinone containing one or more of the fullerenes described above, but the scope of the present invention is not limited thereto. 1 -CH 2 -NH 2 ), o-carboxybenzaldehyde as raw material, o-dichlorobenzene as solvent, heating reaction in air to synthesize fullerene pyrrolidinoisoindolinone R 1 for R 2 is one of an alkyl group, a halo group, and an alkoxy group, wherein C n It is C 60 To C 84 of fullerenes.

[0107] The synthesis equation is:

[0108]

[0109] The fullerene C used in the above examples n Raw materials include

[60] fullerene, fullerene Cn The number n of carbon atoms contained is 60, 70, 76, 78, 82, 84, 90, 94 or 96, very preferably 60 or 70. 2 It is one of alkyl, halo and alkoxy. The present invention does not limit the size of m, and preferably m=1 to 2, which has been verified to be synthesized by the method of the present invention.

[0110] Pyrrolidine is a nitrogen-containing five-membered ring with special chemical properties and wide applications. It can be used to prepare various chemicals such as drugs and plastics, and can also be used as solvents and promoters, playing an important role in chemical reactions. Indolinone compounds are an important intermediate in organic synthesis. They can not only synthesize some biologically active compounds, but can also be used in the dye industry and pesticide industry. Its wide application shows that the study of indolinone compounds is of great significance, but there is no reaction to link pyrrolidine and indolinone structural fragments in fullerene derivatization. Therefore, the synthesis of such complex fullerene derivatives is of great significance. Huang Fei et al. described the application of a fullerene pyrrolidine derivative as a catalyst carrier in "A fullerene pyrrolidine derivative and its preparation method and application". The prepared fullerene pyrrolidine derivative can be used as a catalyst carrier, loaded with Cu nanoparticle catalyst, and used to catalyze the oxidation of benzyl alcohol; it has high catalytic efficiency and good selectivity, and the catalyst can maintain a yield of more than 93% after being recycled for 5 times, and the catalytic activity is relatively stable.

[0111] Application Example 1

[0112] Cyclic voltammetry (CV) is a commonly used test method in electrochemistry. Its measurement principle is to make the potential on the working electrode scan as a triangle wave, that is, the potential changes from the starting potential E to the current potential E at a given rate v. 0 Scan to the end potential E λ Then scan back to E at the same rate. 0 , and record the corresponding current-potential (IE) curve, also known as the voltammetric curve.

[0113] like Fig.18 As shown, we used cyclic voltammetry to test the redox potential diagram of

[60] fullerene isoindolinone D and found that the oxidation potential peak of the compound appeared at around 1.28V and the reduction potential peak of the compound appeared at around -1.09V. These two peaks indicate that it has a certain redox potential, indicating that such compounds may have certain application potential in the field of solar cells.

[0114] (1) Related studies have shown that TiO, a widely used electron transport layer in perovskite solar cells, 2It is one of the main reasons for the poor stability of the device. 2 The low electron mobility and its photocatalytic effect lead to hysteresis and degradation of part of the perovskite layer at the interface. A

[60] fullerene pyrrolidine derivative prepared by the present invention has higher electron mobility, conductivity and more suitable lowest unoccupied molecular orbital energy level, and can be used as an interface modification material for the electron transport layer and the perovskite light absorption layer to improve the efficiency of the device;

[0115] (2) Currently, the main solution-processable fullerene electron transport layers are C 60 Derivatives [6,6]-phenyl-C 61 -Butyric acid methyl ester (PCBM), however, the preparation of PCBM must go through multi-step synthesis, there are problems of low yield and difficulty in separation and purification, resulting in high cost. In contrast, the synthesis of fullerene pyrrolidine derivatives is relatively simple and easy to be chemically modified. The method for preparing fullerene pyrrolidine and isoindolinone of the present invention is simple, the product can be obtained after a one-step thermal reaction in the air, and most of the substrates are cheap and readily available. The obtained product has excellent solubility and selectivity, and is easy to separate and purify.

Claims

1. A method for preparing fullerene pyrrolidinoisoindolinone based on o-carboxybenzaldehyde, characterized in that: Fullerene, aromatic alkylamine, and o-carboxybenzaldehyde are used as raw materials, basic lead acetate is used as a promoter, and o-dichlorobenzene is used as a solvent. Fullerene pyrrolidine and isoindolinone are synthesized by heating in air. Aromatic alkyl amine is R1-CH2-NH2, R1 is R2 is one of an alkyl group, a halo group, and an alkoxy group. n It is C 60 To C 84 of fullerenes.

2. The method for preparing fullerene pyrrolidinoisoindolinone based on o-carboxybenzaldehyde according to claim 1, characterized in that: The synthesis equation is:

3. The method for preparing fullerene pyrrolidinoisoindolinone based on o-carboxybenzaldehyde according to claim 2, characterized in that: Aromatic alkyl amine is aromatic methyl amine, and the synthesis formula is:

4. The method for preparing fullerene pyrrolidinoisoindolinone based on o-carboxybenzaldehyde according to claim 2, characterized in that: Aromatic alkyl amine can be replaced by aromatic ethyl amine, and the synthesis formula is:

5. The method for preparing fullerene pyrrolidinoisoindolinone based on o-carboxybenzaldehyde according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: adding raw materials of fullerene, o-carboxybenzaldehyde and aromatic alkylamine into a reaction container, adding basic lead acetate as a promoter, adding solvent o-dichlorobenzene, and fully dissolving it under an ultrasonic instrument, then placing the reaction container on a constant temperature heater for heating and stirring, and after the reaction is completed, first cooling the reaction liquid with room temperature water, then directly adding the reaction liquid into a silica gel column for separation, first obtaining unreacted fullerene with carbon disulfide as an eluent, then continuing to separate with carbon disulfide and dichloromethane as eluents, and finally obtaining brown solid fullerene pyrrolidinoisoindolinone.

6. The preparation method according to claim 5, characterized in that: The constant temperature heating is 170° C., and the molar ratio of the fullerene, o-carboxybenzaldehyde, aromatic alkylamine, and basic lead acetate is 1:7-20:11-22:3-6.

7. A fullerene pyrrolidinoisoindolinone prepared by the method according to claim 5, characterized in that: Fullerene pyrrolidinoisoindolinone is R1 is R2 is one of an alkyl group, a halo group, and an alkoxy group. n It is C 60 To C 84 of fullerenes.

8. Fullerene pyrrolidinoisoindolinone prepared by the method according to claim 5, characterized in that: C n It is C 60 Fullerenes and fullerene pyrrolidinoisoindolinones include one of the following compounds:

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