CN101434576B - Fluorescent fullerene aziridine derivative and preparation thereof - Google Patents
Fluorescent fullerene aziridine derivative and preparation thereof Download PDFInfo
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- CN101434576B CN101434576B CN2008102039706A CN200810203970A CN101434576B CN 101434576 B CN101434576 B CN 101434576B CN 2008102039706 A CN2008102039706 A CN 2008102039706A CN 200810203970 A CN200810203970 A CN 200810203970A CN 101434576 B CN101434576 B CN 101434576B
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- fullerene
- naphthalimide
- aziridine
- fluorescence
- nitrine
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Abstract
The invention relates to a fluorescent aziridine fullerene derivative and a preparation method thereof. The structural formula of the derivative is Formula 1, wherein, R1 is an alkyl of C1 to C32. Indicated by an ultraviolet and fluorescence performance test, the compound realizes the fluorescence transformation of fullerene by the introduction of a fluorescence block and has an abrupt change in fluorescence performance in comparison with the fluorescence performance of the fullerene so as to greatly improve the fluorescence performance of the fullerene, thereby initially completing the fluorescence transformation of the fullerene. The significance of the transformation is that the invention of the product can provide a new thinking path for research on the application of the fullerene, and can also enhance the value of the fullerene applied to the fields of biomedicine, materials science and the like.
Description
Technical field
The present invention relates to a kind of fluorescent fullerene aziridine derivative and preparation method thereof.
Background technology
At biomedical sector, since the no fluorescence of most of biomolecules itself or fluorescence a little less than, detection sensitivity is relatively poor, people generate reagent with the labelled reagent of hyperfluorescence or fluorescence and determinand is carried out mark or derive, generation has the covalently or non-covalently bonded material of high fluorescent, detection limit is reduced greatly, the fluorescent probe technique that development in recent years that Here it is is very fast.Its basic characteristics are to possess high sensitivity and extremely wide dynamic response time.Along with the continuous development of biotechnology, more and more higher to the requirement of protein, nucleic acid and cell marking, no matter traditional Radiolabelling method is can not adapt to the development today needs far away from safety performance or from application performance.
Find C from F.Curl in 1985 and R.E.Smalley
60, and obtained since the Nobel chemistry Prize in 1996 years, the research in this field shows its unprecedented vitality.What wherein gain a special interest is the research of its derivative to anti AIDS virus, once carries out the molecular model Calculation and Study as far back as Friedman in 1993 etc., finds by using C
60Molecule and the effect of HIVP active part, block active hole, can suppress HIVP toxicity, and at first synthesized first and contained the HIVP inhibitor of soccerballene, this compound can suppress the toxicity of HIVP well by with the virus protease active part very strong Vander Waal ' s effect taking place.This makes C
60Derivative has demonstrated wide biomedical applications prospect.
Because the special construction of soccerballene has limited the generation of its fluorescence property, in addition, almost have no talent through the document fluorescence modification work of fullerene derivate as can be known of consulting and to do.Can better be studied visually and be used in order to make fullerene derivate potential biological activity, our combined with fluorescent probe technique, the fluorescence modified with functional group is carried out on the soccerballene surface, wish to make it become the soccerballene fluorescent derivative of the novel traceable research of a class.At present, our soccerballene fluorescence modification work mainly is to introduce the fluorescence building block on soccerballene, the result shows, resulting fullerene aziridine fluorescent derivative fluorescence property is compared with soccerballene has tangible enhancing, for a new direction has been opened up in the fluorescence work of the fullerene derivate of carrying out biologically active from now on.Fullerene aziridine fluorescent derivative of the present invention is a fullerene three membered heterocycle derivatives, and productive rate height (nearly 70%), and fluorescence property is strong, has laid working foundation for further studying.
Summary of the invention
One of purpose of the present invention is to provide a kind of fluorescent fullerene aziridine derivative.
Two of purpose of the present invention is to provide the preparation method of this compound.
For achieving the above object, reaction equation of the present invention is:
Wherein, R
1Be expressed as C
1～C
32Alkyl.
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of fluorescent fullerene aziridine derivative is characterized in that the structural formula of this derivative is:
Wherein, R
1Be C
1～C
32Alkyl.
A kind of method for preparing above-mentioned fluorescent fullerene aziridine derivative is characterized in that the concrete steps of this method are: under inert atmosphere, with 4-nitrine-1, the dichlorobenzene solution of 8-naphthalimide is added drop-wise to C
60O-dichlorobenzene solution in, at 100-200 ℃, reacted 1-20 hour, the elimination insoluble matter is used column chromatography purification, the product fluorescent fullerene aziridine derivative; Described 4-nitrine-1, the structural formula of 8-naphthalimide is:
, wherein, R
1Be C
1～C
32Alkyl; 4-nitrine-1,8-naphthalimide and C
60Mol ratio be: 1: be reasonable between the 1-10.
The concrete steps of aforesaid method are: under inert atmosphere, with 4-nitrine-1, the dichlorobenzene solution of 8-naphthalimide is added drop-wise to C
60O-dichlorobenzene solution in, at 100-200 ℃, reacted 1-20 hour, the elimination insoluble matter is used column chromatography purification, the product fluorescent fullerene aziridine derivative; Described 4-nitrine-1, the structural formula of 8-naphthalimide is:
, wherein, R
1Be C
1～C
32Alkyl; 4-nitrine-1,8-naphthalimide and C
60Mol ratio be: 1: 3.
A kind of method for preparing above-mentioned fluorescent fullerene aziridine derivative is characterized in that the concrete steps of this method are: with C
60With 4-nitrine-1, the 8-naphthalimide is (by 1: the mol ratio of 1-10) be dissolved in the orthodichlorobenzene, under inert atmosphere, microwave reaction 1-60min, microwave power is between 100-1000W, and reaction removes by filter insoluble matter after finishing, filtrate is used column chromatography purification, gets the product fluorescent fullerene aziridine derivative; Described 4-nitrine-1, the structural formula of 8-naphthalimide is:
, wherein, R
1Be C
1～C
32Alkyl.
Compound of the present invention is found by ultraviolet and fluorescence property test, introducing by the fluorescence building block has realized the transformation of soccerballene fluorescence, and the enhancing of jumping has taken place in this compounds than the fluorescence property of soccerballene itself, improved the fluorescence property of soccerballene greatly, finished the fluorescence retrofit work of soccerballene, and the meaning of this transformation is that the invention of this class product will provide a new study route to the applied research of soccerballene, and may strengthen it in biomedicine, the using value of material science (fluorescence spectrum is seen accompanying drawing).
The inventive method utilizes heating method and two kinds of methods of microwave assistant one kettle way to synthesize fluorescent fullerene aziridine derivative, wherein, the microwave assistant method have the reaction times short, condition is easy to operate, product is easily separated and the advantage of clean and effective.
Description of drawings
Fig. 1 is the fluorescent absorption of soccerballene fluorescent chemicals of the present invention and the comparison of emmission spectrum and soccerballene, wherein C
1Be N-normal-butyl-4-aziridine [C60]-1,8-naphthalimide, C
2Be N-dodecyl-4-aziridine [C60]-1,8-naphthalimide, C
3Be N-n-hexadecyl-4-aziridine [C60]-1,8-naphthalimide.
Embodiment
The 4-nitrine-1 of one of raw material of the present invention, the preparation method of 8-naphthalimide sees also Chinese patent: 200810040021.0.
Embodiment one: N-normal-butyl-4-aziridine [C60]-1, the preparation of 8-naphthalimide
Method one: the C that gets 0.1mmol
60Be dissolved in the 50ml orthodichlorobenzene; nitrogen protection under the normal temperature; slowly be heated to 130 ℃; in 1 hour, slowly drip N-normal-butyl-4-nitrine-1; 8-naphthalimide solution (N-normal-butyl-4-nitrine-1 of 0.6mmol, the 8-naphthalimide is dissolved in the orthodichlorobenzene of 5ml) dropwises; slowly be warming up to 160 ℃; reacting by heating 10 hours, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains N-normal-butyl-4-aziridine [C60]-1,8-naphthalimide, productive rate 28% to constant weight.
Method two: with C
60With N-normal-butyl-4-nitrine-1; the 8-naphthalimide is dissolved in the orthodichlorobenzene of 10ml microwave reaction 800W under the situation of nitrogen protection with 1: 4 mixed; 3min; after reaction finishes, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains N-normal-butyl-4-aziridine [C60]-1,8-naphthalimide, productive rate 55% to constant weight.
The structural formula of this product is:
Title: N-normal-butyl-4-aziridine [C60]-1,8-naphthalimide
Color: brown
Product structure characterizes:
IR(KBr，cm
-1)：v?2958，2910，2867，1699，1654，1588，1348，1260，1077，1022，801，784，525；
1H?NMR(500MHz，CDCl
3)：δ8.69(d，J＝7Hz，1H)，8.62(d，J＝8.5Hz，1H)，8.53(d，J＝8Hz，1H)，7.84-7.92(m，2H)，4.20(t，J＝7.5Hz，2H)，1.71-1.77(m，2H)，1.45-1.50(m，2H)，1.01(t，J＝7.5Hz，2H)。
Embodiment two: N-dodecyl-4-aziridine [C60]-1, the preparation of 8-naphthalimide
Method one: the C that gets 0.1mmol
60Be dissolved in the 50ml orthodichlorobenzene; nitrogen protection under the normal temperature; slowly be heated to 130 ℃; in 1 hour, slowly drip the positive dodecyl of N--4-nitrine-1; 8-naphthalimide solution (the positive dodecyl of the N-of 0.6mmol-4-nitrine-1, the 8-naphthalimide is dissolved in the orthodichlorobenzene of 5ml) dropwises; slowly be warming up to 160 ℃; reacting by heating 6 hours, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains the positive dodecyl of N--4-aziridine [C60]-1,8-naphthalimide, productive rate 52% to constant weight.
Method two: with C
60With the positive dodecyl of N--4-nitrine-1; the 8-naphthalimide is dissolved in the orthodichlorobenzene of 10ml microwave reaction 800W under the situation of nitrogen protection with 1: 3 mixed; 4min; after reaction finishes, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains N-dodecyl-4-aziridine [C60]-1,8-naphthalimide, productive rate 67% to constant weight.
This product N-dodecyl-4-aziridine [C60]-1, the structural formula of 8-naphthalimide is:
Title: N-dodecyl-4-aziridine [C60]-1,8-naphthalimide
Color: brown
IR(KBr，cm
-1)：v?2960，2920，2849，1696，1661，1582，1261，1096，1022，802，526；
1H?NMR(500MHz，CDCl
3)：δ9.30(d，J＝8.5Hz，1H)，8.69(d，J＝7.5Hz，2H)，7.90-7.94(m，2H)，4.16(t，J＝7Hz，2H)，1.71-1.74(m，2H)，1.25-1.44(m，18H)，0.87(t，J＝6.5Hz，3H)；
13C?NMR(125MHz，CDCl
3)：δ163.7，163.3，146.5，145.5，145.4，145.2，145.1，144.7，144.4，144.0，143.8，143.3，143.2，143.1，143.0，142.2，141.3，134.9，131.8，131.6，129.8，128.5，127.8，127.3，125.2，124.1，119.9，82.6，40.57，32.2，30.2，30.0，29.9，29.8，28.7，28.4，27.4，23.1，14.5。
Embodiment three: N-n-hexadecyl-4-aziridine [C60]-1, the preparation of 8-naphthalimide
Method one: the C that gets 0.1nmol
60Be dissolved in the 50ml orthodichlorobenzene; nitrogen protection under the normal temperature; slowly be heated to 130 ℃; in 1 hour, slowly drip N-n-hexadecyl-4-nitrine-1; 8-naphthalimide solution (N-n-hexadecyl-4-nitrine-1 of 0.6nmol, the 8-naphthalimide is dissolved in the orthodichlorobenzene of 5ml) dropwises; slowly be warming up to 160 ℃; reacting by heating 6 hours, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains N-n-hexadecyl-4-aziridine [C60]-1,8-naphthalimide, productive rate 52% to constant weight.
Method two: with C
60With N-n-hexadecyl-4-nitrine-1; the 8-naphthalimide is dissolved in the orthodichlorobenzene of 10ml microwave reaction 800W under the situation of nitrogen protection with 1: 5 mixed; 4min; after reaction finishes, elimination insoluble matter, concentrated liquid; isolate product with the toluene column chromatography purification; vacuum-drying obtains N-n-hexadecyl-4-aziridine [C60]-1,8-naphthalimide, productive rate 70% to constant weight.
This product N-n-hexadecyl-4-aziridine [C60]-1,8-naphthalimide structure formula is:
Title: N-n-hexadecyl-4-aziridine [C60]-1,8-naphthalimide
Color: brown
IR(KBr，cm
-1)：v?2963，2920，2850，1661，1531，1261，801，701，520；
1H?NMR(500MHz，CDCl
3)：δ8.76(d，J＝7.5Hz，1H)，7.96-8.00(m，1H)，7.55(d，J＝8Hz，1H)，7.37(d，J＝8.5Hz，1H)，7.15(d，J＝8.5Hz，1H)，4.23(t，J＝7Hz，2H)，1.78-1.79(m，2H)，1.29-1.48(m，26H)，0.91(t，J＝6.5Hz，3H)；
13C?NMR(125MHz，CDCl
3)：δ164.1，163.9，146.6，145.5，145.4，145.2，145.1，144.7，144.4，144.0，143.8，143.3，143.2，143.0，142.2，142.1，141.2，141.0，131.8，131.6，129.7，128.6，127.3，125.2，124.0，123.9，119.9，118.9，82.5，44.1，40.6，32.0，31.5，30.2，29.8，29.77，29.75，29.70，29.6，29.5，29.4，28.3，27.3，22.8，14.2。
MS：m/z(％)：1153(M-1，12)，720(C
60，100)。
Claims (3)
1. fluorescent fullerene aziridine derivative is characterized in that the structural formula of this derivative is:
Wherein, R
1Be C
1～C
32Alkyl.
2. method for preparing fluorescent fullerene aziridine derivative according to claim 1, it is characterized in that the concrete steps of this method are: under inert atmosphere, with 4-nitrine-1, the dichlorobenzene solution of 8-naphthalimide is added drop-wise to C
60O-dichlorobenzene solution in, at 100-200 ℃, reacted 1-20 hour, the elimination insoluble matter is used column chromatography purification, the product fluorescent fullerene aziridine derivative; Described 4-nitrine-1, the structural formula of 8-naphthalimide is:
Wherein, R
1Be C
1～C
32Alkyl; 4-nitrine-1,8-naphthalimide and C
60Mol ratio be: 1: 3.
3. a method for preparing fluorescent fullerene aziridine derivative according to claim 1 is characterized in that the concrete steps of this method are: with C
60With 4-nitrine-1, the 8-naphthalimide is dissolved in the orthodichlorobenzene by 1: 3 mol ratio, under inert atmosphere, microwave reaction 1-30min, microwave power 800W is after reaction finishes, remove by filter insoluble matter, filtrate is used column chromatography purification, gets the product fluorescent fullerene aziridine derivative; Described 4-nitrine-1, the structural formula of 8-naphthalimide is:
Wherein, R
1Be C
1～C
32Alkyl.
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| CN102516228A (en) * | 2011-12-21 | 2012-06-27 | 上海大学 | 1'-(N-alkyl-1, 8-naphthalimide)-3'-(substituted phenyl)pyrazoline fullerene compound and its preparation method |
| CN102911002A (en) * | 2012-10-23 | 2013-02-06 | 中国科学院化学研究所 | Fullerene derivative containing double-benzene nucleus and preparation method and application thereof |
| CN103214418A (en) * | 2013-04-10 | 2013-07-24 | 上海大学 | 1-(N-fluorenyl)-3-fluorinated phenyl pyrazoline fullerene C60 and preparation method thereof |
| CN104925779B (en) * | 2014-03-21 | 2016-09-07 | 国家纳米科学中心 | A kind of fullerene derivate and its preparation method and application |
| CN107216267B (en) * | 2017-07-03 | 2019-02-22 | 广东工业大学 | A kind of azobenzene grafting fullerene nano hybridization compound and preparation method |
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