CN108047179B - Fullerene dihydrofuran compound and preparation method thereof - Google Patents
Fullerene dihydrofuran compound and preparation method thereof Download PDFInfo
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- CN108047179B CN108047179B CN201810054759.6A CN201810054759A CN108047179B CN 108047179 B CN108047179 B CN 108047179B CN 201810054759 A CN201810054759 A CN 201810054759A CN 108047179 B CN108047179 B CN 108047179B
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a fullerene dihydrofuran compound and a preparation method thereof, wherein the preparation method of the fullerene dihydrofuran compound comprises the following steps: in the presence of a catalyst and an oxidant, fullerene and an ethylene derivative react in an organic solvent to obtain a fullerene dihydrofuran compound. The method is simple and feasible, is suitable for preparing the fullerene dihydrofuran compounds with various different substituent groups, and has the characteristic of wide application range.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a fullerene dihydrofuran compound and a preparation method thereof.
Background
The fullerene dihydrofuran compound has good biological activity, thus having potential medicinal valueOther industrial values. The compounds mainly use beta-diketone and beta-ketonic acid ester compounds as substrates, and are prepared by using Mn (OAc)3-2H2With C under the action of O or ferric perchlorate60Prepared by free radical reactions (Si Chen, Zong-Jun Li, and Xiaoing Gao, J.Org.Chem.2016,81, 121-Bu 128; Li Fa Bao, Zhu San E, You Xin, Wang Guan Wu, Chin.Sci.Bull,2012,57, 2269-Bu 2272.). The Wang officer Wu subject group uses ethyl acetoacetate as a substrate to react with C under the action of high-frequency oscillation60The fullerene dihydrofuran compound is synthesized by reaction.
In summary, in the prior art, the range of the substrate used in the process of preparing the fullerene dihydrofuran compound is relatively narrow, which results in a relatively single structure of the product fullerene dihydrofuran compound, thereby limiting the development and application of the fullerene dihydrofuran compound.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a fullerene dihydrofuran compound.
The second purpose of the invention is to provide a preparation method of fullerene dihydrofuran compound, which can prepare a plurality of fullerene dihydrofuran compounds with different substituents and has simple preparation method.
In order to achieve the purpose, the invention provides a fullerene dihydrofuran compound, the molecular formula of which is shown as a formula (I),
wherein X is selected from H, C1～C12Alkyl, -OR of2、-COOR2、-NHR2Aryl and heterocyclic aryl, wherein R2Selected from substituted aryl, heterocyclic aryl, C2～C12One of the alkyl groups of (a);
y is selected from-COOR1、
-CN and-OCOR1Wherein R is1Selected from phosphine, silicon, aryl, C2～C12One of the alkyl groups of (1).
The invention also provides a preparation method of the fullerene dihydrofuran compound, which comprises the following steps: in the presence of a catalyst and an oxidant, fullerene and an ethylene derivative react in an organic solvent to obtain a fullerene dihydrofuran compound.
Through the technical scheme, the invention has the following technical effects:
the method is simple and feasible, is suitable for preparing fullerene dihydrofuran compounds with various different substituent groups, and has wide application range.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1: preparation of the target product P1 in inventive example 11H NMR chart;
FIG. 2: preparation of the target product P1 in inventive example 113C NMR chart;
FIG. 3: preparation of the target product P2 in inventive example 21H NMR chart;
FIG. 4: preparation of the target product P2 in inventive example 213C NMR chart;
FIG. 5: preparation of the target product P3 in inventive example 31H NMR chart;
FIG. 6: preparation of the target product P4 in inventive example 41H NMR chart;
FIG. 7: preparation of the target product P5 in inventive example 51H NMR chart;
FIG. 8: preparation of the target product P6 in inventive example 61H NMR chart.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the purpose, the invention provides a fullerene dihydrofuran compound, the molecular formula of which is shown as a formula (I),
wherein X is selected from H, C1～C12Alkyl, -OR of2、-COOR2、-NHR2Aryl and heterocyclic aryl, wherein R2Selected from substituted aryl, heterocyclic aryl, C2～C12One of the alkyl groups of (a); preferably H, C1～C12One of the alkyl groups of (a) may be, for example, H or-CH3、-C2H5And the like.
Y is selected from-COOR1、
-CN and-OCOR1Wherein R is1Selected from phosphine, silicon, aryl, C2～C12Y is selected from C3～C13And one of the ester group and-CN.
The invention also provides a preparation method of the fullerene dihydrofuran compound, which comprises the following steps: in the presence of a catalyst and an oxidant, fullerene and an ethylene derivative react in an organic solvent to obtain a fullerene dihydrofuran compound, wherein the synthetic route is as follows:
in the preparation process of the fullerene dihydrofuran compound, the content ratio of each substance is an important factor influencing the yield of a reaction product, and in order to improve the yield of the fullerene dihydrofuran compound, the molar ratio of the fullerene, the catalyst and the oxidant is (0.8-1.2): (0.1-0.2): 4-6) under the preferable conditions.
According to the invention, the catalyst and the oxidant can initiate the reaction of the fullerene and the ethylene derivative, under the preferable condition, the catalyst is palladium acetate, and the oxidant is copper trifluoromethanesulfonate.
The organic solvent is a medium for organic reaction, and is selected from at least one of dichlorobenzene, acetonitrile, toluene and chlorobenzene, and preferably comprises o-dichlorobenzene and acetonitrile; further preferably, the volume ratio of the o-dichlorobenzene to the acetonitrile is (5-6): (0.5-1), and further, the ratio of the fullerene to the o-dichlorobenzene is (6-7) mg (0.8-1.2) mL.
Under the preferable conditions, the ethylene derivative can be one of ethyl acrylate, n-butyl acrylate, phenyl acrylate, acrylonitrile, phenyl vinyl sulfone and ethyl crotonate.
Preferably, the reaction is carried out under oxygen-containing conditions.
The reaction temperature and the reaction time are one of important factors influencing the synthesis reaction efficiency, and in order to improve the synthesis efficiency of the fullerene dihydrofuran compound, the reaction temperature is 100-150 ℃ and the reaction time is 8-24 h under the preferable conditions.
More specifically, the preparation method of the fullerene dihydrofuran compound comprises the following steps:
(1) dissolving fullerene, a catalyst and an oxidant in an organic solvent, and then reacting for 8-24 hours in an oil bath at 100-150 ℃;
(2) distilling under reduced pressure to remove the organic solvent to obtain a reaction mixture;
(3) dissolving the reaction mixture by using carbon disulfide, and separating by using column chromatography to obtain the fullerene dihydrofuran compound.
In order to improve the purity of the fullerene dihydrofuran compound, the reaction mixture is separated and purified by a column chromatography separation method, and under the preferable conditions, the column chromatography separation process comprises the following steps: and removing the fullerene which is not completely reacted by using carbon disulfide as an eluent, and eluting by using an eluent to obtain the fullerene dihydrofuran compound. Further preferably, the eluent is at least one selected from carbon disulfide, dichloromethane, chloroform, ethyl acetate, and the like.
The present invention will be described in detail below by way of examples.
Example 1
This example uses ethyl acrylate and fullerene (C)60) The reaction is carried out, and the synthetic route is as follows:
taking 36mg of C6025mg of ethyl acrylate was put into a pressure tube, 2.3mg of palladium acetate and 90mg of copper trifluoromethanesulfonate were added as oxidants, 5mL of ODCB (o-dichlorobenzene) and 1mL of acetonitrile were added as solvents to the pressure tube, and the mixture was reacted in an oil bath at 130 ℃ with spotting followed for 10 hours, and the reaction was stopped. The reaction solution was transferred to a 50mL round-bottom flask, o-dichlorobenzene and acetonitrile were removed by using a rotary evaporator to obtain a reaction mixture, and the obtained reaction mixture was dissolved with carbon disulfide and subjected to column separation. Firstly, carbon disulfide is used as eluent to prepare C60The product was separated, eluted with a mixed solvent of carbon disulfide and dichloromethane (volume ratio 1:1), and the eluted solution was dried by spinning and dried in a vacuum oven for 24 hours to obtain 13.6mg of product P1 with a yield of 33%.
1H NMR(400MHz,CDCl3)δ8.13(s,1H),4.19(q,J＝7.1Hz,2H),1.20(t,J＝7.1Hz,3H).13C NMR(100MHz,CS2-CDCl3)δ163.09,157.01,147.98,147.58,147.20,146.98,146.38,146.21,146.07,145.94,145.90,145.50,145.41,145.12,144.98,144.62,144.08,143.50,142.99,142.74,142.71,142.64,142.43,142.37,142.26,142.22,141.59,141.38,139.82,139.79,137.47,135.30,111.34,60.68,29.99,138.66,135.43,131.99,129.09,128.82,128.63,128.54,127.46,127.09,124.95,54.75,21.41,14.15.HRMS(MALDI-TOF)m/z calcd for C65H6O3[M]+834.10,found 834.03.
Preparation of the desired product P1 from the above example1H NMR，13C NMR is shown in FIGS. 1 to 2.
Example 2
The procedure of example 1 was followed, except that n-butyl acrylate and fullerene (C60) were used for the reaction, and the synthetic route was as follows:
the yield of the product P2 was 30%, among others, which1H NMR，13C NMR is shown in FIGS. 3 and 4, respectively.
1H NMR(400MHz,CDCl3)δ8.11(s,1H),4.11(t,J＝6.6Hz,2H),1.57-1.50(m,2H),1.32-1.22(m,4H),0.79(t,J＝7.4Hz,3H).
13C NMR(100MHz,CS2-CDCl3)δ163.19,157.06,147.99,147.58,147.21,146.96,146.38,146.22,146.08,145.95,145.91,145.51,145.41,145.13,144.99,144.62,144.43,144.09,143.51,142.998,142.75,142.72,142.64,142.44,142.37,142.26,142.23,141.58,141.39,139.83,139.78,137.48,135.32,111.43,64.56,31.48,29.99,19.73,14.04.
Example 3
The procedure is as in example 1, except that phenyl acrylate and fullerene (C) are used60) The reaction is carried out, and the synthetic route is as follows:
the yield of the product P3 was 41%, among others, which1The H NMR spectra are shown in FIG. 5.
1H NMR(400MHz,CDCl3)δ8.37(s,1H),7.22-7.03(m,5H)。
Example 4
The procedure is as in example 1, except that acrylonitrile and fullerene (C) are used60) The reaction is carried out, and the synthetic route is as follows:
the yield of the product P4 was 28%, among others, which1H NMR is shown in FIG. 6.
1H NMR(400MHz,CDCl3)δ8.20(s,1H)。
Example 5
The procedure is as in example 1, except that phenylvinylsulfone and fullerene (C) are used60) The reaction is carried out, and the synthetic route is as follows:
the yield of the product P5 was 36%, among others, which1H NMR is shown in FIG. 7.
1H NMR(400MHz,CDCl3)δ8.35(s,1H),7.99(d,J＝7.6Hz,2H),7.54-7.21(m,3H)。
Example 6
The procedure is as in example 1, except that ethyl crotonate and fullerene (C) are used60) The reaction is carried out, and the synthetic route is as follows:
the yield of the product P6 was 36%, among others, which1H NMR is shown in FIG. 8.
1H NMR(400MHz,CDCl3)δ4.13(t,J＝7.1Hz,2H),2.68(s,3H),1.13(t,J＝7.1Hz,3H)。
Example 7
The process of example 1 is followed except that the molar ratio of the fullerene, catalyst and oxidant is 0.8:0.2: 4;
the volume ratio of the o-dichlorobenzene to the acetonitrile is 6: 0.5.
The ratio of the fullerene to the o-dichlorobenzene is 6mg to 0.8 mL.
The temperature of the contact reaction is 100 ℃, and the time of the contact reaction is 24 h.
The product P1 was obtained in 34% yield.
Example 8
The process of example 1 is followed except that the molar ratio of the fullerene, catalyst and oxidant is 1.2:0.4: 6.
The volume ratio of the o-dichlorobenzene to the acetonitrile is 5: 1.
The ratio of the fullerene to the o-dichlorobenzene is 7mg:1.2 mL.
The temperature of the contact reaction is 150 ℃, and the time of the contact reaction is 8 h.
The product P1 was obtained in a yield of 36%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A preparation method of a fullerene dihydrofuran compound is characterized in that the molecular formula of the fullerene dihydrofuran compound is shown as a formula (I),
wherein X is selected from H, C1～C12Alkyl, -OR of2、-COOR2、-NHR2Aryl and heterocyclic aryl, wherein R2Selected from aryl, C2～C12One of the alkyl groups of (a);
y is selected from-COOR1、
-CN and-OCOR1Wherein R is1Selected from aryl, C2～C12One of the alkyl groups of (a);
the preparation method comprises the following steps: reacting fullerene and an ethylene derivative in an organic solvent in the presence of a catalyst and an oxidant to obtain a fullerene dihydrofuran compound;
the catalyst is palladium acetate;
the oxidant is copper trifluoromethanesulfonate;
the organic solvent is at least one of o-dichlorobenzene, acetonitrile, toluene and chlorobenzene.
2. The method for producing a fullerene dihydrofuran compound according to claim 1, wherein the molar ratio of the fullerene, the catalyst and the oxidant is (0.8-1.2): (0.1-0.2): (4-6).
3. The method for producing a fullerene dihydrofuran compound according to claim 1, wherein the organic solvent is o-dichlorobenzene and acetonitrile, and the volume ratio of the o-dichlorobenzene to the acetonitrile is (5-6): (0.5 to 1);
the ratio of the fullerene to the o-dichlorobenzene is (6-7) mg, (0.8-1.2) mL.
4. The method for producing a fullerene dihydrofuran compound according to claim 1, wherein the reaction temperature is 100 to 150 ℃ and the reaction time is 8 to 24 hours.
5. A method of producing a fullerene dihydrofuran compound according to claim 1, comprising the steps of:
(1) dissolving fullerene, a catalyst and an oxidant in an organic solvent, and then reacting for 8-24 hours in an oil bath at 100-150 ℃;
(2) distilling under reduced pressure to remove the organic solvent to obtain a reaction mixture;
(3) dissolving the reaction mixture by using carbon disulfide, and separating by using column chromatography to obtain the fullerene dihydrofuran compound.
6. The method for producing a fullerene dihydrofuran compound according to claim 5, wherein the column chromatography separation process is: and removing the fullerene which is not completely reacted by using carbon disulfide as an eluent, and eluting by using an eluent to obtain the fullerene dihydrofuran compound.
7. The method according to claim 6, wherein the eluting agent is at least one selected from the group consisting of carbon disulfide, methylene chloride, chloroform, and ethyl acetate.
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