CN102417476A - Synthesis method of soluble fulleropyrrolidine derivate - Google Patents
Synthesis method of soluble fulleropyrrolidine derivate Download PDFInfo
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- CN102417476A CN102417476A CN2011102512621A CN201110251262A CN102417476A CN 102417476 A CN102417476 A CN 102417476A CN 2011102512621 A CN2011102512621 A CN 2011102512621A CN 201110251262 A CN201110251262 A CN 201110251262A CN 102417476 A CN102417476 A CN 102417476A
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- soccerballene
- solubility
- fulleropyrrolidine
- derivate
- pyrrolidin derivatives
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Abstract
The invention belongs to the technical field of organic synthesis, and specifically relates to a synthesis method of a soluble fulleropyrrolidine derivate. The solubilities of the fulleropyrrolidine derivate in methyl benzene and tetrahydrofuran solvents can be respectively up to 16mg/mL and 10mg/mL or above. The method can greatly improve the solubility of fullerene. The fulleropyrrolidine derivate prepared by the method has fine solubility property, film-forming property and photoelectric property; the preparation method has the advantages of convenient process, high yield, low cost, wide application prospects, large-scale production and the like; and the product prepared by the preparation method is a new generation green environment-friendly high-performance chemical product, and can be used in the fields of organic polymer solar cells, field-effect transistors, organic optical conductors and the like.
Description
Technical field
The invention belongs to the technical field of organic synthesis, be specifically related to a kind of compound method of solubility soccerballene pyrrolidin derivatives.
Background technology
Soccerballene as electron acceptor(EA) is one of the most popular organic photovoltaic material of research at present; Yet itself is slightly soluble in organic solvent soccerballene, make itself and organic polymer just must carry out its solvability in organic solvent of organically-modified raising to it compatible on the molecular level.Mainly contain two kinds of common soccerballene method of modifying at present; One type is nucleophilic addition; Soccerballene has electron deficiency alkene character, and it can carry out addition reaction with nucleophilic reagents such as organometallic reagent such as lithium alkylide, grignard reagent, ylide reagent, aminated compounds, cyanogen negative ion, oxyhydroxide, and soccerballene can also be through the nucleophilic attack of carbanion; And then lose a negative ion, thereby obtain the verivate of methylene radical soccerballene; Another kind of is cycloaddition reaction, comprises [4+2] cycloaddition reaction, [3+2] cycloaddition reaction, [2+2] cycloaddition reaction and [2+1] cycloaddition reaction, and wherein important is the reaction of imines ylide, diazonium compound and triazo-compound and soccerballene.
Though the verivate of many soccerballenes is produced out; And be used in the opto-electronic devices such as organic polymer solar cell, field-effect transistor and organic photoconductor; But most popular so far still still is fullerene derivate PCBM ([6,6]-benzene-carbon 61-methyl-butyrate).In order to improve the solubility property of soccerballene acceptor material, and improve its photoelectric properties, the present invention's design has also prepared a kind of novel solubility soccerballene pyrrolidin derivatives.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of compound method of solubility soccerballene pyrrolidin derivatives is provided.
The compound method of a kind of solubility soccerballene pyrrolidin derivatives that the present invention proposes, concrete steps are following:
With 100-1000 mg C
60, 100-500 mg 4-hydroxy benzaldehyde, 100-1000 mg sarcosine and 10-100 mL toluene adds in the reaction flask; Vacuumize repeatedly and inflated with nitrogen 2-5 time, 60-120 ℃ following stirring reaction 1-12 hour, be cooled to 25 ℃; Above-mentioned reaction soln is passed through 200～600 purpose silica gel column chromatography separating purifications; Obtain a kind of soccerballene pyrrolidin derivatives solution, rotary evaporation is removed organic solvent toluene again, obtains a kind of solubility soccerballene pyrrolidin derivatives at last.
Among the present invention, the eluent that uses in the said silica gel column chromatography separating purification is 1:1 ~ 10:1 as vinyl acetic monomer and methylene dichloride mixed solvent, its volume ratio.
Advantage of the present invention is: 1. the present invention is a kind of compound method of solubility soccerballene pyrrolidin derivatives; The solubility property of this soccerballene pyrrolidin derivatives in organic solvents such as hexanaphthene, chloroform, THF, acetone and N-Methyl pyrrolidone all is significantly improved; For example their solubleness in toluene and tetrahydrofuran solvent is by original slightly soluble with insolublely can be increased to 16 mg/mL respectively and more than 10 mg/mL, can improve the solvability of soccerballene significantly through present method; 2. the product that utilizes the present invention to prepare has good solubility property, film forming properties and photoelectric properties; 3. preparation method of the present invention has that technology is easy, productive rate is high, with low cost, advantage such as application prospect big and be produced on a large scale; The product that utilizes the present invention to prepare; Be new generation of green environment-friendly and high-performance Chemicals, can be used for fields such as organic polymer solar cell, field-effect transistor and organic photoconductor.
Description of drawings
Fig. 1 is the synthetic synoptic diagram of solubility soccerballene pyrrolidin derivatives.
Fig. 2 is digital photograph (the left figure: C of the toluene solution of solubility soccerballene pyrrolidin derivatives
60Right figure: the soccerballene pyrrolidin derivatives).
Fig. 3 is the infrared spectrogram of solubility soccerballene pyrrolidin derivatives.
Fig. 4 is the ultraviolet-visible light spectrogram of solubility soccerballene pyrrolidin derivatives.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1
With 720 mg C
60, 183 mg 4-hydroxy benzaldehydes, 535 mg sarcosines and 80 mL toluene add in the 150 mL reaction flasks; Vacuumize repeatedly and inflated with nitrogen 3 times; 100 ℃ of following stirring reactions 5 hours are cooled to 25 ℃, with above-mentioned reaction soln through 300 purpose silica gel column chromatography separating purifications (eluent: vinyl acetic monomer/methylene dichloride mixed solvent; Its volume ratio is 2:1) obtain a kind of soccerballene pyrrolidin derivatives solution; Rotary evaporation is removed organic solvent again, obtains a kind of solubility soccerballene pyrrolidin derivatives at last, and productive rate is 45%.
Fig. 1 is the synthetic synoptic diagram of this solubility soccerballene pyrrolidin derivatives; Fig. 2 is the digital photograph of the toluene solution of this soccerballene pyrrolidin derivatives; The infrared spectrogram of this soccerballene pyrrolidin derivatives and ultraviolet-visible light spectrogram are respectively like Fig. 3 and shown in Figure 4, and table 1 is the solubility property of this soccerballene pyrrolidin derivatives.
Table 1
| ? | Normal hexane | Hexanaphthene | Benzene | Toluene | Chlorobenzene | Dichlorobenzene |
| C 60 | － | － | ﹢ | ﹢ | ﹢ | ﹢ |
| C 60Pyrrolidin derivatives | － | ± | ﹢ | ﹢ | ﹢ | ﹢ |
| ? | Chloroform | THF | Acetone | N-Methyl pyrrolidone | Ethanol | Methyl alcohol |
| C 60 | － | － | － | ± | － | － |
| C 60Pyrrolidin derivatives | ± | ﹢ | ± | ﹢ | － | － |
Wherein " ﹢ " represents Yi Rong, the insoluble or slightly soluble of "-" representative, and " ± " represents indissoluble.
Embodiment 2
Identical with embodiment 1, but the consumption of 4-hydroxy benzaldehyde and sarcosine becomes 122 mg and 267 mg, and other are constant.
Embodiment 3
Identical with embodiment 1, but the consumption of 4-hydroxy benzaldehyde becomes 122 mg, and other are constant.
Embodiment 4
Identical with embodiment 1, but the consumption of 4-hydroxy benzaldehyde and sarcosine becomes 122 mg and 891 mg, and other are constant.
Embodiment 5
Identical with embodiment 1, but the consumption of 4-hydroxy benzaldehyde becomes 244 mg by 183 mg, and other are constant.
Embodiment 6
Identical with embodiment 1, but the consumption of sarcosine becomes 891 mg by 535 mg, and other are constant.
Embodiment 7
Identical with embodiment 1, but temperature of reaction is by 100
oC becomes 110
oC, the reaction times became 3 hours by 5 hours, and other are constant.
Embodiment 8
Identical with embodiment 1, but temperature of reaction is by 100
oC becomes 90
oC, the reaction times became 7 hours by 5 hours, and other are constant.
The solubility soccerballene pyrrolidin derivatives and the embodiment 1 that obtain among the embodiment 2-8 have similar performance.
Claims (2)
1. the compound method of a solubility soccerballene pyrrolidin derivatives is characterized in that concrete steps are:
With 100-1000 mg C
60, 100-500 mg 4-hydroxy benzaldehyde, 100-1000 mg sarcosine and 10-100 mL toluene joins in the reaction flask; Vacuumize repeatedly and inflated with nitrogen 2-5 time; 60-120 ℃ following stirring reaction 1-12 hour, be cooled to 25 ℃, above-mentioned reaction soln is obtained a kind of soccerballene pyrrolidin derivatives solution through 200～600 purpose silica gel column chromatography separating purifications; Rotary evaporation is removed organic solvent toluene again, obtains solubility soccerballene pyrrolidin derivatives.
2. compound method according to claim 1 is characterized in that the eluent that uses in the said silica gel column chromatography separating purification is vinyl acetic monomer and methylene dichloride mixed solvent, and its volume ratio is 1:1 ~ 10:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396354A (en) * | 2013-07-22 | 2013-11-20 | 西南科技大学 | Synthesis method of fullerene pyrrolidine derivative |
| CN105461615A (en) * | 2015-11-24 | 2016-04-06 | 山东大学 | Preparation method of non-ionic fullerene-containing amphiphilic molecule |
| CN109627204A (en) * | 2018-12-13 | 2019-04-16 | 黄山学院 | A kind of preparation method and application of methoxyl group containing 3- -4- (5- bromine amoxy) phenyl fullerene chemistry |
| CN110066238A (en) * | 2019-05-10 | 2019-07-30 | 西南科技大学 | Fullerene phenylate class pyrrolidines phenylate analog derivative and its preparation method and application |
| CN111574465A (en) * | 2019-02-18 | 2020-08-25 | 中国科学院化学研究所 | Soluble graphyne derivative and preparation method and application thereof |
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| CN1530385A (en) * | 2003-03-14 | 2004-09-22 | 中国科学院化学研究所 | Flexible composite membrane with optical limiting characteristic and preparing method thereof |
| US7692187B2 (en) * | 2006-03-20 | 2010-04-06 | National Institute Of Advanced Industrial Science And Technology | Organic semiconductor material and organic device using the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396354A (en) * | 2013-07-22 | 2013-11-20 | 西南科技大学 | Synthesis method of fullerene pyrrolidine derivative |
| CN103396354B (en) * | 2013-07-22 | 2015-09-16 | 西南科技大学 | The synthetic method of fulleropyrrolidine derivative |
| CN105461615A (en) * | 2015-11-24 | 2016-04-06 | 山东大学 | Preparation method of non-ionic fullerene-containing amphiphilic molecule |
| CN109627204A (en) * | 2018-12-13 | 2019-04-16 | 黄山学院 | A kind of preparation method and application of methoxyl group containing 3- -4- (5- bromine amoxy) phenyl fullerene chemistry |
| CN111574465A (en) * | 2019-02-18 | 2020-08-25 | 中国科学院化学研究所 | Soluble graphyne derivative and preparation method and application thereof |
| CN111574465B (en) * | 2019-02-18 | 2021-06-22 | 中国科学院化学研究所 | Soluble graphyne derivative and preparation method and application thereof |
| CN110066238A (en) * | 2019-05-10 | 2019-07-30 | 西南科技大学 | Fullerene phenylate class pyrrolidines phenylate analog derivative and its preparation method and application |
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Application publication date: 20120418 |