CN108047179A - Fullerene dihydrofuran compound and preparation method thereof - Google Patents
Fullerene dihydrofuran compound and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of organic synthesis, and in particular to fullerene dihydrofuran compound and preparation method thereof, the preparation method of the fullerene dihydrofuran compound comprise the following steps：Under the conditions of existing for catalyst and oxidant, fullerene with ethene derivatives is reacted in organic solvent, obtains fullerene dihydrofuran compound.Fullerene dihydrofuran compound is prepared using one-step method in the present invention, and method is simple and practicable, and the method for the present invention is suitble to the preparation of the fullerene dihydrofuran compound of a variety of different substituents, has the characteristics that applied widely.
Description
Technical field
The present invention relates to technical field of organic synthesis, are specifically related to fullerene dihydrofuran compound and its preparation side
Method.
Background technology
Fullerene dihydrofuran compound has good bioactivity, therefore, has potential medical value and other
Industrial value.Such compound is mainly by the use of beta-diketon, beta-keto acid ester type compound as substrate, at Mn (OAc)3-2H2O or
Under the action of person ferric perchlorate with C60Generation radical reaction is prepared (Si Chen, Zong-Jun Li, and Xiang
Gao, J.Org.Chem.2016,81,121-128；Li Fa Bao, Zhu San E, You Xun, Wang Guan Wu,
Chin.Sci.Bull,2012,57,2269-2272.).Officials of feudal dynasties' force seminar is substrate using ethyl acetoacetate, is shaken in high frequency
Under the action of swinging with C60Reaction has synthesized fullerene dihydrofuran compound.
To sum up, in the prior art, during fullerene dihydrofuran compound is prepared used substrate scope ratio
Relatively narrow, the structure for causing product fullerene dihydrofuran compound is relatively simple, so as to limit fullerene dihydrofuran chemical combination
The development and application of object.
The content of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of fullerene dihydrofuran compounds.
The second object of the present invention is to provide a kind of preparation method of fullerene dihydrofuran compound, can prepare a variety of
Fullerene dihydrofuran compound with different substituents, and preparation method is simple.
To achieve these goals, the present invention provides a kind of fullerene dihydrofuran compound, molecular formula such as formula (I) institute
Show,
Wherein, X is selected from H, C1~C12Alkyl ,-OR2、-COOR2、-NHR2, one kind in aryl and heterocyclic aryl, wherein
R2Selected from substituted aryl, heterocyclic aryl, C2~C12Alkyl in one kind；
Y is selected from-COOR1、- CN and-OCOR1In one kind, wherein R1Selected from phosphine, silicon, aryl, C2~C12Alkane
One kind in base.
The present invention also provides a kind of preparation methods of the fullerene dihydrofuran compound, comprise the following steps：
Under the conditions of catalyst and oxidant are existing, fullerene with ethene derivatives is reacted in organic solvent, obtains fullerene two
Hydrogen furan compound.
Through the above technical solutions, the present invention has following technique effect：
Fullerene dihydrofuran compound is prepared using one-step method in the present invention, and method is simple and practicable, and the present invention
Method is suitble to the preparation of the fullerene dihydrofuran compound of a variety of different substituents, applied widely.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is together for explaining the present invention, but be not construed as limiting the invention.In the accompanying drawings：
Fig. 1：Target product P1 in the embodiment of the present invention 11H NMR scheme；
Fig. 2：Target product P1 in the embodiment of the present invention 113C NMR scheme；
Fig. 3：Target product P2 in the embodiment of the present invention 21H NMR scheme；
Fig. 4：Target product P2 in the embodiment of the present invention 213C NMR scheme；
Fig. 5：Target product P3 in the embodiment of the present invention 31H NMR scheme；
Fig. 6：Target product P4 in the embodiment of the present invention 41H NMR scheme；
Fig. 7：Target product P5 in the embodiment of the present invention 51H NMR scheme；
Fig. 8：Target product P6 in the embodiment of the present invention 61H NMR scheme.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For numberical range, between the endpoint value of each scope, respectively
It between the endpoint value of a scope and individual point value and can be individually combined with each other between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
To achieve these goals, the present invention provides a kind of fullerene dihydrofuran compound, molecular formula such as formula (I) institute
Show,
Wherein, X is selected from H, C1~C12Alkyl ,-OR2、-COOR2、-NHR2, one kind in aryl and heterocyclic aryl, wherein
R2Selected from substituted aryl, heterocyclic aryl, C2~C12Alkyl in one kind；Preferably H, C1~C12Alkyl in one kind, example
Such as can be H ,-CH3、-C2H5Deng.
Y is selected from-COOR1、- CN and-OCOR1In one kind, wherein R1Selected from phosphine, silicon, aryl, C2~C12Alkyl
In one kind, the Y be selected from C3~C13Ester group, one kind in-CN.
The present invention also provides a kind of preparation methods of the fullerene dihydrofuran compound, comprise the following steps：
Under the conditions of catalyst and oxidant are existing, fullerene with ethene derivatives is reacted in organic solvent, obtains fullerene two
Hydrogen furan compound, synthetic route are as follows：
In the preparation process of fullerene dihydrofuran compound, the content proportioning of each substance is to influence reaction product yield
An important factor for, in order to improve the yield of the fullerene dihydrofuran compound, under optimum condition, the fullerene, catalysis
The molar ratio of agent and oxidant is (0.8~1.2):(0.1~0.2):(4~6).
According to the present invention, catalyst and oxidant can trigger fullerene to be reacted with ethene derivatives, optimum condition
Under, the catalyst is palladium, and the oxidant is trifluoromethayl sulfonic acid copper.
Organic solvent is the medium of organic reaction, the organic solvent in dichloro-benzenes, acetonitrile, toluene and chlorobenzene extremely
Few a kind of, under optimum condition, the organic solvent includes o-dichlorohenzene and acetonitrile；It is further preferred that the o-dichlorohenzene with
The volume ratio of the acetonitrile is (5~6)：(0.5~1), further, the ratio of the fullerene and the o-dichlorohenzene is
(6~7) mg:(0.8~1.2) mL.
Under optimum condition, the ethene derivatives can be ethyl acrylate, n-butyl acrylate, phenyl acrylate, third
One kind in alkene nitrile, phenyl vinyl sulfone, ethyl crotonate.
Under optimum condition, the reaction carries out under the conditions of oxygen-containing.
Reaction temperature and reaction time are to influence one of synthesis efficiency and key factor, in order to improve fullerene dihydro
The combined coefficient of furan compound, under optimum condition, the temperature of the reaction is 100~150 DEG C, time of reaction for 8~
24h。
More specifically, the preparation method of the fullerene dihydrofuran compound, comprises the following steps：
(1) by the dissolving of fullerene, catalyst and oxidant in organic solvent, it is then anti-in 100~150 DEG C of oil bath
Answer 8~for 24 hours；
(2) it is evaporated under reduced pressure, removes organic solvent, obtain reaction mixture；
(3) reaction mixture with carbon disulfide is dissolved, and with pillar layer separation, obtains fullerene dihydrofuran chemical combination
Object.
In order to improve the purity of fullerene dihydrofuran compound, reaction is mixed using column chromatography in the present invention
Object carries out separating-purifying, and under optimum condition, the pillar layer separation technique is：First using carbon disulfide as eluant, eluent, removal is not
The fullerene reacted, then eluted with eluent, obtain fullerene dihydrofuran compound.It is it is further preferred that described
Eluent is selected from least one of carbon disulfide, dichloromethane, chloroform and ethyl acetate etc..
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is with ethyl acrylate and fullerene (C60) reacted, synthetic route is as follows：
Take the C of 36mg60, the ethyl acrylate of 25mg into pressure pipe, add in 2.3mg palladium make and 90mg trifluoro
For Loprazolam copper as oxidant, the acetonitrile that the ODCB (o-dichlorohenzene) and 1mL of 5mL are then added in into pressure pipe is solvent,
It is reacted in 130 DEG C of oil bath pan, contact plate tracking reacts 10h, stops reaction.Reaction solution is transferred to the round-bottomed flask of 50mL
In, o-dichlorohenzene and acetonitrile are removed using Rotary Evaporators, reaction mixture is obtained, reaction mixture curing will be obtained
Carbon dissolution crosses post separation.First make eluent by C with carbon disulfide60It separates, then the mixing with carbon disulfide and dichloromethane
Solvent (volume ratio 1:1) product elution is got off, after the solution after elution is spin-dried for, dries for 24 hours, obtain in vacuum drying chamber
To the product P1 of 13.6mg, yield 33%.
1H NMR(400MHz,CDCl3) δ 8.13 (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.
Target product P1's prepared by above-described embodiment1H NMR,13C NMR are respectively as shown in Fig. 1~2.
Embodiment 2
According to the method for embodiment 1, the difference is that, it is reacted, is closed using n-butyl acrylate and fullerene (C60)
It is as follows into route：
Wherein, the yield of product P2 is 30%,1H NMR,13C NMR difference is as shown in Figure 3,4.
1H NMR(400MHz,CDCl3) δ 8.11 (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.
Embodiment 3
According to the method for embodiment 1, the difference is that, using phenyl acrylate and fullerene (C60) reacted, it synthesizes
Route is as follows：
Wherein, the yield of product P3 is 41%,1H NMR difference is as shown in Figure 5.
1H NMR(400MHz,CDCl3)δ8.37(s,1H),7.22-7.03(m,5H)。
Embodiment 4
According to the method for embodiment 1, the difference is that, using acrylonitrile and fullerene (C60) reacted, synthetic route
It is as follows：
Wherein, the yield of product P4 is 28%,1H NMR are as shown in Figure 6.
1H NMR(400MHz,CDCl3)δ8.20(s,1H)。
Embodiment 5
According to the method for embodiment 1, the difference is that, using phenyl vinyl sulfone and fullerene (C60) reacted, it closes
It is as follows into route：
Wherein, the yield of product P5 is 36%,1H NMR are as shown in Figure 7.
1H NMR(400MHz,CDCl3) δ 8.35 (s, 1H), 7.99 (d, J=7.6Hz, 2H), 7.54-7.21 (m, 3H).
Embodiment 6
According to the method for embodiment 1, the difference is that, using ethyl crotonate and fullerene (C60) reacted, it synthesizes
Route is as follows：
Wherein, the yield of product P6 is 36%,1H NMR are as shown in Figure 8.
1H NMR(400MHz,CDCl3) δ 4.13 (t, J=7.1Hz, 2H), 2.68 (s, 3H), 1.13 (t, J=7.1Hz,
3H)。
Embodiment 7
According to the method for embodiment 1, the difference is that, the molar ratio of the fullerene, catalyst and oxidant is 0.8:
0.2:4；
The volume ratio of the o-dichlorohenzene and the acetonitrile is 6:0.5.
The ratio of the fullerene and the o-dichlorohenzene is 6mg:0.8mL.
The catalytic temperature is 100 DEG C, and the catalytic time is for 24 hours.
The yield of obtained product P1 is 34%.
Embodiment 8
According to the method for embodiment 1, the difference is that, the molar ratio of the fullerene, catalyst and oxidant is 1.2:
0.4:6。
The volume ratio of the o-dichlorohenzene and the acetonitrile is 5:1.
The ratio of the fullerene and the o-dichlorohenzene is 7mg:1.2mL.
The catalytic temperature is 150 DEG C, and the catalytic time is 8h.
The yield of obtained product P1 is 36%.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of fullerene dihydrofuran compound, which is characterized in that shown in its molecular formula such as formula (I),
Wherein, X is selected from H, C1~C12Alkyl ,-OR2、-COOR2、-NHR2, one kind in aryl and heterocyclic aryl, wherein R2Choosing
From aryl, C2~C12Alkyl in one kind；
Y is selected from-COOR1、- CN and-OCOR1In one kind, wherein R1Selected from phosphine, silicon, aryl, C2~C12Alkyl in
One kind.
2. fullerene dihydrofuran compound according to claim 1, wherein, the X is selected from H and C1~C12Alkyl in
One kind；And/or
Y is selected from C3~C13Ester group, one kind in-CN.
3. the preparation method of fullerene dihydrofuran compound according to claim 1 or 2, which is characterized in that including with
Lower step：Under the conditions of existing for catalyst and oxidant, fullerene with ethene derivatives is reacted in organic solvent, is obtained
Fullerene dihydrofuran compound.
4. the preparation method of fullerene dihydrofuran compound according to claim 3, wherein, the fullerene, catalysis
The molar ratio of agent and oxidant is (0.8~1.2):(0.1~0.2):(4~6).
5. the preparation method of fullerene dihydrofuran compound according to claim 3, wherein, the catalyst is acetic acid
Palladium；And/or
The oxidant is trifluoromethayl sulfonic acid copper；And/or
The organic solvent is selected from least one of o-dichlorohenzene, acetonitrile, toluene and chlorobenzene.
6. the preparation method of fullerene dihydrofuran compound according to claim 2, wherein, the o-dichlorohenzene and institute
The volume ratio for stating acetonitrile is (5~6)：(0.5~1)；And/or
The ratio of the fullerene and the o-dichlorohenzene is (6~7) mg:(0.8~1.2) mL.
7. the preparation method of fullerene dihydrofuran compound according to claim 3, wherein, the reaction is in oxygen-containing item
It is carried out under part；And/or
The temperature of the reaction is 100~150 DEG C, time of reaction for 8~for 24 hours.
8. the preparation method of the fullerene dihydrofuran compound according to claim 3~7, wherein, comprise the following steps：
(1) by the dissolving of fullerene, catalyst and oxidant in organic solvent, then 8 are reacted in 100~150 DEG C of oil bath
~for 24 hours；
(2) it is evaporated under reduced pressure, removes organic solvent, obtain reaction mixture；
(3) reaction mixture with carbon disulfide is dissolved, and with pillar layer separation, obtains fullerene dihydrofuran compound.
9. the preparation method of fullerene dihydrofuran compound according to claim 8, wherein, the pillar layer separation work
Skill is：First using carbon disulfide as eluant, eluent, the complete fullerene of removal unreacted, then eluted with eluent, obtain fowler
Alkene dihydrofuran compound.
10. the preparation method of fullerene dihydrofuran compound according to claim 9, wherein, the eluent is selected from
At least one of carbon disulfide, dichloromethane, chloroform and ethyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260104A (en) * | 2022-07-31 | 2022-11-01 | 合肥学院 | Preparation method of fullerene tetrahydropyridazine compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405252A (en) * | 2006-03-24 | 2009-04-08 | 独立行政法人科学技术振兴机构 | Fullerene derivative and method for producing same |
| RU2371441C1 (en) * | 2008-02-12 | 2009-10-27 | ИНСТИТУТ НЕФТЕХИМИИ И КАТАЛИЗА Российской Академии Наук | Method of producing 2,5-dialkyl(2,2,5,5-tetraalkyl)-3,4-fullero[60]tetradihydrofuranes |
| CN105153182A (en) * | 2015-09-29 | 2015-12-16 | 苏州大学 | A5-alkyl-2, 3-dihydrobenzofuran-C60fullerene double adduct, its prepn. method and use |
-
2018
- 2018-01-19 CN CN201810054759.6A patent/CN108047179B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405252A (en) * | 2006-03-24 | 2009-04-08 | 独立行政法人科学技术振兴机构 | Fullerene derivative and method for producing same |
| RU2371441C1 (en) * | 2008-02-12 | 2009-10-27 | ИНСТИТУТ НЕФТЕХИМИИ И КАТАЛИЗА Российской Академии Наук | Method of producing 2,5-dialkyl(2,2,5,5-tetraalkyl)-3,4-fullero[60]tetradihydrofuranes |
| CN105153182A (en) * | 2015-09-29 | 2015-12-16 | 苏州大学 | A5-alkyl-2, 3-dihydrobenzofuran-C60fullerene double adduct, its prepn. method and use |
Non-Patent Citations (5)
| Title |
|---|
| HUI-LEI HOU等: "Aerobic Oxidations of C602-in the Presence of PhCN and PhCH2CN:Oxygenation versus Dehydrogenation Reactions", 《J. ORG. CHEM.》 * |
| LI FABAO等: "Ferric perchlorate-promoted reaction of [60]fullerene with β-keto esters", 《CHIN SCI BULL》 * |
| MARINELLA ROBERTI等: "Thermal and catalytic reactions of ethyl diazopyruvate with [60]fullerene", 《TETRAHEDRON》 * |
| YI-TENG YAN等: "Palladium-Catalyzed Reaction of [60]Fullerene with Aroyl Compounds via Enolate-Mediated sp2 C−H Bond Activation and Hydroxylation", 《J. ORG. CHEM.》 * |
| 李法宝 等: "醋酸锰促进的[60]富勒烯与溴1-萘乙酸的自由基反应研究乙酸、3-氯丙酸、1-萘乙酸的自由基反应研究", 《科学通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260104A (en) * | 2022-07-31 | 2022-11-01 | 合肥学院 | Preparation method of fullerene tetrahydropyridazine compound |
| CN115260104B (en) * | 2022-07-31 | 2023-10-27 | 合肥学院 | Preparation method of fullerene tetrahydropyridazine compound |
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