CN107382825A - A kind of preparation method of 3,4 fullerene chemistries of N methyl 2 (hydroxy phenyl of 3 methoxyl group 4) - Google Patents
A kind of preparation method of 3,4 fullerene chemistries of N methyl 2 (hydroxy phenyl of 3 methoxyl group 4) Download PDFInfo
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- CN107382825A CN107382825A CN201710537598.1A CN201710537598A CN107382825A CN 107382825 A CN107382825 A CN 107382825A CN 201710537598 A CN201710537598 A CN 201710537598A CN 107382825 A CN107382825 A CN 107382825A
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- 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
Abstract
A kind of preparation method of 3,4 fullerene chemistries of N methyl 2 (hydroxy phenyl of 3 methoxyl group 4), comprises the following steps：(1) by C60Powder, which is dissolved in non-polar solven, obtains solution；(2) heating, backflow after methyl amimoacetic acid and vanillic aldehyde are added into step (1) resulting solution；(3) backflow terminates rear mixed solution cooling, removes toluene, obtains solid product；(4) solid product obtained by thin layer chromatography post elution step (3)；(5) elution products therefrom solution is removed into solvent, washing, is dried to obtain target product.The preparation method of the present invention is simple, and product purity is high, yield is high.
Description
Technical field
The invention belongs to the preparation method field of fullerene derivate, and in particular to a kind of N- methyl -2- (3- methoxyl groups -
4- hydroxy phenyls) -3,4- fullerene chemistries preparation method.
Background technology
Fullerene (Fullerene) is the third allotrope that simple substance carbon is found.It is any by a kind of element group of carbon
Into, with spherical, ellipticity, or material existing for tubular structure, fullerene can be called, fullerene refers to a kind of thing
Matter.Fullerene is similar with graphite-structure, but there was only hexatomic ring in the structure of graphite, and five-membered ring is there may be in fullerene.
Unique spherical pi-electron structure and photoelectric properties causes fullerene to be received much concern in materials science field.1985
Robert Curl et al. have prepared C60.1989, Germany scientist Huffman and Kraetschmer experiment confirmed
C60Cagelike structure, push a brand-new conceptual phase to from the fullerene that this physicist is had found by scientific circles.Fullerene
Structure it is similar with architect Fuller masterpiece, so referred to as fullerene.Primary Study shows that fullerene compound exists
AntiHIV1 RT activity, inhibition of enzyme activity, cutting DNA, photodynamic therapy etc. have the effect of uniqueness.
Mathematically, the structure of fullerene is all the convex polyhedron formed with pentagon and hexagonal surfaces.Minimum fowler
Alkene is C20, there is the construction of regular dodecahedron.Without the fullerene on 22 summits, C afterwards all be present2nFullerene, n=12,
13、14…….The pentagon number of all fullerene structures is 12, and hexagon number is n-10.Because C60It is fullerene man
It is relative in front yard to be most readily available, be easiest to purification and most cheap all kinds of, therefore C60And its derivative is studied and using most
More fullerenes.
As CN 103936660A disclose a kind of N- methyl -2- phenyl -3,4- fowler alkenyl pyrrolidines and its preparation side
Method and application.The invention is with fullerene C60, benzaldehyde and methyl amimoacetic acid be that raw material prepares N- methyl -2- phenyl -3,4- fowler alkenyls
Pyrrolidines and N- methyl -2- phenyl -3,4- fowler alkenyl pyrrolidines with micron acicular texture, and use micron needle-like
N- methyl -2- phenyl -3,4- fowler alkenyl the pyrrolidines of structure prepares Catalytic Hydrogenation of Nitrobenzene para-aminophenol as carrier
Catalyst.
The content of the invention
It is an object of the invention to provide a kind of N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene pyrroles
The preparation method of alkane.The preparation method of the present invention is simple to operate, and products collection efficiency is relatively high, and product is easily isolated, and purity is good.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistries, including such as
Lower step：
(1) by C60Powder, which is dissolved in non-polar solven, obtains purple clear solution；
(2) heating, backflow after methyl amimoacetic acid and vanillic aldehyde are added into step (1) resulting solution, stops mixing after heating molten
Liquid color is changed into the endless all-transparent of sepia from purple is transparent；
(3) backflow terminates rear mixed solution cooling, removes toluene, obtains brown solid；
(4) solid product obtained by thin layer chromatography post elution step (3)；
(5) elution products therefrom solution is removed into solvent, washs, be dried to obtain the powder target product of brownish black.
Step of the present invention is simple, easy to operate, by the mating reaction of above-mentioned steps make to be made product have it is higher pure
Degree and yield.Products therefrom can characterize its nucleus magnetic hydrogen spectrum, infrared spectrum, illustrate that its purity is preferable, otherwise can not be characterized
Its hydrogen is composed and infrared spectrum.
Preferably, C in step (1)60The ratio of powder and non-polar solven is 1:0.5-1.5mg/mL, for example, 1:
0.7mg/mL、1:0.85mg/mL、1:0.96mg/mL、1:1.1mg/mL、1:1.25 mg/mL、1:1.37mg/mL、1:
1.45mg/mL etc., preferably 1:1-1.1mg/mL.
Preferably, dissolving is carried out under an inert atmosphere, such as is carried out under rare gas such as Ar, and it is hollow to remove reaction unit
Gas is to protect reactant.
Preferably, dissolve at room temperature, such as carried out at 20-25 DEG C, can be stirred to C60Powder is dissolved completely in
In toluene.
Preferably, toluene used is the toluene newly distilled.
Preferably, C in methyl amimoacetic acid, vanillic aldehyde and step (1) in step (2)60The mass ratio of powder is 1:1-2:1-2,
For example, 1:1:1.5、1:1.5:2、1:2:1.5、1:1:1、1:1.5:2、1:1:2 etc., above-mentioned quality may be such that secondary anti-than scope
It should lack, yield is high, and product separation is easy, and preferably 1:1-1.5:1.5-2.
Vanillic aldehyde (chemical name：Vanillin) it is preferably the vanillic aldehyde recrystallized.
In order to reduce side reaction, yield is improved, it is preferable that the temperature of heating is 110-140 DEG C, for example, 113 DEG C, 116
DEG C, 119 DEG C, 122 DEG C, 124 DEG C, 128 DEG C, 133 DEG C, 136 DEG C, preferably 139 DEG C etc., 120-130 DEG C, the time of backflow is 1h
More than, preferably 2-3h.Heating can be carried out in oil bath.
Preferably, during being heated to reflux, at interval of a period of time, such as 10-50min, such as 10 min, 20min,
30min or 40min draws reaction solution point on silica gel plate with glass capillary, then the silica gel plate is put into and fills toluene and stone
Climb plate in the exhibition cylinder of the mixed solution of oily ether, take out under ultraviolet lamp observe the silica gel plate baseline above have a color compared with
Stop heating when deeply, putting larger product point (size diameter of point e.g., about 0.5-1mm), be heated to reflux such as 2-2.5h
Stop heating afterwards, now mixed solution color is changed into the endless all-transparent of sepia from purple is transparent.
Preferably, toluene and petroleum ether volume ratio are 1:1-5, toluene within this range, are easier to petroleum ether volume ratio
First the C for not participating in reaction completely60Elution is got off, and can preferably separate C60, accessory substance and product, preferably 1:3.
Preferably, the boiling range of toluene and petroleum ether mixed solution is 60-90 DEG C.
Preferably, the time for climbing plate is 15-20min.
Preferably, cooling is carried out under an inert atmosphere in step (3), such as carried out under rare gas such as Ar.
Preferably, toluene can be removed by evaporating, such as evaporate reaction mixture 20- by using Rotary Evaporators
30min is removed.
Preferably, elution process is as follows in step (4)：Using petroleum ether as solvent, with column chromatography silica gel powder packed layer
Chromatographic column is analysed, dry method loads solid product, first using toluene and petroleum ether mixed solution as eluent, then using toluene as eluent
Eluted product, when a large amount of brown product bands are presented in thin layer chromatography post, persistent pressure thin layer chromatography post, make the brown product stream
Descend and collect to obtain elution products therefrom solution.
Preferably, petroleum ether boiling range used is 60-90 DEG C.
Preferably, the mesh number of column chromatography silica gel powder is 200-400 mesh, can preferably separate C60, accessory substance and product, preferably
For 300 mesh.
Preferably, internal diameter × length of thin layer chromatography post is 26mm × 30cm, according to product polarity, can preferably be separated
C60, accessory substance and product.
Preferably, toluene and toluene in petroleum ether mixed solution and petroleum ether volume ratio are 1:1-5, preferably 1:3.
Preferably, the boiling range of toluene and petroleum ether mixed solution is 60-90 DEG C.
Preferably, the time of elution is more than 20min, preferably 50-60min, to elute the C for not participating in reaction completely60。
Preferably, toluene used is new toluene distillation.
Preferably, solvent can remove by evaporating in step (5), such as reaction mixture is evaporated by using Rotary Evaporators
Remove.
Preferably, the washing is carried out using the other methanol of high-efficiency liquid chromatographic-grade, is preferably washed more than 2 times.
Preferably, the temperature of the drying is 20-30 DEG C, and the time is more than 6h, preferably 12h.
Preferably, the drying is vacuum drying.
The system for providing a kind of N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistries of the present invention
Preparation Method, this method is simple to operate, and products collection efficiency is relatively high, and product is easily isolated, and purity is good.
Brief description of the drawings
Fig. 1 is the heat of N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistries prepared by embodiment 1
Weight analysis figure.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
(1) according to Prato reaction principles, the toluene solution and 72mg that 78mL newly distills are added in 250mL three-neck flasks
C60Powder, pure rare gas Ar is continually fed at room temperature, remove air in reaction unit, to protect reactant, is in temperature
At 20-25 DEG C, magnetic agitation to C60Powder is dissolved completely in toluene solution, obtains purple clear solution；
(2) the 63.1mg vanillic aldehyde (chemical names of 45mg methyl amimoacetic acids and recrystallization are separately added into again：3- methoxyl group -4- hydroxyls
Benzaldehyde), 120-130 DEG C of oil bath heating, condensing reflux 2-3h.
In this course of reaction, reaction solution point is drawn on silica gel plate with glass capillary at interval of 20min, then this
Silica gel plate, which is put into, fills volume ratio as 1:3 toluene in the exhibition cylinder of petroleum ether (boiling range is 60-90 DEG C) mixed solution with " climbing plate "
15-20min, take out the product point observed under ultraviolet lamp and have that a color is relatively deep, point is larger above the silica gel plate baseline
When, stop heating, now mixed solution color is changed into the endless all-transparent of sepia from purple is transparent.
(3) reaction unit is taken out from oil bath again, is continually fed into Ar and is cooled to room temperature, evaporated and reacted with Rotary Evaporators
Mixed solution 20-30min, toluene solvant in mixed solution is removed, obtains brown solid.
(4) using the petroleum ether that boiling range is 60-90 DEG C as solvent, with mesh number be 300 mesh column chromatography silica gel powder fill 26mm ×
30cm (internal diameter × length) thin layer chromatography post, dry method load obtained solid product；First using volume ratio as 1:3 toluene and oil
Ether (boiling range is 60-90 DEG C) mixed solution elutes the C for not participating in reaction completely as eluent6050-60min, then newly to distill
Toluene is eluent eluted product, when a large amount of brown product bands are presented in thin layer chromatography post, persistent pressure thin layer chromatography post, is made
The brown product is flowed down and is collected in conical flask.
(5) by products therefrom solution Rotary Evaporators solvent evaporated, then with the other methanol of high-efficiency liquid chromatographic-grade 2 are washed
It is secondary, then be dried in vacuo 12h, that is, brown-black powder shape product, yield 32.5% are obtained, the product is dissolved in SC2、CHCl3, toluene
Equal solvent, its synthetic route is as shown in following formula 1.
Products therefrom can characterize its nucleus magnetic hydrogen spectrum, infrared spectrum, illustrate that its purity is preferable, otherwise can not carry out characterizing it
Hydrogen is composed and infrared spectrum, specific data are as follows.
N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistries characterize
1. outer absorption spectrum characterizes
In its infrared absorption spectroscopy (KBr tablettings), 526cm-1、574cm-1、1186cm-1、1431cm-1The absworption peak at place
It is attributed to C60Characteristic absorption peak, 3541cm-1- OH stretching vibrations, 1462cm-1, 1514cm-1, 1602cm-1Locate as phenyl ring
Skeleton stretching vibration absworption peak；In addition in 2777cm-1, 2835cm-1, 2918cm-1, it is attributed to hydrocarbon stretching vibration peak.
2. uv-visible absorption spectra characterizes
In uv-visible absorption spectra, nearby there is the small spike of 1 feature in 431nm, this peak is [6,6] closed loop knot
The C of structure60The characteristic absorption peak of single additive derivative, there is a weak parcel peak near 700nm, relative to C60In 620nm suction
Receive, be moved to long wave direction.
3. proton nmr spectra characterizes
1In H nuclear magnetic resoance spectrums, wherein 2.90 (3H, s) are attributed to-N-CH3, 4.31 (1H, d) and 5.05 (1H, d) return
Belong to for pyrrole ring C60-CH2- N hydrogen, 4.94 (1H, s) are attributed to pyrrole ring C60- CH-N hydrogen, 5.71 (1H, s) ownership hydroxyls
Hydrogen, 7.05 (1H, d), 7.69 (2H, m) belong to the hydrogen of phenyl ring.
N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistry heat endurances
Heat endurance of the product under air atmosphere is studied using DTA-60 type microcomputer differential thermal analyzers.Aluminum oxide pond
Heating rate is 10 DEG C/min, test temperature scope be room temperature to 600 DEG C, its thermogravimetric analysis is as shown in Figure 1.
From figure 1 it appears that being decomposed after product is heated, exothermic decomposition is shown as, the peak temperature at decomposition caused heat release peak is
405.92 DEG C, it is believed that product has good heat endurance, is the further derivative of single additive derivative at relatively high temperatures
Change provides possibility.
Embodiment 2
It is same as Example 1, except following difference：
C in step (1)60Powder is 72mg, toluene 36mL；
Methyl amimoacetic acid is 36mg in step (2), and vanillic aldehyde 70mg, heating-up temperature is 110 DEG C, return time 4h；
Drying time is 6h in step (5).
Product yield is 28.3%.
By being characterized with embodiment identical, C is as a result attributed to60.Heat endurance and photoluminescent property produce with the gained of embodiment 1
Thing it is suitable.
Embodiment 3
It is same as Example 1, except following difference：
C in step (1)60Powder is 72mg, toluene 100mL；
Methyl amimoacetic acid is 70mg in step (2), and vanillic aldehyde 70mg, heating-up temperature is 140 DEG C, return time 1h；
Drying time is 24h in step (5).
Product yield is 27.6%.
By being characterized with embodiment identical, C is as a result attributed to60.Heat endurance and photoluminescent property produce with the gained of embodiment 1
Thing it is suitable.
Embodiment 4
It is same as Example 1, except following difference：
C in step (1)60Powder is 72mg, toluene 50mL；
Methyl amimoacetic acid is 50mg in step (2), and vanillic aldehyde 60mg, heating-up temperature is 125 DEG C, return time 2.5h；
Drying time is 15h in step (5).
Product yield is 30.2%.
By being characterized with embodiment identical, C is as a result attributed to60.Heat endurance and photoluminescent property produce with the gained of embodiment 1
Thing it is suitable.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of N- methyl -2- (3- methoxyl group -4- hydroxy phenyls) -3,4- fullerene chemistries, including it is as follows
Step：
(1) by C60Powder, which is dissolved in non-polar solven, obtains solution；
(2) heating, backflow after methyl amimoacetic acid and vanillic aldehyde are added into step (1) resulting solution；
(3) backflow terminates rear mixed solution cooling, removes toluene, obtains solid product；
(4) solid product obtained by thin layer chromatography post elution step (3)；
(5) elution products therefrom solution is removed into solvent, washing, is dried to obtain target product.
2. preparation method according to claim 1, it is characterised in that C in step (1)60The ratio of powder and non-polar solven
Example is 1:0.5-1.5mg/mL；
Preferably, dissolving is carried out under an inert atmosphere；
Preferably, the non-polar solven is combination one kind or two or more in n-hexane, benzene, carbon disulfide, carbon tetrachloride, excellent
Elect toluene as；
Preferably, toluene used is the toluene newly distilled.
3. preparation method according to claim 1 or 2, it is characterised in that methyl amimoacetic acid, vanillic aldehyde and step in step (2)
(1) C in60The mass ratio of powder is 1:1-2:1-2；
Preferably, the temperature of heating is 110-140 DEG C, and preferably 120-130 DEG C, the time of backflow is more than 1h, preferably 2-
3h。
4. according to the preparation method described in claim any one of 1-3, it is characterised in that during being heated to reflux, at interval of
A period of time draws reaction solution point on silica gel plate with glass capillary, then the silica gel plate is put into and fills toluene and petroleum ether
Mixed solution exhibition cylinder in climb plate, take out observed under ultraviolet lamp have above the silica gel plate baseline color it is relatively deep,
Stop heating when putting larger product point.
5. preparation method according to claim 4, it is characterised in that toluene is 1 with petroleum ether volume ratio:1-5；
Preferably, the boiling range of toluene and petroleum ether mixed solution is 60-90 DEG C；
Preferably, the time for climbing plate is 15-20min.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that step is cooled in inert atmosphere in (3)
Lower progress.
7. according to the preparation method described in claim any one of 1-6, it is characterised in that elution process is as follows in step (4)：With
Petroleum ether fills chromatography chromatographic column, dry method loads solid product, first with toluene and petroleum ether as solvent with column chromatography silica gel powder
Mixed solution as eluent, then using toluene as eluent eluted product treats that a large amount of brown product bands are presented in thin layer chromatography post
When, persistent pressure thin layer chromatography post, flow down the brown product and collect to obtain elution products therefrom solution.
8. preparation method according to claim 7, it is characterised in that petroleum ether boiling range used is 60-90 DEG C；
Preferably, the mesh number of column chromatography silica gel powder is 200-400 mesh；
Preferably, internal diameter × length of thin layer chromatography post is 26mm × 30cm.
9. the preparation method according to claim 7 or 8, it is characterised in that in toluene and petroleum ether mixed solution toluene with
Petroleum ether volume ratio is 1:1-5；
Preferably, the boiling range of toluene and petroleum ether mixed solution is 60-90 DEG C；
Preferably, the time of elution is more than 20min, preferably 50-60min；
Preferably, toluene used is new toluene distillation.
10. according to the preparation method described in claim any one of 1-9, it is characterised in that step (5) washing uses efficient
The other methanol of liquid chromatographic grade is carried out, and is preferably washed more than 2 times；
Preferably, the temperature of the drying is 20-30 DEG C, and the time is more than 6h；
Preferably, the drying is vacuum drying.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232527A (en) * | 2018-08-10 | 2019-01-18 | 浙江大学 | The organic photovoltaic cell of self-doping type fullerene pyridiniujm electron transport material and its composition |
Citations (2)
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|---|---|---|---|---|
| CN103936660A (en) * | 2014-05-07 | 2014-07-23 | 黄山学院 | Preparation method and application of micron acicular-structure N-methyl-2-phenyl-3,4-fullerenylpyrrolidine |
| CN103951606A (en) * | 2014-05-07 | 2014-07-30 | 黄山学院 | Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure |
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2017
- 2017-07-04 CN CN201710537598.1A patent/CN107382825A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936660A (en) * | 2014-05-07 | 2014-07-23 | 黄山学院 | Preparation method and application of micron acicular-structure N-methyl-2-phenyl-3,4-fullerenylpyrrolidine |
| CN103951606A (en) * | 2014-05-07 | 2014-07-30 | 黄山学院 | Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure |
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| ROBERT CZOCHARA，ET AL.: ""Fullerene C60 Derivatives as High-Temperature Inhibitors of Oxidative Degradation of Saturated Hydrocarbons"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232527A (en) * | 2018-08-10 | 2019-01-18 | 浙江大学 | The organic photovoltaic cell of self-doping type fullerene pyridiniujm electron transport material and its composition |
| CN109232527B (en) * | 2018-08-10 | 2020-05-19 | 浙江大学 | Self-doping type fullerene pyridinium electron transport material and organic solar cell formed by same |
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Application publication date: 20171124 |
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| RJ01 | Rejection of invention patent application after publication |