A method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde

Abstract

The invention discloses a method for preparing fullerene pyrrolidinoisoquinoline based on the participation of o-phenylacetylene benzaldehyde, which belongs to the field of fullerene derivative synthesis. Fullerene, aromatic alkylamine and o-phenylacetylene benzaldehyde are used as raw materials, and o-dichlorobenzene is used as solvent. Under light-proof conditions, a one-step thermal reaction in the air is performed to obtain the target product, fullerene pyrrolidinoisoquinoline. The invention has the advantages of simple and novel synthesis method, good substrate universality and high yield, and has broad application prospects.

Description

Technical Field

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

[0002] Fullerenes have attracted special attention from many researchers in recent years due to their unique zero-dimensional structure, special optoelectronic properties and chemical properties. However, due to the symmetrical carbon cage structure of fullerenes themselves, they have poor polarity, resulting in very low solubility in water or organic polar solvents, which limits further research and application in various fields. It is particularly important to greatly improve the solubility of fullerenes in water or organic polar solvents through functionalization of fullerenes. The introduction of nitrogen heterocycles is conducive to enhancing the electron acceptance ability of fullerenes, making them more widely used in the field of optoelectronic materials. The construction of fullerene nitrogen heterocyclic compounds is generally through 1,3-dipolar cycloaddition reaction to form carbon-nitrogen atomic bonds. A series of fullerene nitrogen heterocyclic derivatives such as fullerene pyrrolidine, fullerene pyrroline, fullerene tetrahydroquinoline, etc. have been successfully synthesized one after another and have been widely used in the fields of energy, chemical industry and basic materials.

[0003] As shown in Formula 1, Martin reported fullerene C in 1998. 60 Three fullerene tetrahydroquinoline compounds were synthesized by reacting with N-methylanilinochlorophenylborane and aldehyde under reflux conditions (J. Org. Chem. 1998, 63, 8074-8076).

[0004]

[0005] As shown in Formula 2, in 2011, the research group of Professor Wang Guanwu of the University of Science and Technology of China studied the cyclization reaction of

[60] fullerene and benzamide promoted by palladium-catalyzed carbon-hydrogen activation reaction, and obtained fullerene isoquinolinone derivatives (J.Org.Chem.2011,76,1599-1604).

[0006]

[0007] As shown in Formula 3, in 2017, the research group of Linlong Deng from Xiamen University used the Prato reaction to synthesize a series of N-phenyl-substituted fullerene pyrrolidine derivatives.

[0008]

[0009] As shown in Formula 4, in 2018, Li Fabao's research group at Hubei University synthesized a series of rare N-alkyl-2,5-unsubstituted / monosubstituted fulleropyrrolidines by reacting

[60] fullerene with primary / secondary amines in the presence of paraformaldehyde through a simple one-step thermal reaction (J. Org. Chem. 2019, 84, 2922-2932).

[0010]

[0011] CN 106458815B discloses fused bis-aryl fullerene derivatives It is used in semiconductors, charge transport, conductivity, photoconductivity, photoactivity, thermoelectric materials or luminescent materials. There is an urgent need to prepare fullerene pyrrolidine derivatives similar to fused bis-aryl fullerene derivatives and expand the preparation method of fullerene pyrrolidine derivatives. Summary of the invention

[0012] 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 pyrrolidinoisoquinoline based on the participation of o-phenylacetylene benzaldehyde, utilize fullerene and o-phenylacetylene benzaldehyde and aromatic amine to react to produce fullerene pyrrolidinoisoquinoline, improve the yield of target derivatives, and verify the universality of the product.

[0013] The method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde is described in the present invention. Fullerene and substrate 1, o-phenylacetylene benzaldehyde are used as raw materials, benzoic acid is used as a catalyst, and o-dichlorobenzene is used as a solvent. Under light-proof conditions, the reaction is heated in the air to synthesize fullerene pyrrolidinoisoquinoline. R 1 for R 3 A hydrogen atom or R 2 , R 4 is one of a hydrogen atom, an alkyl group, a halogen group, an aryl group, and an alkoxy group, wherein Cn is a fullerene of C60 to C84, and the substrate 1 is

[0014] Preferably, the synthesis equation is:

[0015]

[0016] Preferably, when R 3 for When the substrate 1 is an aromatic alkyl amine, the molar ratio of the fullerene, o-bromophenylbenzaldehyde, aromatic alkyl amine and benzoic acid is 1:2:5-8:2, and the heating reaction temperature is 110-150°C.

[0017] Preferably, the aromatic alkylamine is aromatic methylamine, and the synthesis equation is:

[0018]

[0019] Preferably, the molar ratio of fullerene, o-bromobenzylbenzaldehyde, aromatic methylamine and benzoic acid is 1:2:8:2, and the heating reaction temperature is 110°C.

[0020] Preferably, the aromatic alkylamine is aromatic ethylamine, and the synthesis equation is:

[0021]

[0022] Preferably, the molar ratio of fullerene, o-phenylethynylbenzaldehyde, aromatic ethylamine and benzoic acid is 1:2:5:2, and the heating reaction temperature is 150°C.

[0023] Preferably, Cn is C60 fullerene, the aromatic alkylamine is aromatic methylamine, and the synthesis equation is:

[0024]

[0025] Preferably, Cn is C60 fullerene, the aromatic alkyl amine is aromatic ethyl amine, and the synthesis formula is:

[0026]

[0027] Preferably, the specific steps for preparing fullerene pyrrolidinoisoquinoline are as follows: adding raw materials

[60] fullerene, o-phenylethynylbenzaldehyde and aromatic alkylamine into a reaction vessel, adding benzoic acid as a catalyst, adding solvent o-dichlorobenzene, and using an ultrasonic instrument to dissolve the reactants and the catalyst, heating the reactants at a constant temperature and stirring, and reacting under light-proof conditions. After the reaction is completed, the reaction mixture is firstly coarsely filtered through a short silica gel column to remove insoluble impurities, and the solvent is evaporated under reduced pressure. After that, the residue is separated by chromatography using carbon disulfide as an eluent. The first thing to be separated is unreacted

[60] fullerene, and then

[60] fullerene pyrrolidinoisoquinoline is obtained.

[0028] The fullerene pyrrolidinoisoquinoline prepared by the method described is R 1 for R 3 A hydrogen atom or R 2 , R 4 is one of a hydrogen atom, an alkyl group, a halogen group, an aryl group, and an alkoxy group, wherein Cn is a fullerene of C60 to C84, and the substrate 1 is

[0029] Based on the fullerene pyrrolidinoisoquinoline prepared by the method, Cn is C60 fullerene, and the fullerene pyrrolidinoisoquinoline includes one of the following compounds,

[0030]

[0031] Compared with the prior art, the present invention has the following outstanding advantages:

[0032] 1. The present invention provides a method for preparing

[60] fullerene pyrrolidinoisoquinoline, which has high yield and is particularly suitable for large-scale production.

[60] fullerene pyrrolidinoisoquinoline has great application prospects in the field of preparation of n-type semiconductors and can be used in semiconductors, charge transport, conductivity, photoconductivity, photoactivity, thermoelectric materials or luminescent materials;

[0033] 2. The fullerene pyrrolidine derivative obtained by this method has a novel structure, which enriches the preparation method of

[60] fullerene pyrrolidine derivatives. The product has good solubility and selectivity and is easy to separate and purify;

[0034] 3. The substrate used in this method has a wide range of applications and good universality. At the same time, the method for preparing

[60] fullerene pyrrolidine and isoquinoline is simple and can be obtained by a one-step thermal reaction in the air under light-proof conditions. The preparation conditions and process are relatively loose compared to the conditions and requirements of other existing technologies, which reduces the barriers to the preparation of fullerene pyrrolidine derivatives. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is the present invention Example 1

[60] fullerene pyrrolidinoisoquinoline A 1 H NMR spectrum;

[0036] Figure 2 is the present invention Example 1

[60] fullerene pyrrolidinoisoquinoline A 13 C NMR spectrum;

[0037] Figure 3 is the present invention Example 2

[60] fullerene pyrrolidinoisoquinoline B 1 H NMR spectrum;

[0038] Figure 4 is the present invention Example 2

[60] fullerene pyrrolidinoisoquinoline B 13 C NMR spectrum;

[0039] Figure 5 is the present invention embodiment 3

[60] fullerene pyrrolidinoisoquinoline C 1 H NMR spectrum;

[0040] Figure 6is the present invention embodiment 3

[60] fullerene pyrrolidinoisoquinoline C 13 C NMR spectrum;

[0041] Figure 7 is the present invention Example 4

[60] fullerene pyrrolidinoisoquinoline D 1 H NMR spectrum;

[0042] Figure 8 is the present invention Example 4

[60] fullerene pyrrolidinoisoquinoline D 13 C NMR spectrum;

[0043] Fig. 9 is the present invention Example 5

[60] fullerene pyrrolidinoisoquinoline E 1 H NMR spectrum;

[0044] Fig.10 is the present invention Example 5

[60] fullerene pyrrolidinoisoquinoline E 13 C NMR spectrum;

[0045] Fig.11 is the present invention Example 6

[60] fullerene pyrrolidinoisoquinoline F 1 H NMR spectrum;

[0046] Fig.12 is the present invention Example 6

[60] fullerene pyrrolidinoisoquinoline F 13 C NMR spectrum;

[0047] Fig.13 is the present invention Example 6

[60] fullerene pyrrolidinoisoquinoline G 1 H NMR spectrum;

[0048] Fig.14 is the present invention Example 6

[60] fullerene pyrrolidinoisoquinoline G 13 C NMR spectrum;

[0049] Fig.15 This is the TLC spot plate image at the end point of the reaction of Example 2 of the present invention;

[0050] Fig.16 This is the TLC spot plate image at the end point of the reaction of Example 3 of 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 pyrrolidinoisoquinoline A Preparation method:

[0054]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenylynylbenzaldehyde 18 μL, 0.1 mmol), p-methylphenylethylamine (36 μL, 0.25 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask. 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 150°C and heated with stirring for 20 minutes under light-proof conditions. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction ended.

[0055] After the reaction, the reaction mixture was filtered through a short silica gel column to remove insoluble matter, the solvent was removed under reduced pressure in a rotary evaporator, and the residue was separated by chromatography using carbon disulfide as an eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

[60] fullerene pyrrolidinoisoquinoline A. The yield of

[60] fullerene pyrrolidinoisoquinoline A in this example was 43%.

[0056] like Figure 1 As shown, it is

[60] fullerene pyrrolidinoisoquinoline A 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.57(d,J=7.40Hz,1H),7.30(d,J=7.60Hz,2H),7.19-7.17(m,5H),7.08(t,J=7.38Hz,1H),7.00(d,J=7.52Hz,1H) ,6.75-6.72(m,1H),5.66(dd,J=11.26,4.38Hz,1H),5.48(s,1H),3.99-3.92(m,1H),3.54(dd,J=13.8,4.16Hz,1H).

[0057] like Figure 2 As shown, it is

[60] fullerene pyrrolidinoisoquinoline A 13 C NMR spectrum 13 C NMR (400MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ154.14,152.86,152.39,151.522,146.33,145.85,145.83,145.65,145.45,145.18,144.98,144.89,144.73(2C) ,144.64,144.51,144.45(3C),144.12,144.04,144.00,143.88,143.86(2C),143.83(2C),143.72,143.63,143.24,143.12(2C) ),142.90,141.90,141.76,141.33(4C),141.27,141.13,140.96,140.89,140.86(2C),140.79,140.71,140.61,140.58,140.3 0,140.16,138.67,138.58,138.55,138.32,135.97,135.25,135.19,134.95,134.68,134.22,133.63,132.45,129.46(4C,aryl C),128.20(4C,aryl C),128.13(2C,aryl C),127.35(5C,aryl C),127.11(2C,aryl C),126.61(2C,aryl C),126.01(aryl C),124.39(2C,aryl C),124.21(2C,aryl C),104.50(2C,aryl C),82.53,75.14(2C),73.66,70.76(2C),29.04,20.55(2C)

[0058] Example 2

[0059] This example introduces

[60] fullerene pyrrolidinoisoquinoline B Preparation method:

[0060]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenyl alkynyl benzaldehyde (18 μL, 0.1 mmol), p-methoxyphenylethylamine (37 μL, 0.25 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 150°C and heated with stirring for 20 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction ended. Fig.15The figure shows the TLC spot plate at the end of the reaction. After the reaction, the reaction mixture was filtered through a short silica gel column to remove insoluble matter, the solvent was removed under reduced pressure in a rotary evaporator, and the residue was separated by chromatography using a chromatographic column with carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

[60] fullerene pyrrolidinoisoquinoline B. The yield of

[60] fullerene pyrrolidinoisoquinoline B in this example was 48%.

[0061] like Figure 3 As shown, it is

[60] fullerene pyrrolidinoisoquinoline B 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.57(d,J=7.36Hz,1H),7.32(d,J=8.20Hz,2H),7.19(t,J=6.80Hz,3H),7.08(t,J=7.42Hz,2H),7.01(d,J=7.48Hz,1H),6.90(d,J=7.482 4Hz,2H),6.76(s,1H),5.65(dd,J=11.32,4.24Hz,1H),5.49(s,1H),3.96(t,J=12.62Hz,1H),3.80(s,3H),3.51(dd,J=13.84,4.20Hz,1H).

[0062] like Figure 4 As shown, it is

[60] fullerene pyrrolidinoisoquinoline A 13 C NMR spectrum 13 C NMR 13 C NMR (400MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ157.08,153.57,152.27,151.81,150.96,145.80,145.26,145.25,145.06,144.86,144.59,144.40,144.30,144. 14(2C),144.05,143.92,143.87(3C),143.53,143.45,143.40,143.29,143.27(2C),143.23(2C),143.14,143.04,142.65,142 .53(2C),142.31,141.32,141.18,140.74(3C),140.69,140.37,140.30,140.27(2C),140.20,140.12,140.02,139.99,139.71 ,139.57,138.08,137.99,137.97,137.73,135.42,134.65,134.36,134.10,133.03,133.18,129.92(3C,arylC),128.50(aryl C),127.70(aryl C),126.77(2C),126.71(aryl C),126.10(aryl C),125.43(aryl C),123.99(aryl C),123.77(aryl C),112.50(3C,aryl C),104.01(2C,arylC),81.95,74.64(2C),73.03,70.11(2C),53.94,29.14,28.49;

[0063] Example 3

[0064] This example introduces

[60] fullerene pyrrolidinoisoquinoline C Preparation method:

[0065]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenyl alkynyl benzaldehyde (18 μL, 0.1 mmol), p-bromophenylethylamine (39 μL, 0.25 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 150°C and heated with stirring for 20 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction ended. Fig.16The figure shows the TLC spot plate at the end of the reaction. After the reaction, the reaction mixture was filtered through a short silica gel column to remove insoluble matter, the solvent was removed under reduced pressure in a rotary evaporator, and the residue was separated by chromatography using a chromatographic column with carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

[60] fullerene pyrrolidinoisoquinoline C. The yield of

[60] fullerene pyrrolidinoisoquinoline C in this example was 44%.

[0066] like Figure 5 As shown, it is

[60] fullerene pyrrolidinoisoquinoline C 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.58(d,J=7.48Hz,1H),7.52(d,J=8.28Hz,2H),7.39(d,J=8.28Hz,2H),7.23-7.17(m,2H),7.10-7.08(m,1H ),7.01(d,J=7.52Hz,1H),6.80(s,1H),5.67-5.63(m,1H),5.50(s,1H),4.05-3.98(m,1H),3.57-3.53(m,1H).

[0067] like Figure 6 As shown, it is

[60] fullerene pyrrolidinoisoquinoline C 13 C NMR spectrum 13 C NMR (400MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ153.73,152.59,152.14,151.07,145.89,145.60,145.57,145.47,145.25,144.96,144.78,144.70,144.54(2C),144.4 4,144.31,144.27,144.25,144.22,143.91,143.81,143.80,143.69,143.66,143.64(2C),143.61,143.52,143.43,143.02,142.92(2C) C),142.67,141.69,141.57,141.14(4C),141.01,140.88,140.75,140.69,140.65(2C),140.58,140.46,140.41,140.37,140.09,13 9.95,138.46,138.34(2C),138.13,136.34,135.74,135.12,134.68,134.44,133.50,132.15,131.23(3C),130.38(3C),128.00(aryl C),127.09(4C,aryl C),126.51(aryl C),125.86(arylC),124.95(aryl C),124.14(aryl C),120.12(aryl C),104.71(aryl C),82.22,74.64(2C),73.42,70.43(2C),29.29,28.82;

[0068] Example 4

[0069] This example introduces

[60] fullerene pyrrolidinoisoquinoline D Preparation method:

[0070]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenyl alkynyl benzaldehyde (18 μL, 0.1 mmol), benzylamine (43 μL, 0.40 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 110°C and heated and stirred for 18 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction end point was reached. After the reaction was completed, the reaction mixture was coarsely filtered through a short silica gel column to remove insoluble substances, and the solvent was decompressed and spun off in a rotary evaporator. The residue was separated by chromatography using carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

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

[60] fullerene pyrrolidinoisoquinoline D was 43%.

[0071] like Figure 7 As shown, it is

[60] fullerene pyrrolidinoisoquinoline D 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.80(d,J=7.44Hz,2H),7.51-7.40(m,5H),7.33-7.28(m,4H),7.18(t,J=6.92 Hz,1H),7.06-7.02(m,2H),6.82(s,1H),6.70(s,1H),5.68(s,1H),4.20(s,1H).

[0072] like Figure 8 As shown, it is

[60] fullerene pyrrolidinoisoquinoline D 13 C NMR spectrum 13 C NMR (400MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ155.26,151.86,151.84,151.50,146.24,145.81,145.70,145.43,145.34,145.02,144.89,144.82,144.65 (4C),144.47,144.43(2C),144.35,143.93,143.89(2C),143.81(2C),143.78,143.75(4C),143.21,143.09,142.96,142 .75,142.62,141.70(2C),141.33,141.29(3C),141.25,140.95,140.86,140.84,140.82(4C),140.71,140.68,140.52,1 40.32,140.21,138.66,138.45,138.31,138.27,137.41,136.36,135.48,134.79(2C),132.82,132.26,128.14(6C,aryl C),127.76(2C,aryl C),126.95(2C,aryl C),126.61(4C,aryl C),126.47(2C,aryl C),126.26(3C,aryl C),125.59(aryl C),124.70(2C,aryl C),124.31(2C,aryl C),104.06(aryl C),82.67,77.21(2C),74.73,73.70(2C),28.96(2C);

[0073] Example 5

[0074] This example introduces

[60] fullerene pyrrolidinoisoquinoline E Preparation method:

[0075]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenyl alkynyl benzaldehyde (18 μL, 0.1 mmol), p-methylbenzylamine (51 μL, 0.40 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 110°C and heated and stirred for 18 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction end point was reached. After the reaction was completed, the reaction mixture was coarsely filtered through a short silica gel column to remove insoluble substances, and the solvent was decompressed and spun off in a rotary evaporator. The residue was separated by chromatography using carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

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

[60] fullerene pyrrolidinoisoquinoline E was 51%.

[0076] like Fig. 9 As shown, it is

[60] fullerene pyrrolidinoisoquinoline E 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.70(d,J=8.04Hz,2H),7.54(br.s,2H),7.48(d,J=7.88Hz,1H),7.32(t,J=2.20Hz,3H),7.25(d,J=8.04Hz ,2H),7.20(dd,J=7.46,1.06Hz,1H),7.10-7.04(m,2H),6.81(s,1H),6.76(s,1H),5.71(s,1H),2.42(s,3H).

[0077] like Fig.10 As shown, it is

[60] fullerene pyrrolidinoisoquinoline E 13 C NMR spectrum 13 C NMR (400MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ155.33,151.94,151.89,151.66,146.32,145.84,145.68,145.42,145.37,145.06,144.89,144.81,144.64(3C),1 44.47,144.43(2C),144.35,143.95,143.89,143.87,143.80(2C),143.77,143.74(3C),143.22,143.08,142.96,142.76,142.6 7,141.82,141.72,141.70,141.33,141.28(2C),141.24,140.95,140.87(2C),140.81(2C),140.78,140.72,140.67,140.51,14 0.31,140.21,138.65,138.44,138.29,138.26,136.40,136.24,135.49,134.82(2C),134.50,132.80,132.30,128.80(4C,aryl C),128.14(2C,aryl C),127.74(2C,aryl C),126.60(4C,aryl C),126.45(2C,aryl C),126.29(3C,aryl C),125.63(aryl C),124.68(2C,aryl C),124.27(2C,aryl C),103.91(aryl C),82.68,77.12(2C),74.79,73.68(2C),28.96,20.42;

[0078] Example 6

[0079] This example describes

[60] fullerene pyrrolidinoisoquinoline F Preparation method:

[0080]

[60] fullerene (36.0 mg, 0.05 mmol), o-phenyl alkynyl benzaldehyde (18 μL, 0.1 mmol), p-chlorobenzylamine (49 μL, 0.40 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 110°C and heated and stirred for 18 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction end point was reached. After the reaction was completed, the reaction mixture was coarsely filtered through a short silica gel column to remove insoluble substances, and the solvent was decompressed and spun off in a rotary evaporator. The residue was separated by chromatography using carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

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

[60] fullerene pyrrolidinoisoquinoline F was 57%.

[0081] like Fig.11 As shown,

[60] fullerene pyrrolidinoisoquinoline F 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ7.82(d,J=8.44Hz,2H),7.53(s,2H),7.50(d,J=7.56Hz,1H),7.44(d,J=8.52Hz,2H),7.33 (s,3H),7.24-7.16(m,2H),7.12-7.06(m,2H),6.83(s,1H),6.72-6.70(m,1H),5.75(s,1H).

[0082] like Fig.12 As shown,

[60] fullerene pyrrolidinoisoquinoline F 13 C NMR spectrum 13 C NMR (600MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ155.07,151.87,151.77,151.16,146.12,145.86,145.83,145.55,145.37,145.01,144.97,144.92,14 4.78(3C),144.60,144.56(2C),144.44,144.01(3C),143.93,143.89(3C),143.31,143.21,143.07,142.83,142.65, 141.92,141.84,141.82,141.43,141.41,141.37(2C),141.05,140.97(3C),140.81(2C),140.63,140.42,140.32,1 38.74,138.59,138.45,138.44,136.36,136.10,135.67,134.88,134.81,132.98(2C),132.24,131.64,129.60(aryl C),128.32(4C,aryl C),128.29(3C,aryl C),127.94(aryl C),126.99(aryl C),126.63(2C,aryl C),125.65(aryl C),124.84(aryl C),124.50(aryl C),104.39(aryl C),82.68,76.84(2C),74.67,73.73(2C),29.06(2C);

[0083] Example 7

[0084] This example introduces

[60] fullerene pyrrolidinoisoquinoline G Preparation method:

[0085]

[60] fullerene (36.0 mg, 0.05 mmol), 2-(4-tert-butyl)phenylethynylbenzaldehyde (18 μL), p-methoxyphenylethylamine (37 μL, 0.25 mmol), and benzoic acid (12.8 mg, 0.1 mmol) were added to a flask, and 5 mL of o-dichlorobenzene was used to completely dissolve the mixture under ultrasonication in an ultrasonicator. The mixture was then immediately placed in an oil bath preset at 110°C and heated and stirred for 18 minutes. The reaction process was tracked by thin layer chromatography (TLC) spot plate, and heating was stopped when the reaction end point was reached. After the reaction was completed, the reaction mixture was coarsely filtered through a short silica gel column to remove insoluble substances, and the solvent was decompressed and spun off in a rotary evaporator. The residue was separated by chromatography using carbon disulfide as the eluent. The first thing separated was unreacted

[60] fullerene, followed by brown solid

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

[60] fullerene pyrrolidinoisoquinoline G was 63%.

[0086] like Fig.13 As shown, it is

[60] fullerene pyrrolidinoisoquinoline G 1 H NMR spectrum MR (400MHz, CS 2 / DMSO-d 6 )δ7.47-7.46(m,3H),7.32(d,J=7.60Hz,2H),7.20(t,J=7.40Hz,1H),7.07-7.02(m,2H), 6.95(d,J=8.20Hz,2H),6.85(s,1H),6.74(s,1H),5.65(s,1H),3.82(s,3H),1.32(s,9H).

[0087] like Fig.14 is

[60] fullerenepyrrolidinoisoquinoline G 13 C NMR spectrum 13 C NMR (600MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ158.05,155.51,152.18,152.12,151.94,150.28,146.51,146.02,145.83,145.56(2C),145.19,145.04,144. 96,144.79(3C),144.61,144.58(2C),144.52,144.19,144.04,144.02,143.94(4C),143.90,143.88,143.37,143.24,143. 13,142.96,142.92,141.88,141.84,141.49(2C),141.43(2C),141.39,141.10,141.08,141.05,140.97(2C),140.95,140. 86(2C),140.66,140.44,140.36,138.80,138.59,138.44(2C),135.66,134.99(2C),133.72,133.04,132.60,129.43(aryl C),128.20(2C,aryl C),127.94(4C,aryl C),126.56(2C,aryl C),126.07(3C,aryl C),125.71(aryl C),124.92(3C,aryl C),124.64(2C,aryl C),124.19(2C,aryl C),113.55(4C,aryl C),103.70(2C,aryl C),82.97,77.00(2C),75.14,73.73(2C),54.14,33.32,30.36(7C),29.12.

[0088] The present invention relates to a method for preparing fullerene pyrrolidinoisoquinoline containing one or more of the above-mentioned fullerene pyrrolidinoisoquinoline, but the scope of the present invention is not limited. In the above embodiment, fullerene, aromatic alkylamine, o-phenylacetylene benzaldehyde are used as raw materials, benzoic acid is used as a catalyst, and o-dichlorobenzene is used as a solvent. Under light-proof conditions, the reaction is heated in the air to synthesize fullerene pyrrolidinoisoquinoline. R 1 for R 3 A hydrogen atom or R 2 , R 4 is one of a hydrogen atom, an alkyl group, a halogen group, an aryl group, and an alkoxy group, wherein Cn is a fullerene of C60 to C84, and the substrate 1 is

[0089] The synthesis equation is:

[0090]

[0091] The fullerene Cn raw material used in the above embodiments includes

[60] fullerene, and the number n of carbon atoms contained in the fullerene Cn is 60, 70, 76, 78, 82, 84, 90, 94 or 96, and is most preferably 60 or 70. 2 , R 3 It is not limited to one of hydrogen atom, alkyl, halide, aryl, and alkoxy. The present invention does not limit the size of m, and preferably m=0 to 3, which has been verified to be synthesized by the method of the present invention.

[0092] Compared with other benzoquinones and naphthoquinones, fullerene is a redox active substance with lower LUMO energy, a good electron acceptor, capable of reversibly accepting multiple electrons and forming stable intermediate anions. In addition, due to the electron transport function, chemical stability and multivalence of fullerene, it also has a profound theoretical and practical basis in the construction of nanoelectronic devices and its application as a carrier of bioactive substances in electrochemical biosensors. However, since C60 has a closed cage-like three-dimensional structure and does not contain hydrogen atoms and other functional groups in the molecule, it has poor polarity, so that its solubility in water or organic polar solvents is very low, which limits further research and application in various fields. Quinoline structures not only have good water solubility, but also have a conjugated aromatic ring and have greater fluorescence intensity. The present invention additionally provides the use of the fullerene pyrrolidinoisoquinoline of the present invention as a chemical sensor or material for detecting and distinguishing DNA sequences. Such uses are described, for example, in L. Chen, DW Mc Branch, H. Wang, R. Helgeson, F. Wudl and DG Hitten, Proc. Natl. Acad. Sci. USA, 1999, 96, 12287; D. Wang, X. Gong, PS Heeger, F. Rininsland, GC Bazan and AJ Heeger, Proc. Natl. Acad. Sci. USA, 2002, 99, 49; N. DiCesare, MR Pinot, KS Schanze and JR Lakowicz, Langmuir, 2002, 18, 7785; DT McQuade, AE Pullen, TMS Wager, Chem. Rev., 2000, 100, 2537.

[0093] The alkoxy group in R2 or R3 of the fullerene pyrrolidine and isoquinoline described above can be converted into a halogenated group through a substitution reaction. The halogenated group on the benzene ring can be converted into a methyl group on the benzene ring with chloromethane under the action of the catalyst AlCl3. The methyl group on the benzene ring can be converted into a methanol group on the benzene ring, and then oxidized to form a formaldehyde group on the benzene ring. That is, R2 or R3 of the fullerene pyrrolidine and isoquinoline described above is converted into an aldehyde group. Shi Lanjuan et al. also described in "DNA electrochemical sensor based on fullerene derivative modified glassy carbon electrode" that the mild and efficient condensation reaction between the aldehyde group and the amino group can modify the 5'amino-modified probe oligonucleotide to the fullerene pyrrolidine derivative to construct a DNA electrochemical sensor. The fullerene pyrrolidine and isoquinoline described above is polar and has solubility in water or organic polar solvents, so it can be used as a chemical sensor or material for detecting and distinguishing DNA sequences.

[0094] The fullerene pyrrolidinoisoquinoline of the present invention is suitable for use as a hole transport layer, a hole blocking layer, an electron transport layer and / or an electron blocking layer in a perovskite-based solar cell. The fullerene pyrrolidinoisoquinoline of the present invention can be dissolved in a formulation and deposited by any suitable means to form a thin layer in a semiconductor device. Perovskite-based solar cells can be manufactured as described in the literature, for example, in Chem. Rev. 2010, 110, 6595-6663, Angew. Chem. Int. Ed. 2014, 53, 2-15 or WO2013171520A1.

Claims

1. A method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde, Features: Using fullerene, substrate 1 (o-phenylethynylbenzaldehyde), benzoic acid as the catalyst, and o-dichlorobenzene as the solvent, under light-shielded conditions, heat the reaction in air to synthesize fullerene pyrrolidinoisoquinoline , R 1 is R 3 -[CH 2 m -, R 3 is , R 2 , R 4 is one of a hydrogen atom, an alkyl group, or an alkoxy group, C n is C 60 fullerene, substrate 1 is R 3 -[CH 2 m+1 -NH 2 , where m = 0, 1, 2, or 3.​​ 2. The method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde according to claim 1, Features: The synthesis equation is: 。 3. The method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde according to claim 2, Features: Substrate 1 is aromatic methylamine, and the synthesis equation is: 。 4. The method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde according to claim 2, Features: Substrate 1 can be replaced by aromatic ethylamine, and the synthesis equation is: 。 5. The method for preparing fullerene pyrrolidinoisoquinoline based on o-phenylacetylene benzaldehyde according to any one of claims 1 to 4, Features: The specific steps for preparing fullerene pyrrolidinoisoquinoline are as follows: adding raw material C into a reaction vessel 60 Fullerene, o-phenylacetylene benzaldehyde and aromatic alkylamine, then add benzoic acid as a catalyst, add solvent o-dichlorobenzene, and use ultrasonic instrument to dissolve the reactants and catalyst, heat and stir the reactants at a constant temperature, and react under light-proof conditions. After the reaction is completed, the reaction mixture is first coarsely filtered through a short silica gel column to remove insoluble impurities, and the solvent is evaporated under reduced pressure. After that, the residue is separated by chromatography column chromatography with carbon disulfide as the eluent. The first thing to be separated is the unreacted C 60 Fullerene, and then fullerene pyrrolidine and isoquinoline.

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