CN113004190B - Preparation method of N-phenyl [60] fullerene pyrroline - Google Patents

Preparation method of N-phenyl [60] fullerene pyrroline Download PDF

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CN113004190B
CN113004190B CN202110244607.4A CN202110244607A CN113004190B CN 113004190 B CN113004190 B CN 113004190B CN 202110244607 A CN202110244607 A CN 202110244607A CN 113004190 B CN113004190 B CN 113004190B
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孙睿
王兴宇
李法宝
彭倩娜
刘修善
李君虞
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Hubei University
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Abstract

The invention discloses a preparation method of N-phenyl [60] fullerene pyrroline, belonging to the field of fullerene derivative synthesis, and the specific method comprises the following steps: the target product N-phenyl [60] fullerene pyrroline derivative is obtained by one-step reaction in air at 120 ℃ by using [60] fullerene, aromatic primary amine and alpha-unsubstituted aldehyde as raw materials, a mixture of manganese acetate and DMAP as a catalyst and o-dichlorobenzene or chlorobenzene as a solvent. The invention has the advantages of simple synthesis method, cheap and easily obtained raw materials, single product and the like, has wide application prospect, and has no report of adopting a one-step method to prepare the N-phenyl [60] fullerene pyrroline derivative at present, and has no report of obviously improving the yield of the N-phenyl [60] fullerene pyrroline derivative and the conversion rate of the raw materials under the condition of extremely small usage amount of a mixed catalyst of manganese acetate and DMAP.

Description

Preparation method of N-phenyl [60] fullerene pyrroline
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of N-phenyl [60] fullerene pyrroline.
Background
In recent decades, the introduction of multifunctional functional groups on fullerene frameworks by chemical modification of fullerenes has attracted much attention, because the functionalization of fullerenes not only improves their solubility in water and/or polar organic solvents, but also adjusts their energy levels and stacking structures to expand their applications in the fields of material science, biological applications, nanotechnology, and the like. Transition metal salts have proven to be a powerful tool for fullerene functionalization in place of traditional peroxide or photoinitiated free radical addition reactions. With the aid of different types of transition metal salts, a number of fullerene derivatives having different structural motifs were successfully prepared. The fullerene is an important fullerene derivative and has wide application prospect in the aspects of designing and synthesizing novel organic photovoltaic materials. A study "Cu (OAc) 2-Mediated Reaction of [60] ]fullerenewith Aldehydes and Primary Amines for The Synthesis of fulleroprolines, 2016-JOC The Journal of Organic Chemistry" by Wu Jun et al of this group in 2016 reported that N-benzyl [60] fullerene pyrroline derivatives could be synthesized with The addition of copper acetate using Aldehydes, benzylamines and [60] fullerenes, but increasing or decreasing The equivalent of copper acetate decreased The yield of N-benzyl [60] fullerene pyrrolines instead. The article also reports the reaction of aromatic amines such as aniline with [60] fullerene under optimized conditions. Unfortunately, the ideal N-phenyl [60] fullerene pyrroline derivative is not obtained due to the conjugation effect resulting from the direct bonding of the aryl group and the amine group.
[60] The mechanism of fullerene and aldehyde and primary amine promoted by copper acetate to react to generate fullerene pyrroline is shown as a formula a-b:
Figure BDA0002963619670000021
aldehyde 1 is first reacted with primary amines 2 or 4 to produce alpha-hydroxylamine intermediate I, which is then dehydrated to form schiff base imine II, which can be equilibrated with enamine intermediate III. The tautomerization of imines has been widely reported in the literature. At C 60 The nucleophilic addition of the enamine intermediate III to the C = C bond, which has been activated by the formation of a pi complex between a copper (II) lewis acid and the C = C bond, may result in the formation of a copper (II) -fullerene complex IV and the loss of one HOAC molecule. Subsequent intramolecular cyclization of complex IV with elimination of another molecule of HOAC produces a new copper (II) -fullerene complex V, which is then reductively eliminated to provide the desired fullerene pyrroline 3 or 5 and Cu0. At the same time, the study suggested that aromatic amines failed to produce the corresponding fullerene pyrroles under standard reaction conditions, probably due to the very difficult formation of the α -hydroxylamine intermediate between aldehyde and aromatic amine, since direct conjugation between aryl and amine groups reduced the nucleophilicity of the nitrogen atom on the aromatic amine to the carbonyl group of the aldehyde, which was previously addressed [60 []The reaction of fullerene with N-phenyl benzylamine was confirmed by study 1: shi, j. -l.; li, F. -B.; zhang, x-f.; wu, j.; zhang, h. -y.; peng, j.; liu, c. -x.; liu, l.; wu, p.; li, j. — x.j.org.chem.2016,81,1769, and study 2: shi, J. -L.; zhang, x. -f.; wang, H. -J.; li, F. -B.; zhong, x. -x.; liu, c. -x.; liu, l.; liu, c. -y.; qin, h. -m.; huang, Y.S.J.org.chem.2016, 81,7662.
At present, no report of N-phenyl [60] fullerene pyrroline derivative synthesized by taking aniline as a raw material through reaction exists.
In addition, the research of the subject group has large copper acetate dosage, short reaction time and difficult control of the reaction. The yield of the product was from 17% to 61% using copper acetate as catalyst. However, the reaction conversion was not high, and the average conversion was 60%, meaning that more other byproducts were produced.
Disclosure of Invention
The invention aims to prepare the N-phenyl [60] fullerene pyrroline derivative with a novel product structure by utilizing the aldehyde-amine reaction of [60] fullerene, aldehyde and aromatic primary amine, the aromatic primary amine is taken as a substrate, the application range is wide, the general applicability is realized, the yield of the target derivative and the substrate conversion rate are improved, the byproducts are reduced, the dosage of an additive manganese acetate is reduced, and the cost is reduced.
The technical scheme of the invention is a preparation method of N-phenyl [60] fullerene pyrroline derivatives, which comprises the following steps:
adding [60] fullerene, alpha-position unsubstituted aldehyde and aromatic primary amine into chlorobenzene or o-dichlorobenzene, uniformly mixing, adding a mixture of acetic acid manganese and DMAP as a catalyst, heating and stirring at a constant temperature, tracking and monitoring the reaction progress by using a thin-layer chromatography, stopping the reaction when the product amount is not increased and the by-products at the origin of a spot plate are gradually increased, passing the reaction solution through a short silica gel chromatographic column, coarsely filtering, removing insoluble substances, distilling off the solvent under reduced pressure, separating the residue by using the chromatographic column, eluting by using an eluent, firstly separating unreacted [60] fullerene, then obtaining an N-phenyl [60] fullerene pyrroline derivative, and collecting the obtained N-phenyl [60] fullerene pyrroline derivative according to the color of the product, wherein the synthesis equation is as follows:
Figure BDA0002963619670000041
wherein R in the aldehyde unsubstituted at the alpha position 1 Is selected from the following substances: -H, -CH 3 、—CH 2 CH 2 CH 3 、—CH 2 (CH 3 )2、CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 、
Figure BDA0002963619670000042
-CH 2 SCH 3 、-CH(CH 3 )-CH 2 -CH(CH 3 ) 3 One of (1);
in aromatic primary amines
Figure BDA0002963619670000043
Selected from the following:
Figure BDA0002963619670000044
Figure BDA0002963619670000045
one of (1);
the molar ratio of the [60] fullerene, alpha-position unsubstituted aldehyde, aromatic primary amine, manganese acetate and DMAP added substances is 1: 15-20: 20:0.25 to 2:0.25 to 2;
preferably, the eluent is one or a mixture of two of carbon disulfide and dichloromethane.
Preferably, the reaction heating temperature is 100 to 120 ℃.
The invention also provides an N-phenyl [60] fullerene pyrroline derivative.
Further, the progress of the reaction is tracked and monitored by adopting thin layer chromatography, and when the product amount is not increased and the by-products at the origin of the spot plate are gradually increased, the heating is stopped to terminate the reaction.
Compared with the existing preparation method, the yield of the N-phenyl [60] fullerene pyrroline derivative is 30-62%, and the conversion rate of the raw material is 45-92%.
When the alpha position is unsubstituted 1 Is selected from the following substances: -H, -CH 3 、—CH 2 CH 2 CH 3 、—CH 2 (CH 3 ) 2 、CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 、
Figure BDA0002963619670000051
-CH 2 SCH 3 、-CH(CH 3 )-CH 2 -CH(CH 3 ) 3-oxo, N-phenyl [60]]The yield of the fullerene pyrroline derivative is 37-62%, the conversion rate of the raw material is 62-93%, the reaction substrate raw material is cheap and easy to obtain, the synthesis process is simple, and the raw material and the product are easy to separate.
At present, no one-step method for preparing N-phenyl [60] fullerene pyrroline derivatives is reported, and the method has no report that the yield of the N-phenyl [60] fullerene pyrroline derivatives and the conversion rate of raw materials can be obviously improved, byproducts are reduced, the dosage of the catalyst is reduced, the cost is reduced, the application range is wide by taking aromatic primary amine as a substrate, and the method has universal applicability.
Drawings
FIG. 1 is a spectrum H of an N-phenyl [60] fullerene pyrroline derivative according to example 1 of the present invention;
FIG. 2 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 1 of the present invention;
FIG. 3 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 2 of the present invention;
FIG. 4 is a spectrum C of N-phenyl [60] fullerene pyrroline derivative according to example 2 of the present invention;
FIG. 5 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 3 of the present invention;
FIG. 6 is a C spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 3 of the present invention;
FIG. 7 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 4 of the present invention;
FIG. 8 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 4 of the present invention;
FIG. 9 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 5 of the present invention;
FIG. 10 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 5 of the present invention;
FIG. 11 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 6 of the present invention;
FIG. 12 is a C spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 6 of the present invention;
FIG. 13 is the spectrum H of N-phenyl [60] fullerene pyrroline derivative according to example 7 of the present invention;
FIG. 14 shows the spectrum C of the N-phenyl [60] fullerene pyrroline derivative in example 7 of the present invention.
FIG. 15 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 8 of the present invention;
FIG. 16 is the spectrum C of the N-phenyl [60] fullerene pyrroline derivative according to example 8 of the present invention;
FIG. 17 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 9 of the present invention;
FIG. 18 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 9 of the present invention;
FIG. 19 is the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to example 10 of the present invention;
FIG. 20 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 10 of the present invention;
FIG. 21 is a spectrum H of an N-phenyl [60] fullerene pyrroline derivative in example 11 of the present invention;
FIG. 22 is a C spectrum of an N-phenyl [60] fullerene pyrroline derivative according to example 11 of the present invention;
detailed description of the preferred embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1
Preparation of N-phenyl [60] fullerene pyrroline derivative 1:
Figure BDA0002963619670000071
the preparation method comprises the following specific steps:
will [60]]Fullerene (36.0 mg, 0.05mmol), isovaleraldehyde
Figure BDA0002963619670000072
(81. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000073
(123.2mg, 1.00mmol), manganese acetate (3.4mg, 0.0125mmol), DMAP (1.6 mg, 0.0125mmol) were charged into the round-bottomed flask. Adding 10mL of chlorobenzene, using an ultrasonic instrument to completely dissolve the solid, immediately placing the mixed solution in an oil bath with the temperature preset to 120 ℃, heating and stirring for 23 minutes, tracking the reaction process by using a Thin Layer Chromatography (TLC) spot plate until the product of the spot plate does not increase any more and stopping the reaction when the byproduct at the original point increases gradually. After the reaction is finished, the reaction mixture is roughly filtered by a short silica gel column to remove metal salt and insoluble impurities, the solvent is spun out in a rotary evaporator under reduced pressure, the residue is separated by chromatographic column chromatography, carbon disulfide is used as eluent, and unreacted C is firstly separated 60 (purple), then N-phenyl [60]]The yield of fullerene pyrroline derivative 1 (tan) was 62%.
N-phenyl [60]]The nuclear magnetic test data of the fullerene pyrroline derivative 1 are as follows: 1 H NMR(800MHz,CS 2 /DMSO-d 6 ) δ 7.48 (d, J =9.0hz, 2h), 6.83 (d, J =9.0hz, 2h), 6.76 (s, 1H), 3.74 (s, 3H), 3.13-3.10 (m, 1H), 1.52 (d, J =6.7hz, 6H). As in fig. 1. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 156.59 (1C, aryl C), 149.07,146.85 (1C), 146.31 (1C), 146.22,145.17,145,13,145.11,144.96,144.89,144.73,144,70,144.66,144.10,144.08,144.05,143.54,143.32,142.10,141.78,141.70,141.67,141.30 (4C), 141.26,141.02,140.81,139.34,138.49,136.39 (1C), 135.30,134.54,130.69 (1C), 127.22 (aryl C), 119.96 (1C), 113.94 (aryl C), 88.75 (1C), 78.31 (1C), 54.35 (1C), 26.33 (1C), 23.89. As shown in fig. 2.
Example 2
Preparation of N-phenyl [60] fullerene pyrroline derivative 2:
Figure BDA0002963619670000081
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), isovaleraldehyde
Figure BDA0002963619670000082
(81. Mu.L, 0.75 mmol), 4-Aminothioanisole
Figure BDA0002963619670000083
(124. Mu.L, 1.00 mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round bottom flask, 10mL of chlorobenzene was dissolved by sonication, and then placed in an oil bath preset at 120 ℃ for 25min under reflux and CS 2 The product was isolated as eluent on a silica gel column. First of all, C is obtained 60 (purple) and secondly N-phenyl [60] is obtained]Fullerene-pyrroline derivative 2 (tan) was produced in 30% yield.
N-phenyl [60]]The fullerene pyrroline derivative 2 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.53 (d, J =8.6hz, 2h), 7.18 (d, J =8.6hz, 2h), 6.87 (s, 1H), 3.17-3.09 (m, 1H), 2.43 (s, 3H), 1.53 (d, J =6.8hz, 6H). As shown in fig. 3. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 148.96,146.78 (1C), 146.23 (1C), 145.78,145.13,145.06,145.04,144.91,144.82,144.66,144.63,144.54,144.04 (4C), 143.99,143.48,143.23,142.03,141.73,41.63,141.57,141.24,141.22,141.17,140.96,140.77,140.73 (1C, aryl C), 139.32,138.35,135.40,134.46 (1C), 134.41,129.91 (1C), 126.88 (aryl C), 125.52 (aryl C), 121.12 (1C), 88.28 (1C), 78.47 (1C), 26.29 (1C), 23.80,15.58 (1C). As shown in fig. 4.
Example 3
Preparation of N-phenyl [60] fullerene pyrroline derivative 3:
Figure BDA0002963619670000091
according to the above synthesis procedure, [60] is]Fullerene (36.0 mg, 0.05mmol), benzenepropanal
Figure BDA0002963619670000092
(100. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000093
(123.2mg, 1.00mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottomed flask, 10mL of chlorobenzene was added and dissolved by ultrasound, and then the mixture was put into an oil bath preset at 120 ℃ for a reflux reaction for 10min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple), followed by N-phenyl [60]]The yield of the fullerene pyrroline derivative 3 (tan) was 51%.
N-phenyl [60]]The fullerene pyrroline derivative 3 has the following nuclear magnetic test data: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.47 (d, J =8.8hz, 2h), 7.45 (d, J =6.6hz, 2h), 7.28 (t, J =7.5hz, 2h), 7,17 (t, J =7.4hz, 1h), 6.82 (d, J =8.8hz, 2h), 6.50 (s, 1H), 4.06 (s, 2H), 3.73 (s, 3H). As shown in fig. 5. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 155.58 (1C, aryl C), 147.43,145.75 (1C), 145.33,145.19 (1C), 144.10,144.01,143.90,143.87,143.77,143.64 (4C), 143.55,143.12,142.97 (4C), 142.43,142.20,140.98,140.63,140.55,140.49,140.18,140.16,140.11,139.93,139.68,138.21,137.35,136.84 (1C), 134.91 (1C), 134.28,133.51,132.15 (1C), 127.73 (aryl C), 126.99 (aryl C), 126.20 (aryl C), 125.04 (1C), 113.11 (aryl C), 111.65 (1C), 87.54 (1C), 76.87 (1C), 53.95 (1C), 32.64 (1C). As shown in fig. 6.
Example 4
Preparation of N-phenyl [60] fullerene pyrroline derivative 4:
Figure BDA0002963619670000101
according to the above synthesis procedure, [60] is]Fullerene (36.0 mg, 0.05mmol), hexanal (92. Mu.L, 0.75 mmol), p-anisyl groupPhenylamine
Figure BDA0002963619670000102
(123.2mg, 1.00mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottomed flask, 10mL of chlorobenzene was added and dissolved by ultrasound, and then the mixture was put into an oil bath preset at 120 ℃ for reflux reaction for 13min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) secondly a brown N-phenyl [60]]The yield of fullerene pyrroline derivative 4 (tan) was 61%.
N-phenyl [60]]The fullerene pyrroline derivative 4 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.49 (d, J =8.7hz, 2h), 6.84 (d, J =8.7hz, 2h), 6.69 (s, 1H), 3.74 (s, 3H), 2.75 (t, J =7.5hz, 2h), 1.94-1.88 (m, 2H), 1.64-1.56 (m, 2H), 1.05 (t, J =7.3hz, 3h). As shown in fig. 7. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 155.69 (1C, aryl C), 147.95,145.97 (1C), 145.66,145.40 (1C), 144.29,144.22,144.14,144.07,143.98,143.82 (6C), 143.29,143.17 (4C), 142.65,142.43,141.20,140.84,140.76 (4C), 140.38 (4C), 140.33,140.11,139.90,138.52,137.54,135.55 (1C), 134.42,133.77,130.09 (1C), 126.28 (aryl C), 113.26 (aryl C), 112.28,87.39 (1C), 77.62 (1C), 54.03 (1C), 28.42 (1C), 25.97 (1C), 21.90 (1C), 13.05 (1C). As shown in fig. 8.
Example 5
Preparation of N-phenyl [60] fullerene pyrroline derivative 5:
Figure BDA0002963619670000111
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), 3-methylthiopropanal
Figure BDA0002963619670000112
(100. Mu.L, 1 mmol), 4-Aminothion
Figure BDA0002963619670000113
(124. Mu.L, 1.00 mmol), manganese acetate (26.8mg, 0.1mmol), DMAP (12.2mg, 0.1mmol) were charged into a 50mL round bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then placed in an oil bath preset at 100 ℃ for 25min under reflux and reacted with CS 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) and secondly brown N-phenyl [60] is obtained]Fullerene pyrroline derivative 5 (tan) with a yield of 32%;
n-phenyl [60]]The fullerene pyrroline derivative 5 nuclear magnetic test data are as follows: 1 H NMR(400MHz,CS 2 /DMSO-d 6 ) δ 7.56 (d, J =8.4hz, 2h), 7.20 (d, J =8.4hz, 2h), 7.10 (s, 1H), 3.92 (s, 2H), 2.44 (s, 3H), 2.27 (s, 3H). As shown in fig. 9. 13 C NMR(100MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 148.69,146.74 (1C), 146.14 (1C), 145.57,145.11,144.95,144.90,144.87,144.79,144.75,144.70,144.61,144.04,144.02,143.93,143.50,143.07,141.93,141.70,141.54,141.54,141.29,141.09,141.00,140.98,140.80,139.74 (1C, aryl C), 139.18,138.30,135.64,134.99 (1C), 134.08 (1C), 133.85,126.78 (aryl C), 125.61 (aryl C), 108.65 (1C), 88.47 (1C), 76.77 (1C), 30.83 (1C), 15.47 (1C), 14.76 (1C). As shown in fig. 10.
Example 6
Preparation of N-phenyl [60] fullerene pyrroline derivative 6:
Figure BDA0002963619670000121
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), propionaldehyde (54. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000122
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then the mixture was put in an oil bath preset at 120 ℃ for reflux reaction for 25min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple), followed by N-phenyl [60]]Fullerene pyrroline derivative 6 (tan) in 55% yield.
N-phenyl [60]]The fullerene pyrroline derivative 6 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.50 (d, J =8.4hz, 2h), 6.84 (d, J =8.4hz, 2h), 6.73 (s, 1H), 3.74 (3H), 2.42 (s, 3H). As shown in fig. 11. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 155.67 (1C, aryl C), 147.68,145.98 (1C), 145.72,145.40 (1C), 144.30,144.23,144.10,144.08,143.97,143.86 (4C), 143.78,143.38,143.17 (4C), 142.66,142.44,141.20,140.82,140.75 (4C), 140.43,140.36,140.33,140.10,139.91,138.62,137.50,135.53 (1C), 134.43,133.94,130.93 (1C), 126.26 (aryl C), 113.30 (aryl C), 107.61 (1C), 87.20 (1C), 77.75 (1C), 54.05 (1C), 11.49 (1C). As shown in fig. 12.
Example 7
Preparation of N-phenyl [60] fullerene pyrroline derivative 7:
Figure BDA0002963619670000131
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), pentanal
Figure BDA0002963619670000132
(80. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000133
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round bottom flask, 10mL of chlorobenzene was dissolved by sonication, and the mixture was put in an oil bath preset at 120 ℃ for 25min under reflux and reacted with CS 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple), followed by N-phenyl [60]]Fullerene-pyrroline derivative 7 (tan) was produced in 60% yield.
N-phenyl [60]]The fullerene pyrroline derivative 7 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.50 (d, J =8.6hz, 2h), 6.84 (d, J =8.6hz, 2h), 6.70 (s, 1H), 3.74 (s, 3H), 2.74 (t, J =7.5hz, 2h), 1.98-1.91 (m, 2H), 1.19 (t, J =7.4hz, 3h) as in fig. 13. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 155.75 (1C, aryl C), 148.01,146.02 (1C), 145.67,145.46 (1C), 144.35,144.27,144.20,144.13,144.04,143.90,143.87 (4C), 143.35,143.22 (4C), 142.71,142.49,141.26,140.90,140.82 (4C), 140.46,140.44,140.39,140.17,139.96,138.59,137.60,135.60 (1C), 134.49,133.82,130.35 (1C), 126.35 (aryl C), 113.31 (aryl C), 112.13 (1C), 87.48 (1C), 77.64 (1C), 54.04 (1C), 28.41 (1C), 20.97 (1C), 13.30 (1C). As shown in fig. 14.
Example 8
Preparation of N-phenyl [60] fullerene pyrroline derivative 8:
Figure BDA0002963619670000141
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), heptanal
Figure BDA0002963619670000142
(104. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000143
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then the mixture was put in an oil bath preset at 120 ℃ for reflux reaction for 25min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) and secondly N-phenyl [60] is obtained]Fullerene pyrroline derivative 8 (tan) in 60% yield.
N-phenyl [60]]The fullerene pyrroline derivative 8 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 )δ7.50(d,J＝8.1Hz,2H),6.84(d,J＝8.1Hz,2H),6.69(s,1H),3.75(s,3H),2.74(t,J＝7.1Hz,2H),1.95-1.90(m,2H),1.58-1.53(m,2H),1.48-1.42(m, 2H), 0.98 (t, J =7.1hz, 3h). As in fig. 15. 13 C NMR(125MHz,CS 2 /DMSO-d 6 ) (all 2C unlessed) δ 155.23 (1C, aryl C), 147.47,145.48 (1C), 145.18,144.92 (1C), 143.80,143.73,143.65,143.58,143.49,143.37,143.33 (4C), 142.81,142.68 (4C), 142.17,141.95,140.71,140.36,140.27 (4C), 139.92,139.90,139.85,139.63,139.41,138.03,137.05,135.07 (1C), 133.94,133.28,129.66 (1C), 125.86 (aryl C), 112.91 (aryl C), 111.82 (1C), 86.91 (1C), 77.14 (1C), 53.90 (1C), 30.31 (1C), 26.62 (1C), 25.77 (1C), 21.19 (1C), 12.66 (1C). As in fig. 16.
Example 9
Preparation of N-phenyl [60] fullerene pyrroline derivative 9:
Figure BDA0002963619670000151
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), octanal
Figure BDA0002963619670000152
(116. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000153
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then the mixture was put in an oil bath preset at 120 ℃ for reflux reaction for 25min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) and secondly N-phenyl [60] is obtained]Fullerene pyrroline derivative 9 (tan) was produced in 37% yield.
N-phenyl [60]]The fullerene pyrroline derivative 8 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.50 (d, J =8.8hz, 2h), 6.84 (d, J =8.8hz, 2h), 6.67 (s, 1H), 3.75 (s, 3H), 2.75 (t, J =7.6hz, 2h), 1.95-1.89 (m, 2H), 1.61-1.55 (m, 2H), 1.45-1.34 (m, 4H), 0.95 (t, J =7.0hz, 3h). As in fig. 17. 13 C NMR(125MHz,CS 2 /DMSO-d 6 )(all 2C unless indexed δ 156.49 (1C, aryl C), 148.79,146.80 (1C), 146.49,146.24 (1C), 145.13,145.05,144.97,144.90,144.81,144.69,144.65 (4C), 144.13,144.00 (4C), 143.49,143.27,142.03,141.68,141.59 (4C), 141.24,141.22,141.17,140.95,140.73,139.36,138.38,136.39 (1C), 135.26,134.60,130.81 (1C), 127.01 (aryl C), 113.88 (aryl C), 113.16 (1C), 88.23 (1C), 78.46 (1C), 54.29 (1C), 31.36 (1C), 29.09 (1C), 28.13 (1C), 27.06 (1C), 22.48 (1C), 13.82 (1C). As in fig. 18.
Example 10
Preparation of N-phenyl [60] fullerene pyrroline derivative 10:
Figure BDA0002963619670000161
according to the above synthesis procedure, [60]]Fullerene (36.0 mg, 0.05mmol), nonanal
Figure BDA0002963619670000162
(130. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000163
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round-bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then the mixture was put in an oil bath preset at 120 ℃ for reflux reaction for 25min, and CS was added 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) and secondly N-phenyl [60] is obtained]Fullerene pyrroline derivative 10 (tan) in 43% yield.
N-phenyl [60]]The fullerene pyrroline derivative 10 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.50 (d, J =8.8hz, 2h), 6.84 (d, J =8.8hz, 2h), 6.68 (s, 1H), 3.75 (s, 3H), 2.74 (t, J =7.6hz, 2h), 1.95-1.89 (m, 2H), 1.60-1.54 (m, 2H), 1.45-1.40 (m, 2H), 1.35-1.34 (m, 4H), 0.92 (t, J =6.5hz, 3h). As shown in fig. 19. 13 C NMR(125MHz,CS 2 /DMSO-d 6 )(all 2C unless indicated)δ156.55(1C,aryl C),148.84,146.84(1C),146.53,146.27(1C),145.16,145.09,145.01,144.94,144.85,144.73,144.69 (4C), 144.16,144.04 (4C), 143.52,143.31,142.07,141.71,141.63 (4C), 141.28,141.20,140.99,140.77,139.39,138.41,136.42 (1C), 135.30,134.64,130.90 (1C), 127.07 (aryl C), 113.92 (aryl C), 113.18 (1C), 88.28 (1C), 78.51 (1C), 54.31 (1C), 31.47 (1C), 29.35 (1C), 28.88 (1C), 28.21 (1C), 27.07 (1C), 22.48 (1C), 13.82 (1C). As in fig. 20.
Example 11
Preparation of N-phenyl [60] fullerene pyrroline derivative 11:
Figure BDA0002963619670000171
according to the above synthesis procedure, [60]]Fullerene (36.0mg, 0.05mmol), 3,5,5-trimethylhexanal
Figure BDA0002963619670000173
(130. Mu.L, 0.75 mmol), 4-methoxyaniline
Figure BDA0002963619670000172
(123.2mg, 1mmol), manganese acetate (3.4 mg,0.0125 mmol) and DMAP (1.6 mg,0.0125 mmol) were added to a 50mL round bottom flask, 10mL of chlorobenzene was dissolved by sonication, and the mixture was put in an oil bath preset at 120 ℃ for 25min under reflux and reacted with CS 2 The product was isolated as eluent on a silica gel column. First, unreacted C is obtained 60 (purple) and secondly N-phenyl [60] is obtained]Fullerene pyrroline derivative 11 (tan) in 54% yield.
N-phenyl [60]]The fullerene pyrroline derivative 11 nuclear magnetic test data are as follows: 1 H NMR(500MHz,CS 2 /DMSO-d 6 ) δ 7.47 (d, J =8.9hz, 2h), 6.84 (d, J =8.9hz, 2h), 6.79 (s, 1H), 3.74 (s, 3H), 3.09-3.03 (m, 1H), 2.12 (dd, J =14.0,7.0hz, 1h), 1.64 (dd, J =14.0,5.0hz, 1h), 1.50 (d, J =6.8hz, 3h), 1.04 (s, 9H). As in fig. 21. 13 C NMR(125MHz,CS 2 /DMSO-d 6 )(all 1C unless indicated)δ156.49(1C,aryl C),149.40,148.22,146.76,146.21(2C),146.11,145.06(2C),144.99(2C),144.85(2C),144.78(2C),144.63(2C),144.58(2C)144.52,144.41,143.98 (2C), 143.96 (4C), 143.94 (2C), 143.44 (2C), 143.26,143.20,142.02,142.00,141.66 (2C), 141.59,141.56 (2C), 141.51,141.23,141.19 (2C), 141.15 (3C), 140.90,140.88,140.71 (2C), 139.42,139.14,138.44,138.26,136.52,135.12,135.08,134.51,134.20,131.12,127.17 (2C, aryl C), 119.92,113.86 (2C, aryl C), 88.61,78.37,54.33,50.90,30.44,29.80 (3C), 29.17,27.31,25.62. As in fig. 22.

Claims (4)

1. A preparation method of N-phenyl [60] fullerene pyrroline is characterized by comprising the following steps:
will [60]]Fullerene, alpha-unsubstituted aldehyde, primary aromatic amine
Figure DEST_PATH_IMAGE002AAA
Adding chlorobenzene or o-dichlorobenzene, mixing, adding mixture of manganese acetate and DMAP as catalyst, heating at constant temperature, stirring, tracking and monitoring reaction progress by thin layer chromatography, stopping reaction when product amount is not increased and by-product at origin of spot plate is gradually increased, passing reaction solution through short silica gel chromatographic column, coarse filtering, removing insoluble substance, evaporating solvent under reduced pressure, separating residue by chromatographic column, eluting with eluent, and separating unreacted [60]]Fullerene, followed by N-phenyl [60]]Fullerene pyrroline derivative, and the obtained N-phenyl [60] according to the color of the product]The fullerene pyrroline derivative is collected, and the synthesis equation is as follows:
Figure 351559DEST_PATH_IMAGE004
wherein R in the aldehyde unsubstituted at the alpha position 1 Is selected from the following substances: -H, -CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、
Figure DEST_PATH_IMAGE006AA
、-CH 2 SCH 3 、-CH(CH 3 )-CH 2 -C(CH 3 ) 3 One of (a) and (b);
in aromatic primary amines
Figure DEST_PATH_IMAGE002AAAA
Selected from the group consisting of
Figure DEST_PATH_IMAGE008A
、
Figure DEST_PATH_IMAGE010A
、
Figure DEST_PATH_IMAGE012A
One of (1);
the molar ratio of the [60] fullerene, alpha-position unsubstituted aldehyde, aromatic primary amine, manganese acetate and DMAP added substances is 1:15 to 20:20:0.25 to 2:0.25 to 2 ℃, and the reaction heating temperature is 100 to 120 ℃.
2. The method of claim 1, wherein the eluent is one or a mixture of carbon disulfide and dichloromethane.
3. The method of claim 1, wherein the progress of the reaction is monitored by thin layer chromatography, and the reaction is terminated by stopping heating when the amount of the product is not increased and the amount of the by-product at the origin of the dot plate is gradually increased.
4. N-phenyl [60] according to claim 1]The preparation method of fullerene pyrroline is characterized in that R in alpha-unsubstituted aldehyde 1 Is selected from the following substances: -H、-CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 、
Figure DEST_PATH_IMAGE006AAA
、-CH 2 SCH 3 、-CH(CH 3 )-CH 2 -C(CH 3 ) 3 (ii) a In the aromatic primary amine
Figure DEST_PATH_IMAGE002_5A
Selected from the following:
Figure DEST_PATH_IMAGE013A
。
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