CN114853608A - Synthetic method of [60] fullerene hydrogen derivative catalyzed by N-heterocyclic carbene - Google Patents

Synthetic method of [60] fullerene hydrogen derivative catalyzed by N-heterocyclic carbene Download PDF

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CN114853608A
CN114853608A CN202210492477.0A CN202210492477A CN114853608A CN 114853608 A CN114853608 A CN 114853608A CN 202210492477 A CN202210492477 A CN 202210492477A CN 114853608 A CN114853608 A CN 114853608A
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fullerene
heterocyclic carbene
hydrogen derivative
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CN114853608B (en
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刘统信
张朋玲
朱雪
张贵生
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Henan Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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    • C07—ORGANIC CHEMISTRY
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    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a synthesis method of [60] fullerene hydrogen derivatives catalyzed by N-heterocyclic carbene, which comprises the step of carrying out three-component reaction on unsaturated aldehyde compounds, [60] fullerene and methanol under the catalysis of N-heterocyclic carbene to efficiently synthesize a series of [60] fullerene hydrogen derivatives. The method uses the N-heterocyclic carbene to catalyze the fullerene reaction, has the advantages of simple operation, no pollution, simple post-treatment and the like, and has the advantages of wide substrate range, good functional group compatibility, high yield, use of organic small molecular catalyst and green and environment-friendly synthesis process.

Description

Synthetic method of [60] fullerene hydrogen derivative catalyzed by N-heterocyclic carbene
Technical Field
The invention belongs to the technical field of synthesis of fullerene derivatives, and particularly relates to a synthesis method of a [60] fullerene hydrogen derivative catalyzed by N-heterocyclic carbene.
Background
Fullerene functionalization is an important research direction of fullerene chemistry, the solubility of fullerene can be improved, and fullerene derivatives with other novel structures and functions are prepared by introducing groups with different functions into fullerene. Therefore, the search for a new fullerene modification method and the construction of different functionalized fullerenes are very important for developing the application of fullerene derivatives in different fields.
Disclosure of Invention
The invention provides a synthetic method of [60] fullerene hydrogen derivatives catalyzed by N-heterocyclic carbene, and provides a novel method for efficiently synthesizing a series of [60] fullerene hydrogen derivatives by carrying out three-component reaction on unsaturated aldehyde compounds, [60] fullerene and methanol under the catalysis of N-heterocyclic carbene. The method uses the N-heterocyclic carbene to catalyze the fullerene reaction, has the advantages of simple operation, no pollution, simple post-treatment and the like, and has the advantages of wide substrate range, good functional group compatibility, high yield, use of organic small molecular catalyst and green and environment-friendly synthesis process.
The invention adopts the following technical scheme to solve the technical problems, namely the N-heterocyclic carbene catalyzed [60]]The synthesis method of the fullerene hydrogen derivative is characterized by comprising the following specific processes: to be provided withα,βUnsaturated aldehydes or 4- (chloromethyl) benzaldehydes, methanol and [ 60%]Fullerene is used as a reaction raw material, N-heterocyclic carbene is used as a catalyst, cesium acetate is used as an accelerant, anhydrous o-dichlorobenzene and anhydrous dichloromethane are used as reaction solvents, and three-component reaction is carried out at 90-110 ℃ in an inert atmosphere, whereinα,βThe-unsaturated aldehyde compound or the 4- (chloromethyl) benzaldehyde compound generates polarity reversal under the catalysis of N-heterocyclic carbene, changes electrophilicity into nucleophilicity, and [60]]The fullerene and the methanol react to prepare a target product [60]]The reaction equation in the synthesis process of the fullerene hydrogen derivative is as follows:
Figure DEST_PATH_IMAGE002
wherein R is 1 Is alkyl, aryl or heteroaryl.
Further preferably, said azacyclocarbene catalyzed [60]The synthesis method of the fullerene hydrogen derivative is characterized by comprising the following specific steps: will [60]]Fullerene,α,βPlacing unsaturated aldehyde compound or 4- (chloromethyl) benzaldehyde compound, N-heterocyclic carbene, cesium acetate and methanol in a dry Schlenk tube, adding anhydrous o-dichlorobenzene and anhydrous dichloromethane, ultrasonically dissolving the system completely, reacting in an oil bath kettle at 90-110 ℃ under the atmosphere of nitrogen, cooling to room temperature after the reaction is stopped, filtering out insoluble substances, spinning out the solvent under reduced pressure, and first using CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]A fullerene hydrogen derivative.
Further preferably, said [60]]Fullerene,α,βThe feeding molar ratio of the unsaturated aldehyde compound or the 4- (chloromethyl) benzaldehyde compound to the N-heterocyclic carbene to the cesium acetate is 1.0:3.0:0.2: 0.5.
Further preferably, theα,βUnsaturated aldehyde compounds or 4- (chloromethyl) benzaldehyde compounds are
Figure DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE006
、
Figure DEST_PATH_IMAGE008
、
Figure DEST_PATH_IMAGE010
、
Figure DEST_PATH_IMAGE012
、
Figure DEST_PATH_IMAGE014
、
Figure DEST_PATH_IMAGE016
Or
Figure DEST_PATH_IMAGE018
。
Further preferably, said [60]]The fullerene hydrogen derivative is
Figure DEST_PATH_IMAGE020
、
Figure DEST_PATH_IMAGE022
、
Figure DEST_PATH_IMAGE024
、
Figure DEST_PATH_IMAGE026
、
Figure DEST_PATH_IMAGE028
、
Figure DEST_PATH_IMAGE030
、
Figure DEST_PATH_IMAGE032
Or
Figure DEST_PATH_IMAGE034
。
Further preferably, the N-heterocyclic carbene is
Figure DEST_PATH_IMAGE036
Or
Figure DEST_PATH_IMAGE038
。
Compared with the prior art, the invention has the following advantages and beneficial effects: the method has the advantages of simple operation, no pollution, simple post-treatment and the like, and has the advantages of wide substrate range, good functional group compatibility, high yield, use of organic micromolecule catalyst and green and environment-friendly synthesis process.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Figure DEST_PATH_IMAGE040
Example 1
Preparation of [60] Fuller-hydrogen derivative 4 aa:
Figure DEST_PATH_IMAGE042
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2a
Figure DEST_PATH_IMAGE044
0.010 mmol catalyst
Figure DEST_PATH_IMAGE045
0.025 mmol of cesium acetate and 30 equiv of methanol in a 25 mL dry Schlenk tube, 4 mL of anhydrous o-dichlorobenzene and 1 mL of anhydrous dichloromethane were added, and the system was completely dissolved by sonication. Reacting for 1 h in an oil bath kettle at 90 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Insoluble matter was filtered off, and the solvent was removed by evaporation under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]The relative yield of the fullerene hydrogen derivative 4aa, the product 4aa was 43%.
4aa:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.87 (d, J = 7.8 Hz, 2H), 7.54 (t, J = 7.8 Hz, 2H), 7.45 (t, J = 7.8 Hz, 1H), 6.68 (s, 1H), 5.16 (dd, J = 4.2, 11.4 Hz, 1H), 4.14 (dd, J = 4.2, 15.6 Hz, 1H), 3.86 (dd, J = 10.8, 15.6 Hz, 1H), 3.69 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.99, 153.84, 153.68, 153.51, 147.59, 147.35, 146.93, 146.86, 146.71, 146.51, 146.34, 146.27, 146.26，145.82, 145.81, 145.63, 145.52, 145.49, 145.48, 145.45, 145.42，144.84, 144.81, 144.58, 144.53, 143.33, 143.31, 142.71, 142.70, 142.67, 142.30, 142.26, 142.16, 142.13, 141.74, 141.70, 141.65, 141.59, 140.39, 140.37, 139.68, 139.50, 138.54, 136.96, 136.58, 136.30, 130.32, 128.95, 128.38, 69.09, 58.49, 55.40, 52.10, 37.89; FT-IR ν/cm-1 (KBr) 1735, 1511, 1428, 1251, 1178, 1020, 904, 765, 729, 700, 662, 573, 524; UV-vis (CHCl3) λmax/nm 256, 330, 433, 704; MALDI-TOF MS m/z calcd for C70H12O2[M]-884.0837, found 884.0856。
Example 2
Preparation of [60] Fuller-hydro derivative 4 ba:
Figure DEST_PATH_IMAGE047
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2b
Figure DEST_PATH_IMAGE049
0.010 mmol catalyst
Figure DEST_PATH_IMAGE050
0.025 mmol of cesium acetate and 30 equiv of methanol in a 25 mL dry Schlenk tube, 4 mL of anhydrous o-dichlorobenzene and 1 mL of anhydrous dichloromethane were added, and the system was completely dissolved by sonication. Reacting for 1 h in an oil bath kettle at 90 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Insoluble matter was filtered off, and the solvent was removed by evaporation under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]The relative yield of the fullerene derivative 4ba and the product 4ba was 46%.
4ba:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.76 (d, J = 9.0 Hz, 2H), 7.03 (d, J = 9.0 Hz, 2H), 6.65 (s, 1H), 5.09 (dd, J = 4.2, 11.4 Hz, 1H), 4.09 (dd, J = 4.2, 15.6 Hz, 1H), 3.86 (s, 3H), 3.79 (dd, J = 11.4, 15.6 Hz, 1H), 3.68 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 170.83, 158.38, 152.86, 152.67, 152.61, 152.57, 146.50, 146.26, 145.88, 145.80, 145.67, 145.55, 145.44, 145.27, 145.20, 145.18, 144.75, 144.74, 144.55, 144.45, 144.40, 144.36, 143.78, 143.74, 143.51, 143.47, 142.27, 142.25, 141.65, 141.61, 141.24, 141.20, 141.10, 141.09, 141.07, 140.70, 140.66, 140.60, 140.53, 139.33, 139.31, 138.66, 138.47, 135.87, 135.49, 135.27, 135.26, 130.23, 129.30, 113.24, 68.33, 57.50, 54.11, 53.67, 50.95, 37.02; FT-IR ν/cm-1 (KBr) 2922, 1731, 1510, 1429, 1247, 1213, 1163, 1031, 988, 828, 806, 766, 573, 524; UV-vis (CHCl3) λmax/nm 259, 330, 434, 704; MALDI-TOF MS m/z calcd for C71H14O3[M]-914.0943, found 914.0956。
Example 3
Preparation of [60] Fullerene Hydrogen derivative 4 ca:
Figure DEST_PATH_IMAGE052
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2c
Figure DEST_PATH_IMAGE054
0.010 mmol catalyst
Figure DEST_PATH_IMAGE055
0.025 mmol of cesium acetate and 30 equiv of methanol in a 25 mL dry Schlenk tube, 4 mL of anhydrous o-dichlorobenzene and 1 mL of anhydrous dichloromethane were added, and the system was completely dissolved by sonication. Reacting for 1 h in an oil bath kettle at 100 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Insoluble matter was filtered off, and the solvent was removed by evaporation under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]The relative yield of the fullerene derivative 4ca, the product 4ca, was 38%.
4ca:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 8.34 (s, 1H), 8.02-7.97 (m, 3H), 7.89 (d, J = 7.8 Hz, 1H), 7.56-7.51 (m, 2H), 6.77 (s, 1H), 5.33 (dd, J = 3.6, 10.8 Hz, 1H), 4.22 (dd, J = 4.2, 16.2 Hz, 1H), 3.97 (dd, J = 10.8, 15.6 Hz, 1H), 3.65 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.86, 153.76, 153.61, 153.45, 147.55, 147.30, 146.89, 146.80, 146.67, 146.47, 146.30, 146.23, 145.78, 145.77, 145.62, 145.48, 145.46, 145.44, 145.37, 144.80, 144.77, 144.53, 144.48, 143.29, 143.28, 142.68, 142.66, 142.64, 142.25, 142.21, 142.12, 142.09, 141.70, 141.66, 141.63, 140.57, 140.36, 140.34, 139.71, 139.51, 136.97, 136.56, 136.26, 136.24, 136.18, 133.41, 133.18, 129.40, 128.63, 128.31, 128.01, 127.95, 126.60, 126.57, 69.17, 58.63, 55.54, 52.06, 37.97; FT-IR ν/cm-1 (KBr) 1731, 1509, 1427, 1253, 1215, 1006, 897, 807, 726, 572, 5246; UV-vis (CHCl3) λmax/nm 254, 330, 433, 704; MALDI-TOF MS m/z calcd for C74H14O2[M]-934.0994, found 934.0978。
Example 4
Preparation of [60] Fullerene Hydrogen derivative 4 da:
Figure DEST_PATH_IMAGE057
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2d
Figure DEST_PATH_IMAGE059
0.010 mmol catalyst
Figure DEST_PATH_IMAGE060
0.025 mmol of cesium acetate and 30 equiv of methanol in a 25 mL dry Schlenk tube, 4 mL of anhydrous o-dichlorobenzene and 1 mL of anhydrous dichloromethane were added, and the system was completely dissolved by sonication. Reacting for 1 h in an oil bath kettle at 100 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Insoluble matter was filtered off, and the solvent was removed by evaporation under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]Loading fullerene by wet method, and performing thin layer chromatography on silica gelColumn separation to obtain target product [60]]The relative yield of the fullerene derivative 4da, the product 4da was 30%.
4da:1H NMR (400 MHz, CDCl3/CS2, v/v = 10:1) δ 7.81 (d, J = 8.8 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 6.61 (s, 1H), 5.14 (dd, J = 4.0, 11.2 Hz, 1H), 4.14 (dd, J = 4.0, 16.0 Hz, 1H), 3.82 (dd, J = 11.2, 16.0 Hz, 1H), 3.70 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.68, 153.50, 153.32, 153.02, 152.87, 147.58, 147.33, 146.81, 146.71, 146.50, 146.33, 146.31, 146.27, 146.25, 145.76, 145.74, 145.65, 145.52, 145.49, 145.47, 145.44, 144.82, 144.79, 144.52, 144.48, 143.32, 143.30, 142.72, 142.70, 142.67, 142.24, 142.20, 142.15, 142.09, 141.74, 141.67, 141.65, 141.58, 140.43, 140.41, 139.73, 139.53, 137.07, 136.89, 136.62, 136.23, 136.17, 134.45, 131.51, 129.11, 68.82, 58.49, 54.84, 52.15, 37.74; FT-IR ν/cm-1 (KBr) 1735, 1487, 1429, 1411, 1208, 1164, 1089, 1010, 729, 572, 552, 524; UV-vis (CHCl3) λmax/nm 260, 319, 433, 703; MALDI-TOF MS m/z calcd for C70H11ClO2[M]-918.0448, found 918.0435。
Example 5
Preparation of [60] Fullerene Hydrogen derivative 4 ea:
Figure DEST_PATH_IMAGE062
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2e
Figure DEST_PATH_IMAGE064
0.010 mmol catalyst
Figure DEST_PATH_IMAGE065
0.025 mmol cesium acetate and 30 equiv methanol in a 25 mL dry Schlenk tube, 4 mL anhydrous o-dichlorobenzene and 1 mL anhydrous dichloromethane were added and the system was completely dissolved by sonication. Reacting for 1 h in an oil bath kettle at 100 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Filtering out insoluble matterThe solvent was spun off under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]The relative yield of the fullerene hydrogen derivative 4ea and the product 4ea is 40%.
4ea:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.75 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 6.60 (s, 1H), 5.12 (dd, J = 4.2, 11.4 Hz, 1H), 4.14 (dd, J = 4.2, 15.6 Hz, 1H), 3.82 (dd, J = 11.4, 16.2 Hz, 1H), 3.71 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 170.65, 152.48, 152.31, 151.99, 151.85, 146.59, 146.33, 145.81, 145.71, 145.50, 145.35, 145.30, 145.27, 145.25, 144.76, 144.74, 144.66, 144.52, 144.47, 144.44, 143.82, 143.79, 143.52, 143.48, 142.32, 141.72, 141.70, 141.67, 141.24, 141.20, 141.15, 141.09, 140.74, 140.67, 140.65, 140.63, 140.58, 139.43, 139.42, 138.74, 138.54, 136.61, 135.91, 135.62, 135.23, 135.17, 131.06, 130.83, 113.24, 68.33, 57.49, 54.11，53.67, 50.95, 37.02; FT-IR ν/cm-1 (KBr) 1735, 1510, 1484, 1429, 1259, 1209, 1164, 1090, 1007, 984, 963, 798, 761, 573, 524; UV-vis (CHCl3) λmax/nm 253, 313, 433, 703; MALDI-TOF MS m/z calcd for C70H11BrO2[M]-961.9942 , found 961.9928。
Example 6
Preparation of [60] Fuller-hydro derivative 4 fa:
Figure DEST_PATH_IMAGE067
the reaction steps are as follows:
accurately weighing 0.05 mmol [60]]Fullerene, 0.15 mmol of substrate 2f
Figure DEST_PATH_IMAGE069
0.010 mmol catalyst
Figure DEST_PATH_IMAGE070
0.025 mmol cesium acetate and 30 equiv methanol in a 25 mL dry Schlenk tube, 4 mL anhydrous o-dichlorobenzene and 1The system was completely dissolved by sonication in mL of anhydrous dichloromethane. Reacting for 1 h in an oil bath kettle at 110 ℃ under the nitrogen atmosphere, and cooling to room temperature after the reaction is stopped. Insoluble matter was filtered off, and the solvent was removed by evaporation under reduced pressure. First use CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]The relative yield of 4fa, a product of the fullerene derivative 4fa, was 30%.
4fa: 1H NMR (400 MHz, CDCl3/CS2, v/v = 10:1) δ 7.84 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 6.59 (s, 1H), 5.09 (dd, J = 4.0, 11.2 Hz, 1H), 4.11 (dd, J = 4.0, 16.0 Hz, 1H), 3.78 (dd, J = 11.2, 16.0 Hz, 1H), 3.69 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.30, 153.36, 153.18, 152.87, 152.74, 147.49, 147.24, 146.71, 146.64, 146.42, 146.38, 146.25, 146.21, 146.18, 146.15, 145.66, 145.63, 145.58, 145.44, 145.41, 145.37, 144.73, 144.70, 144.42, 144.39, 143.23, 143.21, 142.64, 142.59, 142.57, 142.15, 142.08, 142.05, 141.99, 141.65, 141.57, 141.52, 141.50, 140.37, 140.34, 139.68, 139.49, 138.17, 137.92, 136.82, 136.54, 136.14, 136.08, 131.92, 94.87, 68.62, 58.49, 54.96, 51.98, 37.59; FT-IR ν/cm-1 (KBr) 1734, 1508, 1428, 1410, 1164, 1046, 1002, 961, 805, 729, 677, 572, 522; UV-vis (CHCl3) λmax/nm 258, 310, 433, 534, 703; MALDI-TOF MS m/z calcd for C70H11IO2[M]-1009.9804, found 1009.9821。
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (6)

1. N-heterocyclic carbene catalyzed [60]]The synthesis method of the fullerene hydrogen derivative is characterized by comprising the following specific processes: to be provided withα,βUnsaturated aldehydes or 4- (chloro)Methyl) benzaldehyde compound, methanol and [60]]Fullerene is used as a reaction raw material, N-heterocyclic carbene is used as a catalyst, cesium acetate is used as an accelerant, anhydrous o-dichlorobenzene and anhydrous dichloromethane are used as reaction solvents, and three-component reaction is carried out at 90-110 ℃ in an inert atmosphere, whereinα,βThe-unsaturated aldehyde compound or the 4- (chloromethyl) benzaldehyde compound generates polarity reversal under the catalysis of N-heterocyclic carbene, changes electrophilicity into nucleophilicity, and [60]]The fullerene and the methanol react to prepare a target product [60]]The reaction equation in the synthesis process of the fullerene hydrogen derivative is as follows:
Figure DEST_PATH_IMAGE001
wherein R is 1 Is alkyl, aryl or heteroaryl.
2. The azacyclocarbene catalyzed [60] of claim 1]The synthesis method of the fullerene hydrogen derivative is characterized by comprising the following specific steps: will [60]]Fullerene,α,βPlacing unsaturated aldehyde compound or 4- (chloromethyl) benzaldehyde compound, N-heterocyclic carbene, cesium acetate and methanol in a dry Schlenk tube, adding anhydrous o-dichlorobenzene and anhydrous dichloromethane, performing ultrasonic treatment to completely dissolve the system, reacting in an oil bath kettle at 90-110 ℃ under nitrogen atmosphere, cooling to room temperature after reaction is stopped, filtering out insoluble substances, removing solvent under reduced pressure, and first using CS 2 Collecting unreacted [60] as eluent]The fullerene is loaded by a wet method and separated by a thin layer chromatography silica gel column to obtain a target product [60]]A fullerene hydrogen derivative.
3. The azacyclocarbene catalysed [60] according to claim 1 or 2]A method for synthesizing a fullerene hydrogen derivative, characterized in that [60]]Fullerene,α,βThe feeding molar ratio of the unsaturated aldehyde compound or the 4- (chloromethyl) benzaldehyde compound to the N-heterocyclic carbene to the cesium acetate is 1.0:3.0:0.2: 0.5.
4. According to claimThe N-heterocyclic carbene catalyzed [60] of claim 1 or 2]A synthesis method of a fullerene hydrogen derivative is characterized in thatα,βUnsaturated aldehydes or 4- (chloromethyl) benzaldehydes as active ingredients
Figure 351254DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
、
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、
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、
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、
Figure DEST_PATH_IMAGE007
、
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Or
Figure DEST_PATH_IMAGE009
。
5. The azacyclocarbene catalysed [60] according to claim 1 or 2]A method for synthesizing a fullerene hydrogen derivative, characterized in that [60]]The fullerene hydrogen derivative is
Figure 539604DEST_PATH_IMAGE010
、
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、
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、
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、
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、
Figure DEST_PATH_IMAGE015
、
Figure 421475DEST_PATH_IMAGE016
Or
Figure DEST_PATH_IMAGE017
。
6. The azacyclocarbene-catalyzed [60] according to claim 1 or 2]The synthesis method of the fullerene hydrogen derivative is characterized by comprising the following steps: the N-heterocyclic carbene is
Figure 775840DEST_PATH_IMAGE018
Or
Figure DEST_PATH_IMAGE019
。
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