CN105906467B - A kind of synthetic method of different three polyindene of organic photoelectrical material - Google Patents
A kind of synthetic method of different three polyindene of organic photoelectrical material Download PDFInfo
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Abstract
A kind of synthetic method of different three polyindene of organic photoelectrical material, is related to electroluminescent organic material.A kind of synthetic method for different three polyindene of organic photoelectrical material that raw material is cheap and easy to get, reaction scale can amplify, method is simple, efficient is provided.1 indone is dissolved in organic acid, 2 indones and another acid solution are sequentially added, solid filtering is precipitated in temperature reaction postcooling to room temperature, and washing obtains filter cake；Filter cake is washed with ketones solvent or chlorinated hydrocarbon solvent, collects leacheate, concentration obtains different three polyindene of organic photoelectrical material after being recrystallized with benzene kind solvent, be in faint yellow solid；It takes the remaining solid of filter cake to be recrystallized with benzene kind solvent, three polyindene of by-product of high-purity can be obtained.The yield of different three polyindene of principal product can be 45%~60%, and purity is more than 95%；The yield of three polyindene of by-product can be 10%~20%, and purity is more than 99%.
Description
Technical field
The present invention relates to electroluminescent organic materials, more particularly, to a kind of synthesis side of different three polyindene of organic photoelectrical material
Method.
Background technology
Different three polyindene is the isomer of three polyindenes, and the two belongs to compound of fluorene class, is led in electroluminescent organic material
Domain has major application potentiality[1,2].However, for a long time, chemist is to the research of different three polyindene but far fewer than three polyindenes.According to
Literature survey, this is mainly due to known different three polyindenes synthetic methods there are many limitations, as condition is harsh, yield is relatively low,
Complex steps, expensive starting materials and being difficult to amplify production etc..
Nineteen sixty, Germanization scholar Lang, Zander and Theiling report the synthetic method of different three polyindene for the first time[3],
Using indenes as raw material, 2h is reacted under 350 DEG C and 20 atmospheric pressures, obtains the mixture of different three polyindenes and three polyindenes, total yield
Rate is 40%.The reaction condition of the method is excessively harsh, is prepared to laboratory and industrial production has severely restricts.
2006, Yang Ji's water seminar of Taiwan Univ. reported a kind of improvement synthetic method of different three polyindene：It is original with indenes
Material, iodine and cesium carbonate are reagent, and different three polyindene is can be obtained under the conditions of normal pressure and 160 DEG C[4].But there are many this method side reaction,
Yield is only 18%, and is difficult to amplify production.2009, which reported the synthesis side of other three kinds different three polyindenes again
Method is constructed out molecular skeleton by cycloaddition, then is modified, and target product is obtained[5].But it is anti-that three kinds of methods are required to multistep
It answers (4~7 step), and total recovery is relatively low (27%~36%), reaction scale is limited (10g grades).
Later, the front yards National Cheng Kung University Wu Yao seminar[6], Liu Qian ability seminar of East China Normal University[7]Add with similar ring
At-modification strategy, a kind of multi-step synthetic methods of different three polyindene are respectively developed.Its total recovery and reaction scale are compared with Yang Ji's water class
The method of topic group is not affected significantly.
Bibliography：
[1]Goubard,F.,Dumur,F.,Truxene:A Promising Scaffold for Future
Materials,RSC Adv.,2015,5,3521-3551.
[2]Shi,K.,Wang,J.-Y.,Pei,J.,π-Conjugated Aromatics Based on Truxene:
Synthesis,Self-Assembly,and Applications,Chem.Rec.,2015,15,52-72.
[3]Lang,K.F.,Zander,M.,Theiling,E.A.,Isotruxene,Chem.Ber.,1960,93,
321-325.
[4]Yang,J.-S.,Lee,Y.-R.,Yan,J.-L.,Lu,M.-C.,Synthesis and Properties
of a Fluorene-Capped Isotruxene:A New Unsymmetrical Star-ShapedΠ-System,
Org.Lett.,2006,8,5813-5816.
[5]Yang,J.-S.,Huang,H.-H.,Lin,S.-H.,Facile Multistep Synthesis of
Isotruxene and Isotruxenone,J.Org.Chem.,2009,74,3974-3977.
[6]Chen,J.-J.,Onogi,S.,Hsieh,Y.-C.,Hsiao,C.-C.,Higashibayashi,S.,
Sakurai,H.,Wu,Y.-T.,Palladium-Catalyzed Arylation of Methylene-Bridged
Polyarenes:Synthesis and Structures of 9-Arylfluorene Derivatives,
Adv.Synth.Catal.,2012,354,1551-1558.
[7]Liu,Q.,Yao,W.,Yang,L.,Li,J.,Huang,X.,Method for Synthesis of
Indenofluorene Derivatives,Isotruxene and Monosubstituted Isotruxene
Derivatives[P],China,CN102627522A,2012.
Invention content
Cheap and easy to get, reaction scale that the purpose of the present invention is to provide raw materials can amplify that (kilogram grade), method be simple, effect
A kind of synthetic method of different three polyindene of the high organic photoelectrical material of rate.
The structural formula of different three polyindene of organic photoelectrical material is：
The present invention is as follows：
1- indones are dissolved in organic acid, sequentially add 2- indones and another acid solution, temperature reaction postcooling is extremely
Room temperature, is precipitated solid filtering, and washing obtains filter cake；Filter cake is washed with ketones solvent or chlorinated hydrocarbon solvent, collects leacheate,
Concentration, obtains different three polyindene of organic photoelectrical material after being recrystallized with benzene kind solvent, be in faint yellow solid；Take the remaining solid of filter cake
It is recrystallized with benzene kind solvent, three polyindene of by-product of high-purity can be obtained.
1- indones can be dissolved in organic acid by described 1- indones are dissolved in organic acid at 0~30 DEG C；The heating is anti-
The temperature answered can be 60~150 DEG C, and the time of temperature reaction can be 3~48h.
The addition of the 2- indones can be the 40%~120% of 1- indones by mass percentage；The temperature reaction
The total mol concentration of reactant can be 0.5~5.0mol/L, and short chain fatty acids can be used in the organic acid；The ketones solvent can
One kind in acetone, butanone, cyclopentanone etc.；The chlorinated hydrocarbon solvent can be selected from dichloromethane, chloroform, 1,2- bis-
One kind in chloroethanes etc.；The benzene kind solvent can be selected from one kind in benzene,toluene,xylene etc..
Experiments have shown that the yield of different three polyindene of principal product can be 45%~60%, purity is more than 95%；Three polyindene of by-product
Yield can be 10%~20%, purity be more than 99%.
The reaction equation of the present invention is as follows：
The present invention provides synthesis and the purification process of above compound：Using 1- indones and 2- indones as raw material, in two kinds of acid
Mixed solution in flow back.Reaction product obtains filter cake through filtering, washing.Continuation is washed with ketones solvent or chlorinated hydrocarbon solvent
Filter cake is washed, leacheate is collected, concentration obtains different three polyindene of high-purity after being recrystallized with benzene kind solvent.Take the residue of filter cake solid
Body is recrystallized with benzene kind solvent, can obtain three polyindene of by-product of high-purity.
The present invention is the novel synthesis that a kind of step high yield largely prepares different three polyindene, and this method raw material is inexpensively easy
, reaction scale can amplify (kilogram grade), and purification process very simple.Its efficiency all known synthesis sides than before
Method has a significant improvement.This can provide enough raw material sources for the synthesis of different trimer indene derivative, promote chemist to its property
The research of matter (especially photoelectric property) and the exploitation of novel optoelectronic materials, have good development potentiality and application prospect.
Specific implementation mode
For ease of further understanding the present invention, the following example elaborates details particularly.
Embodiment 1
10g 1- indones and 60mL acetic acid, magnetic agitation 10min are added in 250mL two-neck bottles.Then divide under stiring
It criticizes and 5g 2- indones and 20mL hydrochloric acid (6mol/L) is added, reaction system is slowly increased to 90 DEG C, reacts 12h, obtain a large amount of
Yellow solid.It filters, washing, gained filter cake is washed (total 100mL) for several times with dichloromethane, collects leacheate, concentration, with two
Re crystallization from toluene obtains the different three polyindenes 7.64g of principal product, is faint yellow solid, yield 59%.Remaining cake is tied again with toluene
Crystalline substance obtains three polyindene 2.07g of by-product, is faint yellow solid, yield 16%.
Embodiment 2
As described in Example 1, the inventory of 2- indones is changed to 8g, remaining synthesis is constant with purification process.Obtain main product
The different three polyindenes 8.08g of object is faint yellow solid, yield 52%；Three polyindene 1.94g of by-product is obtained, is faint yellow solid, yield
12%.
Embodiment 3
150g1- indones and 1 liter of acetic acid, machine are added in 2 liters of three-necked bottles equipped with electric mixer and reflux condensate device
Tool stirs 10min, forms suspension, 100g2- indones and 500mL concentrated hydrochloric acids (12mol/L) are then added portionwise under stiring,
Temperature of reaction system is slowly increased to 140 DEG C of back flow reaction 40h, obtains a large amount of yellow solids.It filters, washing, gained filter cake is used
Acetone washs for several times (total 300mL), collects leacheate, and concentration is recrystallized with dimethylbenzene, obtains different three polyindene of principal product
119g is faint yellow solid, yield 55%.By remaining cake re crystallization from toluene, three polyindene 25.9g of by-product is obtained, is light
Yellow solid, yield 12%.
The Spectroscopic Characterization data of principal product and by-product are as follows：
Different three polyindenes data：
1H NMR(400MHz,CDCl3):δ 8.60 (t, J=8.0Hz, 2H), 7.94 (d, J=7.2Hz, 1H), 7.71 (d,
J=7.2Hz, 1H), 7.64 (t, J=7.2Hz, 2H), 7.51-7.45 (m, 3H), 7.42-7.34 (m, 3H), 4.28 (s, 2H),
4.01(s,4H)。
13C NMR(400MHz,CDCl3):δ144.08,144.05,143.87,142.37,142.04,141.80,
139.09,137.46,136.85,136.48,136.09,135.69,126.89,126.79,126.53,126.29,126.17,
126.14,125.16,125.12,125.05,123.54,123.33,122.12,36.57,35.90,35.72。
MS(EI)m/z:342[M]+。
HRMS(EI):m/z 342.1411.Calcd.for C27H18 +:342.1409。
Three polyindene data：
1H NMR(500MHz,CDCl3):δ 7.97 (d, J=7.5Hz, 3H), 7.71 (d, J=7.5Hz, 3H), 7.51 (t,
J=7.5Hz, 3H), 7.40 (t, J=7.5Hz, 3H), 4.30 (s, 6H).
13C NMR(400MHz,CDCl3):δ143.80,141.71,137.11,135.28,126.94,126.31,
125.14,121.89,36.55.
MS(EI)m/z:342[M]+。
HRMS(EI):m/z 342.1405.Calcd.for C27H18 +:342.1409。
Claims (8)
1. a kind of synthetic method of different three polyindene of organic photoelectrical material, it is characterised in that different three polyindene of organic photoelectrical material
Structural formula is：
The synthetic method is as follows：
1- indones are dissolved in organic acid, sequentially add 2- indones and another acid solution, temperature reaction postcooling to room temperature,
Solid filtering is precipitated, washing obtains filter cake；Filter cake is washed with ketones solvent or chlorinated hydrocarbon solvent, collects leacheate, is concentrated,
Different three polyindene of organic photoelectrical material is obtained after being recrystallized with benzene kind solvent；
The addition of the 2- indones is the 40%~120% of 1- indones by mass percentage；
The total mol concentration of the reactant of the temperature reaction is 0.5~5.0mol/L.
2. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the filter cake
Remaining solid is recrystallized with benzene kind solvent, obtains three polyindene of by-product.
3. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that described by 1- indenes
It is that 1- indones are dissolved in organic acid at 0~30 DEG C that ketone, which is dissolved in organic acid,.
4. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the organic acid
Using short chain fatty acids.
5. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the ketone is molten
The one kind of agent in acetone, butanone, cyclopentanone.
6. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the chlorohydrocarbon
The one kind of class solvent in dichloromethane, chloroform, 1,2- dichloroethanes.
7. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the benzene class is molten
The one kind of agent in benzene,toluene,xylene.
8. a kind of synthetic method of different three polyindene of organic photoelectrical material as described in claim 1, it is characterised in that the heating is anti-
The temperature answered is 60~150 DEG C, and the time of temperature reaction is 3~48h.
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