CN113004190A - Preparation method of N-phenyl [60] fullerene pyrroline - Google Patents

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

Info

Publication number
CN113004190A
CN113004190A CN202110244607.4A CN202110244607A CN113004190A CN 113004190 A CN113004190 A CN 113004190A CN 202110244607 A CN202110244607 A CN 202110244607A CN 113004190 A CN113004190 A CN 113004190A
Authority
CN
China
Prior art keywords
fullerene
phenyl
pyrroline
reaction
pyrroline derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110244607.4A
Other languages
Chinese (zh)
Other versions
CN113004190B (en
Inventor
孙睿
王兴宇
李法宝
彭倩娜
刘修善
李君虞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hubei University
Original Assignee
Hubei University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hubei University filed Critical Hubei University
Priority to CN202110244607.4A priority Critical patent/CN113004190B/en
Publication of CN113004190A publication Critical patent/CN113004190A/en
Application granted granted Critical
Publication of CN113004190B publication Critical patent/CN113004190B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/96—Spiro-condensed ring systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)
  • Indole Compounds (AREA)
  • Catalysts (AREA)

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 by Wujun et al in 2016, "Cu (OAc) 2-medial Reaction of [60] Fullerene with Aldehydes and Primary Amines for The Synthesis of fulleropyrrolines, 2016-JOC The Journal of Organic Chemistry" reported The Synthesis of N-benzyl [60] Fullerene derivatives with The addition of copper acetate using Aldehydes, benzylamines and [60] Fullerene, but increasing or decreasing The equivalent of copper acetate decreased The yield of N-benzyl [60] Fullerene pyrroline. 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 C60Nucleophilic addition of an enamine intermediate III to the C ═ C bond which has been activated by pi complex formation between the copper (II) lewis acid and the C ═ C bond can lead to the formation of a copper (II) -fullerene complex IV and the loss of one HOAC molecule. Subsequent intramolecular cyclization of complex IV with another molecule of HOACThe elimination produces a new copper (II) -fullerene complex V, which is then reductively eliminated to provide the desired fullerene pyrroline 3 or 5 and Cu 0. 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 study of the reaction of fullerenes with N-phenylbenzylamine confirmed that 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 product yield 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, has wide application range and universal applicability by taking the aromatic primary amine as a substrate, improves the yield of the target derivative and the conversion rate of the substrate, reduces byproducts, reduces the dosage of additive manganese acetate and reduces the cost.
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 position1Is selected from the following substances: -H, -CH3、—CH2CH2CH3、—CH2(CH3)2、CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH2CH3CH2CH2CH2CH2CH3、
Figure BDA0002963619670000042
-CH2SCH3、-CH(CH3)-CH2-CH(CH3)3One 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: 0.25-2: 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 100-120 ℃.
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 unsubstituted1Is selected from the following substances: -H, -CH3、—CH2CH2CH3、—CH2(CH3)2、CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH2CH3CH2CH2CH2CH2CH3、
Figure BDA0002963619670000051
-CH2SCH3、-CH(CH3)-CH2-CH(CH3)3 is, N-phenyl [60]]The yield of the fullerene pyrroline derivative is 37-62%, the conversion rate of raw materials is 62-93%, the reaction substrate raw materials are cheap and easy to obtain, the synthesis process is simple, and the raw materials 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 the H spectrum of 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 C spectrum 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 an N-phenyl [60] fullerene pyrroline derivative according to example 6 of the present invention;
FIG. 13 is the H spectrum 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 according to 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 the H spectrum of N-phenyl [60] fullerene pyrroline derivative according to 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 (36.0mg,0.05mmol), isovaleraldehyde
Figure BDA0002963619670000072
(81. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000073
(123.2mg,1.00mmol), manganese acetate (3.4mg,0.0125mmol), DMAP (1.6mg,0.0125mmol) were added to the round bottom 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, metal salt and insoluble impurities are removed, the solvent is decompressed and spun out in a rotary evaporator, the residue is separated by chromatographic column chromatography, and carbon disulfide is used as elutionAgent, unreacted C being first separated off60(purple) followed by 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:1H NMR(800MHz,CS2/DMSO-d6) 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. 1.13C NMR(125MHz,CS2/DMSO-d6) (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 (36.0mg,0.05mmol), isovaleraldehyde
Figure BDA0002963619670000082
(81. mu.L, 0.75mmol), 4-Aminothioanisole
Figure BDA0002963619670000083
(124. mu.L, 1.00mmol), manganese acetate (3.4mg,0.0125mmol), DMAP (1.6mg,0.0125mmol) were added to a 50mL round bottom flask, 10mL of chlorobenzene was added and dissolved by sonication, and then placed in an oil bath preset at 120 ℃ for 25min for reflux reaction with CS2The product was isolated as eluent on a silica gel column. First of all, C is obtained60(purple) and secondly gives N-phenyl [60]]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:1H NMR(500MHz,CS2/DMSO-d6) 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. 3.13C NMR(125MHz,CS2/DMSO-d6) (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]]Fullerene (36.0mg,0.05mmol), phenylpropylaldehyde
Figure BDA0002963619670000092
(100. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000093
(123.2mg,1.00mmol), manganese acetate (3.4mg,0.0125mmol), DMAP (1.6mg,0.0125mmol) were added to a 50mL round bottom flask, 10mL of chlorobenzene was added and dissolved by ultrasound, and then placed in an oil bath preset at 120 ℃ for 10min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives 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:1H NMR(500MHz,CS2/DMSO-d6)δ7.47(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. 5.13C NMR(125MHz,CS2/DMSO-d6) (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]]Fullerene (36.0mg,0.05mmol), hexanal (92. mu.L, 0.75mmol), p-anisidine
Figure BDA0002963619670000102
(123.2mg,1.00mmol), manganese acetate (3.4mg,0.0125mmol), DMAP (1.6mg,0.0125mmol) 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 13min, and CS was added2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) secondly brown N-phenyl [60]]The yield of the fullerene pyrroline derivative 4 (tan) was 61%.
N-phenyl [60]]The fullerene pyrroline derivative 4 nuclear magnetic test data are as follows:1H NMR(500MHz,CS2/DMSO-d6) 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. 7.13C NMR(125MHz,CS2/DMSO-d6)(all2C unless indicated)δ155.69(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 (36.0mg,0.05mmol), 3-methylthiopropanal
Figure BDA0002963619670000112
(100. mu.L, 1mmol), 4-Aminothioanisole
Figure BDA0002963619670000113
(124. mu.L, 1.00mmol), manganese acetate (26.8mg,0.1mmol), DMAP (12.2mg,0.1mmol) were added to 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 a reflux reaction for 25min with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(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:1H NMR(400MHz,CS2/DMSO-d6) 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. 9.13C NMR(100MHz,CS2/DMSO-d6)(all 2C unless indicated)δ148.69,146.74(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),133.85,12678(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 (36.0mg,0.05mmol), propionaldehyde (54. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000122
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives 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:1H NMR(500MHz,CS2/DMSO-d6) 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. 11.13C NMR(125MHz,CS2/DMSO-d6) (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 in fig. 12.
Example 7
Preparation of N-phenyl [60] fullerene pyrroline derivative 7:
Figure BDA0002963619670000131
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), pentanal
Figure BDA0002963619670000132
(80. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000133
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives 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:1H NMR(500MHz,CS2/DMSO-d6) 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. 13.13C NMR(125MHz,CS2/DMSO-d6) (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 in fig. 14.
Example 8
Preparation of N-phenyl [60] fullerene pyrroline derivative 8:
Figure BDA0002963619670000141
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05 mmo)l) heptanal
Figure BDA0002963619670000142
(104. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000143
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives N-phenyl [60]]Fullerene pyrroline derivative 8 (tan) in 60% yield.
N-phenyl [60]]The fullerene pyrroline derivative 8 nuclear magnetic test data are as follows:1H NMR(500MHz,CS2/DMSO-d6) δ 7.50(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. 15.13C NMR(125MHz,CS2/DMSO-d6) (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 (36.0mg,0.05mmol), octanal
Figure BDA0002963619670000152
(116. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000153
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives N-phenyl [60]]Fullerene pyrroline derivative 9 (tan) in 37% yield.
N-phenyl [60]]The fullerene pyrroline derivative 8 nuclear magnetic test data are as follows:1H NMR(500MHz,CS2/DMSO-d6) 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. 17.13C NMR(125MHz,CS2/DMSO-d6) (all 2C unlessed) 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 (36.0mg,0.05mmol), nonanal
Figure BDA0002963619670000162
(130. mu.L, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000163
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives N-phenyl [60]]Fullerene pyrroline derivative 10 (tan) in 43% yield.
N-phenyl [60]]The fullerene pyrroline derivative 10 nuclear magnetic test data are as follows:1H NMR(500MHz,CS2/DMSO-d6) 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 in fig. 19.13C NMR(125MHz,CS2/DMSO-d6) (all 2C unlessed) δ 156.55(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, 0.75mmol), 4-methoxyaniline
Figure BDA0002963619670000172
(123.2mg,1mmol), manganese acetate (3.4mg,0.0125mmol) and DMAP (1.6mg,0.0125mmol) 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 25min of reflux reaction with CS2The product was isolated as eluent on a silica gel column. First, unreacted C is obtained60(purple) and secondly gives N-phenyl [60]]Fullerene pyrroline derivative 11 (tan) in 54% yield.
N-phenyl [60]]The fullerene pyrroline derivative 11 nuclear magnetic test data are as follows:1H NMR(500MHz,CS2/DMSO-d6) 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. 21.13C NMR(125MHz,CS2/DMSO-d6) (all 1C unlessed) δ 156.49(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 (6)

1. A preparation method of N-phenyl [60] fullerene pyrroline is characterized by comprising 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 RE-FDA0003071642380000011
wherein R in the aldehyde unsubstituted at the alpha position1Is selected from the following substances: -H, -CH3、—CH2CH2CH3、—CH2(CH3)2、CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH2CH3CH2CH2CH2CH2CH3、
Figure RE-FDA0003071642380000012
-CH2SCH3、-CH(CH3)-CH2-CH(CH3)3One of (1);
in aromatic primary amines
Figure RE-FDA0003071642380000013
Selected from the following:
Figure RE-FDA0003071642380000014
Figure RE-FDA0003071642380000015
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: 0.25-2: 0.25 to 2.
2. The method of claim 1, wherein the eluent is one or a mixture of carbon disulfide and dichloromethane.
3. The method for producing N-phenyl [60] fullerene pyrroline according to claim 1, wherein the reaction heating temperature is 100 to 120 ℃.
4. 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.
5. N-phenyl [60] according to claim 1]The preparation method of fullerene pyrroline is characterized in that-H, -CH3、—CH2CH2CH3、—CH2(CH3)2、CH2CH2CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH2CH3CH2CH2CH2CH2CH3、
Figure RE-FDA0003071642380000021
-CH2SCH3、-CH(CH3)-CH2-CH(CH3)3(ii) a In the aromatic primary amine
Figure RE-FDA0003071642380000022
Selected from the following:
Figure RE-FDA0003071642380000023
6. an N-phenyl [60] fullerene pyrroline derivative prepared by the method for preparing N-phenyl [60] fullerene pyrroline according to any one of claims 1 to 4.
CN202110244607.4A 2021-03-05 2021-03-05 Preparation method of N-phenyl [60] fullerene pyrroline Active CN113004190B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110244607.4A CN113004190B (en) 2021-03-05 2021-03-05 Preparation method of N-phenyl [60] fullerene pyrroline

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110244607.4A CN113004190B (en) 2021-03-05 2021-03-05 Preparation method of N-phenyl [60] fullerene pyrroline

Publications (2)

Publication Number Publication Date
CN113004190A true CN113004190A (en) 2021-06-22
CN113004190B CN113004190B (en) 2022-11-18

Family

ID=76406610

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110244607.4A Active CN113004190B (en) 2021-03-05 2021-03-05 Preparation method of N-phenyl [60] fullerene pyrroline

Country Status (1)

Country Link
CN (1) CN113004190B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053471A (en) * 2018-09-20 2018-12-21 中国科学院武汉物理与数学研究所 A kind of synthetic method of [60] fullerene cyclopentene derivatives
CN109096174A (en) * 2018-10-23 2018-12-28 中国科学院武汉物理与数学研究所 A kind of synthetic method of unsubstituted [60] fulleropyrrolidine derivative of N- alkyl -2,5-

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053471A (en) * 2018-09-20 2018-12-21 中国科学院武汉物理与数学研究所 A kind of synthetic method of [60] fullerene cyclopentene derivatives
CN109096174A (en) * 2018-10-23 2018-12-28 中国科学院武汉物理与数学研究所 A kind of synthetic method of unsubstituted [60] fulleropyrrolidine derivative of N- alkyl -2,5-

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
HUMBERTO RODRÍGUEZ-SOLLA ET AL.: "The use of samarium or sodium iodide salts as an alternative for the aza-Henry reaction", 《TETRAHEDRON》 *
JIE PENG ET AL.: "DMAP-Mediated Synthesis of Fulleropyrrolines: Reaction of [60]Fullerene with Aromatic Aldehydes and Arylmethanamines in the Absence or Presence of Manganese(III) Acetate", 《THE JOURNAL OF ORGANIC CHEMISTRY》 *
JUN WU ET AL.: "Cu(OAc)2-Mediated Reaction of [60]Fullerene with Aldehydes and Primary Amines for the Synthesis of Fulleropyrrolines", 《THE JOURNAL OF ORGANIC CHEMISTRY》 *
KIYOSHI TOMIOKA ET AL.: "Enantioselective Addition of Thiazolyllithiumto Aldimines with the Aid of Chiral Ligand. Asymmetric Synthesis of (S)Doe, a Component of Marine Natural Product, Dolastatin 10", 《HETEROCYCLES》 *
任友达等: "《基础有机化学》", 30 June 1991, 高等教育出版社 *

Also Published As

Publication number Publication date
CN113004190B (en) 2022-11-18

Similar Documents

Publication Publication Date Title
TW518329B (en) Process for preparing derivatives of the taxoid family
JP5738185B2 (en) Process for preparing amines from alcohols and ammonia
Gao et al. Mn (OAc) 3-mediated synthesis of β-hydroxyphosphonates from P (O)–H compounds and alkenes
CN112898192B (en) Preparation method of N-acyl indole compound
CN109053471A (en) A kind of synthetic method of [60] fullerene cyclopentene derivatives
CN114195711B (en) Preparation method of quinoline-4 (1H) -ketone compound
CN109096174B (en) Synthesis method of N-alkyl-2, 5-unsubstituted [60] fullerene pyrrolidine derivative
CN113004190B (en) Preparation method of N-phenyl [60] fullerene pyrroline
CN110878099B (en) Preparation method of pyrrole [1,2, alpha ] indole alkaloid derivative
CN114853608B (en) Synthesis method of [60] fullerene derivative catalyzed by N-heterocyclic carbene
CN115785122A (en) Indole derivative piperidine compound and synthetic method thereof
CN115772157A (en) Preparation method of 2-alkoxy indole compound
CN110668991B (en) Method for cyanoalkylation reaction of 1,6-eneyne compound
Mosslemin et al. B (HSO4) 3 as an Efficient Catalyst for the Syntheses of Bis (1H‐Indol‐3‐yl) ethanones and Bis (benzotriazol‐1‐yl) ethanones
JP5629473B2 (en) Process for producing soluble monosubstituted phthalocyanines having amino groups
CN115057808B (en) Synthesis method of Z-3-vinyl substituted isoindolinone compound
CN115724747B (en) Preparation method of ethylenediamine compound
CN113024464B (en) Method for preparing [60] fullerene tetrahydroquinoline derivative based on triflic acid/p-toluenesulfonic acid catalysis
WO2002055477A1 (en) RUTHENIUM COMPOUND, DIAMINE COMPOUND, AND PROCESS FOR PRODUCING β-AMINO -ALCOHOL
CN112239456B (en) Preparation method of substituted 2, 3-dihydroquinolone compound
CN115572217B (en) Synthesis method of palladium-catalyzed decarboxylated [60] fullerene-cyclopenta-4-ketone derivative
CN117164555A (en) Preparation method of indole formamide compound
CN114702492B (en) Ruthenium (II) -based metal-organic cage compound and preparation method and application thereof
KR102418587B1 (en) Catalyst composition for carbon dioxide fixation
CN115286553A (en) Preparation method of indole compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant