CN113004190A - Preparation method of N-phenyl [60] fullerene pyrroline - Google Patents
Preparation method of N-phenyl [60] fullerene pyrroline Download PDFInfo
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- 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
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 aromatic primary amine Chemical class 0.000 claims abstract description 37
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract description 17
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 17
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000047 product Substances 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004809 thin layer chromatography Methods 0.000 claims description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 150000003142 primary aromatic amines Chemical class 0.000 claims 1
- 238000010898 silica gel chromatography Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 44
- 229910003472 fullerene Inorganic materials 0.000 description 44
- 125000003118 aryl group Chemical group 0.000 description 38
- 238000001228 spectrum Methods 0.000 description 22
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 9
- 238000000527 sonication Methods 0.000 description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 3
- YKFROQCFVXOUPW-UHFFFAOYSA-N 4-(methylthio) aniline Chemical compound CSC1=CC=C(N)C=C1 YKFROQCFVXOUPW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 description 1
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 108010007425 oligomycin sensitivity conferring protein Proteins 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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:
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:
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、
-CH2SCH3、-CH(CH3)-CH2-CH(CH3)3One of (1);
in aromatic primary amines
Selected from the following:
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、
-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:
the preparation method comprises the following specific steps:
will [60]]Fullerene (36.0mg,0.05mmol), isovaleraldehyde
(81. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), isovaleraldehyde
(81. mu.L, 0.75mmol), 4-Aminothioanisole
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), phenylpropylaldehyde
(100. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), hexanal (92. mu.L, 0.75mmol), p-anisidine
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), 3-methylthiopropanal
(100. mu.L, 1mmol), 4-Aminothioanisole
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), propionaldehyde (54. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), pentanal
(80. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05 mmo)l) heptanal
(104. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), octanal
(116. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), nonanal
(130. mu.L, 0.75mmol), 4-methoxyaniline
(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:
according to the above synthesis procedure, [60]]Fullerene (36.0mg,0.05mmol), 3,5, 5-trimethylhexanal
(130. mu.L, 0.75mmol), 4-methoxyaniline
(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.
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| 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- |
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| 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- |
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