CN110183452A - A kind of perfluoro butyl substituted compound and its preparation method and application - Google Patents

A kind of perfluoro butyl substituted compound and its preparation method and application Download PDF

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CN110183452A
CN110183452A CN201910406735.7A CN201910406735A CN110183452A CN 110183452 A CN110183452 A CN 110183452A CN 201910406735 A CN201910406735 A CN 201910406735A CN 110183452 A CN110183452 A CN 110183452A
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CN110183452B (en
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岳晚
徐玉淳
王亚洲
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Sun Yat Sen University
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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Abstract

The invention discloses a kind of perfluoro butyl substituted compounds and its preparation method and application；The compound is the perfluoro butyl substituted compound of Dithiophene pyrrolo-pyrrole-dione, bioxindol and thiophene bioxindol, its chemical structural formula is respectively as shown in formula (III), (VI), (X), wherein R is branched paraffin or linear paraffin with 8~16 carbon atoms, and the compound has preferable solubility property, and each step yield is higher than 10%.There is better air stability compared with the compound not replaced by fluoroalkyl, its LUMO, HOMO energy level reduces, be conducive to electron injection and transmission, and maximum absorption wavelength has potential application prospect in visible regime, in organic field effect tube (OFET), the organic solar batteries field (OPV).

Description

A kind of perfluoro butyl substituted compound and its preparation method and application
Technical field
The invention belongs to organic semiconductor synthesis technical fields, more particularly, to a kind of perfluoro butyl substituted compound And its preparation method and application.
Background technique
The materials such as dione pyrrolo-pyrrole, bioxindol and its derivative are current widely used organic semiconductor materials Material.Its electron-transport can be enhanced in the preferable flatness of dione pyrrolo-pyrrole and bioxindol and its derivative, therefore is having It is used widely in field effect transistors (OFET), organic photovoltaic battery (OPV).But this kind of compound is in n-type semiconductor Many problems are still remained in material, such as energy level mismatches, dissolubility, stability is not high.
Currently, the prior art is usually to modify pyrrolopyrrole two by introducing side group on aromatic rings or aromatic heterocycle Ketone and bioxindol, however generally require first to generate halogenated compound, then generate final goal object by coupling reaction, there is reaction The problem of step is complicated, and reaction yield is low, generates pollution or harmful by-products；Therefore, one kind is found to be simple and efficient and yield Relatively high synthetic method is also extremely urgent.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, provide it is a kind of it is novel, stable, dissolubility is good Perfluoro butyl substituent.
A second object of the present invention is to provide the preparation methods of the perfluoro butyl substituent.
Above-mentioned purpose of the invention is to give realization by the following technical programs:
A kind of perfluoro butyl substituted compound, shown in general formula of the chemical structure such as formula (III), (VI) or (X):
Wherein, R is the branched paraffin or linear paraffin of 8~16 C.
Full compound of the present invention is side group by the branched paraffin or linear paraffin for introducing 8~16 carbon atoms, is made The compound has good dissolubility energy；It is strong electron-withdrawing due to fluorine atom by carrying out perfluoro butyl substitution, it can be with Make the fluoroalkylation compound in the present invention that its lumo energy and HOMO energy level be effectively reduced, can also be changed by fluoroalkyl chain Molecules align mode, avoids the entrance of water oxygen molecule, to improve its air stability, is conducive to electron injection and transmission, and And maximum absorption wavelength is in visible regime.
Preferably, the R is isooctane base.
The preparation method of the compound (III), comprising the following steps:
S1. under nitrogen protection, potassium tert-butoxide and solvent are added in the reaction vessel and stirs, then sequentially adds cyano Thiophene, dimethyl succinate tert-amyl alcohol solution continue stirring and are reacted, post-treated after the reaction was completed to obtain compound (I)； Its chemical equation is as follows:
S2. under nitrogen protection, compound (I), potassium carbonate and crown ether -6 18- are added into reaction vessel, are then added Solvent simultaneously stirs, and is eventually adding brominated alkanes and is reacted, and processing obtains compound (II) after the reaction was completed；Its chemical reaction side Formula is as follows:
S3. under nitrogen protection, compound (II), copper nanoparticle are added into reaction vessel, solvent is then added and stirs It mixes, is eventually adding perfluor butyl iodide and is reacted, processing obtains compound (III) after the reaction was completed；Its chemical reaction equation Formula is as follows:
Preferably, solvent described in S1 is tert-pentyl alcohol.
Preferably, the reaction molar concentration of 2- cyano thiophene described in S1 is 1mol/L~1.1mol/L, such as 1mol/L, 1.05mol/L or 1.1mol/L.
Preferably, the molar ratio of 2- cyano thiophene, dimethyl succinate and potassium tert-butoxide described in S1 is 3:1:3.15.
Preferably, reaction described in S1 is in 90~110 DEG C of 7~9h of reaction, such as in 110 DEG C of reaction 8h.
Preferably, post-reaction treatment described in S1 is that first alcohol and water is added at 80 DEG C to continue to stir 45min, is cooled to room temperature Hydrochloric acid and methanol are added afterwards and stirs 45min, finally filters and washs filter residue with methanol and obtain solid product.
Preferably, solvent described in S2 is DMF.
Preferably, the reaction molar concentration of compound described in S2 (I) be 0.1~0.3mol/L, such as 0.1mol/L, 0.2mol/L or 0.3mol/L.
Preferably, the molar ratio of compound described in S2 (I), brominated alkanes, potassium carbonate and 18- crown ether -6 is 1:4:5:4.
Preferably, described in S2 reaction for 80~120 DEG C reaction 4~for 24 hours, such as 120 DEG C reaction for 24 hours.
Preferably, then post-processing described in S2 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:3.
Preferably, solvent described in S3 is DMSO.
Preferably, the reaction molar concentration of compound described in S3 (II) is 0.04~0.05mol/L, such as 0.04mol/L Or 0.05mol/L.
Preferably, compound described in S3 (II), perfluor butyl iodide, copper nanoparticle molar ratio be 1:4:15.
Preferably, reaction described in S3 is 80~120 DEG C of 2~5h of reaction, such as 120 DEG C of reaction 4h.
Preferably, then post-processing described in S3 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:5.
The preparation method of the compound (VI), comprising the following steps:
S1. isatin, 2- indolone and hydrochloric acid are added into reaction vessel, stirring solvent is then added and is reacted, reacts Post-processing obtains compound (IV)；Its chemical equation is as follows:
S2. under nitrogen protection, compound (IV) and potassium carbonate are added into reaction vessel, solvent is then added and stirs It mixes, is eventually adding brominated alkanes and is reacted, processing obtains compound (V) after the reaction was completed；Its chemical equation is as follows It is shown:
S3. under nitrogen protection, compound (V), copper nanoparticle are added into reaction vessel, solvent is then added and stirs It mixes, is eventually adding perfluor butyl iodide and is reacted, processing obtains compound (VI) after the reaction was completed；Its chemical equation It is as follows:
Preferably, solvent described in S1 is acetic acid.
Preferably, the reaction molar concentration of isatin described in S1 is 0.1mol/L~0.2mol/L, such as 0.1mol/L, 0.15mol/L or 0.2mol/L.
Preferably, isatin described in S1,2- indolone molar ratio be 1:1.
Preferably, concentration of hydrochloric acid solution described in S1 is 1mL/150mL.
Preferably, reaction described in S1 is in 100~120 DEG C of reaction 3-12h, such as in 115 DEG C of reaction 5h.
Preferably, post-reaction treatment described in S1 is to reaction solution cooled and filtered, and with cold methanol, water, sodium bicarbonate Solution and pentane wash filter residue, obtain solid product
Preferably, solvent described in S2 is DMF.
Preferably, the reaction molar concentration of compound described in S2 (IV) be 0.1~0.3mol/L, such as 0.1mol/L, 0.2mol/L or 0.3mol/L.
Preferably, the molar ratio of compound described in S2 (IV), brominated alkanes and potassium carbonate is 1:2.5:10.
Preferably, described in S2 reaction for 80~120 DEG C reaction 4~for 24 hours, such as 110 DEG C reaction for 24 hours.
Preferably, then post-processing described in S2 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:3.
Preferably, solvent described in S3 is DMSO.
Preferably, the reaction molar concentration of compound described in S3 (V) be 0.05~0.06mol/L, such as 0.05mol/L or 0.06mol/L。
Preferably, compound described in S3 (V), perfluor butyl iodide, copper nanoparticle molar ratio be 1:8:25.
Preferably, reaction described in S3 is 80~120 DEG C of 2~6h of reaction, such as 120 DEG C of reaction 5h.
Preferably, then post-processing described in S3 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:5.
The preparation method of the compound (X), comprising the following steps:
S1. under nitrogen protection, cuprous iodide, potassium carbonate are added into reaction vessel, solvent is then added and stirs, most 3 bromo thiophene, 2- isobutyryl cyclohexanone and amino alkane are added afterwards to be reacted, is handled after the reaction was completed, in oxalyl chloride Middle addition reaction solution and triethylamine, processing obtains compound (VIII) after the reaction was completed；Its chemical equation is as follows:
S2. under nitrogen protection, compound (VIII) and lawesson reagent are added into reaction vessel, solvent is then added and stirs It mixes and is reacted, processing obtains compound (IX) after the reaction was completed；Its chemical equation is as follows:
S3. under nitrogen protection, compound (IX), copper nanoparticle are added into reaction vessel, solvent is then added and stirs It mixes, is eventually adding perfluor butyl iodide and is reacted, processing obtains compound (X) after the reaction was completed；Its chemical equation It is as follows:
Preferably, first step solvent described in S1 is DMF.
Preferably, the reaction molar concentration of 3 bromo thiophene described in S1 be 2mol/L~2.5mol/L, such as 2mol/L or 2.5mol/L。
Preferably, mole of 3 bromo thiophene, octodrine described in S1, cuprous iodide, 2- isobutyryl cyclohexanone and potassium carbonate Than are as follows: 20:30:1:4:4.
Preferably, reaction described in S1 is in 100~120 DEG C of reaction 3-12h, such as in 120 DEG C of reaction 4h.
Preferably, then reaction first step processing described in S1 passes through layer for solution after reaction to be first evaporated under reduced pressure It analyses column to rapidly purify, eluant, eluent is methylene chloride.
Preferably, second step solvent described in S1 is methylene chloride.
Preferably, the reaction molar concentration of 3- secondary amine thiophene described in S1 be 0.2~0.3mol/L, such as 0.2mol/L, 0.25mol/L or 0.3mol/L.
Preferably, the molar ratio of 3- secondary amine thiophene, oxalyl chloride and triethylamine described in S1 is 1:1.35:4.5.
Preferably, reaction described in S1 is in 10-25 DEG C of reaction 8-12h, such as in 25 DEG C of reaction 12h.
Preferably, post-reaction treatment described in S1 is first to be evaporated under reduced pressure solution after reaction, then passes through chromatographic column Purifying, eluant, eluent is ethyl acetate: petroleum ether 1:8.
Preferably, solvent described in S2 is ortho-xylene.
Preferably, the reaction molar concentration of compound described in S2 (VIII) be 0.1~0.3mol/L, such as 0.1mol/L, 0.2mol/L or 0.3mol/L.
Preferably, compound described in S2 (VIII), lawesson reagent molar ratio be 2:1.
Preferably, reaction described in S2 is 50~60 DEG C of 2~4h of reaction, such as 60 DEG C of reaction 2h.
Preferably, then post-processing described in S2 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:3.
Preferably, solvent described in S3 is DMSO.
Preferably, the reaction molar concentration of compound described in S3 (IX) is 0.05~0.06mol/L, such as 0.05mol/L Or 0.06mol/L.
Preferably, compound described in S3 (IX), perfluor butyl iodide, copper nanoparticle molar ratio be 1:4:15.
Preferably, reaction described in S3 is 80~120 DEG C of 2~6h of reaction, such as 120 DEG C of reaction 3h.
Preferably, then post-processing described in S3 passes through column chromatography for solution after reaction to be first evaporated under reduced pressure, The ratio of eluant dichloromethane and petroleum ether is 1:6.
Dithiophene pheno pyrrolo-pyrrole-dione of the invention, the perfluoro butyl substituent of bioxindol and thiophene bioxindol lead to It crosses the branched paraffin for introducing 8~16 carbon atoms or linear paraffin is side group, enable the compound that there is good dissolubility； The compound has better air stability compared with not carrying out the substituted compound of perfluor alkane, and lumo energy reduces, has Conducive to electron injection and transmission, and maximum absorption wavelength is in visible regime, in organic field effect tube (OFET), organic The solar battery field (OPV) has potential application prospect.
Therefore, the present invention also protects the Dithiophene pheno pyrrolo-pyrrole-dione, the perfluor of bioxindol and thiophene bioxindol Butyl substituent is preparing the application in organic semiconducting materials or organic field effect tube or organic solar battery material.
Compared with prior art, the invention has the following advantages:
(1) present invention synthesis has obtained Dithiophene pheno pyrrolo-pyrrole-dione, the perfluor fourth of bioxindol and thiophene bioxindol Base substituent has preferable solubility property, is soluble in the organic solvents such as methylene chloride, n-hexane.With do not carry out perfluor alkane substitution Compound compare, due to forming F-H key in fluoroalkyl chain and alkyl chain, the entrance of water oxygen molecule is prevented, so that compound has Better air stability, LUMO, HOMO energy level reduce, and are conducive to electron injection and transmission, and maximum absorption wavelength exists Visible regime, before organic field effect tube (OFET), the organic solar batteries field (OPV) have potential application Scape.
(2) Dithiophene pheno pyrrolo-pyrrole-dione of the invention, the perfluoro butyl substituent of bioxindol and thiophene bioxindol Synthetic method is simple, at low cost, and yield is relatively high, eliminates the harm using heavy metal catalyst, reduces toxic pair The generation of product is conducive to purification.
Detailed description of the invention
The perfluoro butyl substituent of the position Fig. 1 invention Dithiophene pheno pyrrolo-pyrrole-dione, bioxindol and thiophene bioxindol Prepare chemical equation.
Fig. 2 is compound (III) in embodiment 11H NMR spectra.
Fig. 3 is the ultraviolet absorption curve of compound (III) in embodiment 1.
Fig. 4 is the cyclic voltammetry curve of compound (III) in embodiment 1.
Fig. 5 is compound (VI) in embodiment 21H NMR spectra.
Fig. 6 is the ultraviolet absorption curve of compound (VI) in embodiment 2.
Fig. 7 is the cyclic voltammetry curve of compound (VI) in embodiment 2.
Fig. 8 is compound (X) in embodiment 31H NMR spectra.
Fig. 9 is the ultraviolet absorption curve of compound (X) in embodiment 3.
Figure 10 is the cyclic voltammetry curve of compound (X) in embodiment 3.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
AVANCE III 400M type Liquid NMR spectrometer that the present invention is produced using Bruker company, Switzerland detects Product obtains 1H NMR, 13C NMR spectra, and solvent is deuterated chloroform (CDCl3) and deuterated dichloromethane (CD2Cl2), tetramethylsilane Alkane (TMS) is internal standard.This experiment uses the solariX quality analysis flight mass spectrometer (Maldi-TOF) of Switzerland Bruker production Molecular weight is characterized, measures the ultraviolet suction of product using the UV-3600 type ultraviolet-uisible spectrophotometer of Shimadzu company Spectrum is received, using the quartz colorimetric utensil of 1 × 1cm as sample cell, using the CHI620E electrification of Shanghai Chen Hua Instrument Ltd. Credit analyzer.
Dithiophene pyrrolo-pyrrole-dione in the following specific embodiments of the present invention, bioxindol and thiophene bioxindol it is complete The preparation chemical equation of fluorine butyl substituent is as shown in Figure 1.Wherein, R is the branched paraffin or straight chain alkane of 8~16 C Hydrocarbon, such as isooctane base.
Embodiment 1
A kind of preparation method of the perfluoro butyl substituent of pyrrolo-pyrrole-dione, includes the following steps:
(1) 29g potassium tert-butoxide is added in three neck round bottom flask, starts degassing then inflated with nitrogen, continuously three times, then 179mL tert-pentyl alcohol is added, in 110 DEG C of stirring 2h.Then 20mL3- cyano thiophene is added dropwise and stirs 45min, is added dropwise with dropping funel 9.4mL dimethyl succinate and 29mL tert-amyl alcohol solution, stirring continue to stir 3h.Solution after reaction adds after being cooled to 80 DEG C Enter 108mL methanol and 29mL deionized water stirring 45min, after solution is cooled to room temperature, 57mL hydrochloric acid and 287mL methanol is added Stir 45min.Treated, and reaction solution is filtered, and washs filter residue with 72mL methanol, obtains compound (I), obtained chemical combination The quality of object is 9.54g, yield 16.3%；Its chemical equation is as follows:
(2) 1.024g compound (I), 2.7642g potassium carbonate and 4.2991g18- crown ether 6 are added in round-bottomed flask, Start degassing then inflated with nitrogen, continuously three times, 20mLN, dinethylformamide (DMF) is then added, then stirring is added 2.84mL bromo-iso-octane, in 120 DEG C of reaction 12h.Obtained solution is first evaporated under reduced pressure, then by column chromatography, is washed The ratio of de- agent methylene chloride and petroleum ether is 1:3, and compound (II) can be obtained by vacuum distillation, obtain the matter of compound Amount is about 1.52g, yield 72%；Its chemical equation is as follows:
(3) 50mg compound (II), 90.9mg copper nanoparticle are added in round-bottomed flask, start degassing then nitrogen charging Then continuously three times 2mL dimethyl sulfoxide (DMSO) is added in gas, then 132mg perfluor butyl iodide is added, 120 in stirring DEG C reaction 3h.Obtained solution is first evaporated under reduced pressure, column chromatography, the ratio of eluant dichloromethane and petroleum ether are then passed through Example is 1:5, compound (III) can be obtained by vacuum distillation, the quality for obtaining compound is about 10.2mg, and yield is 14.4%；Its chemical equation is as follows:
Fig. 2 is compound (III's)1H NMR spectra, the compound that can prove synthesis by hydrogen nuclear magnetic resonance spectrogram are Structure (III)；Fig. 3 is the ultraviolet absorption curve figure of compound (III), and the compound of synthesis can be learnt by the spectrogram (III) a length of 551nm of maximum absorption wave is located at visible-range；The cyclic voltammetry curve figure of the position Fig. 4 compound (III), passes through The lumo energy that compound (III) is calculated in curve is -3.30eV, and HOMO energy level is -5.24eV.
Embodiment 2
A kind of preparation method of the perfluoro butyl substituent of bioxindol, includes the following steps:
(1) 3.7754g isatin, 3.4472g2- indolone and 1mL hydrochloric acid are added in round-bottomed flask, are then added 150mL acetic acid, stirring, in 115 DEG C of reaction 12h；By the solution filtering after reaction, with methanol, water, sodium bicarbonate solution and pentane Filter residue is washed, is obtained solid chemical compound (IV), the quality of compound is 4.8537g, yield 79%；Its chemical equation It is as follows:
(2) 1.5g compound (IV), 7.905g potassium carbonate are added in round-bottomed flask, start degassing then inflated with nitrogen, Continuously three times, 30mLN, dinethylformamide (DMF) is then added, then 2.76g bromo-iso-octane is added, 100 in stirring DEG C reaction for 24 hours.Obtained solution is first evaporated under reduced pressure, then by column chromatography, eluant dichloromethane and petroleum ether Ratio is 1:3, be can be obtained compound (V) by vacuum distillation, and the quality of compound is 2.56g, yield 92%；Its chemistry Reaction equation is as follows:
(3) 50mg compound (V), 163.4mg copper nanoparticle are added in round-bottomed flask, start degassing then nitrogen charging Then continuously three times 2mL dimethyl sulfoxide (DMSO) is added in gas, then 284.8mg perfluor butyl iodide is added in stirring, 120 DEG C of reaction 5h.Obtained solution is first evaporated under reduced pressure, column chromatography, eluant dichloromethane and petroleum ether are then passed through Ratio be 1:5, can be obtained compound (VI) by vacuum distillation, the quality of compound is 18mg, yield 26%；It is changed It is as follows to learn reaction equation:
Fig. 5 is compound (VI's)1H NMR spectra, the compound that can prove synthesis by hydrogen nuclear magnetic resonance spectrogram are Structure (VI)；Fig. 6 is the ultraviolet absorption curve figure of compound (VI), can learn the compound (VI) of synthesis most by the spectrogram Big absorbing wavelength is 500nm, is located at visible-range；Fig. 7 is the cyclic voltammetry curve figure of compound (VI), is calculated by curve The lumo energy for obtaining compound (VI) is -3.69eV, and HOMO energy level is -5.53eV.
Embodiment 3
A kind of preparation method of the perfluoro butyl substituent of thiophene bioxindol, includes the following steps:
(1) 0.2g cuprous iodide, 5.6g potassium carbonate are added in round-bottomed flask, start degassing then inflated with nitrogen, continuously Three times, be then added 10mLN, dinethylformamide (DMF), stirring, be then added 2mL3- bromothiophene, 5mL octodrine, Obtained solution is first evaporated under reduced pressure in 120 DEG C of reaction 12h, then passes through flash chromatography by 0.74g2- isobutyryl cyclohexanone Column, eluant, eluent are methylene chloride, obtain 3- secondary amine thiophene；0.75mL oxalyl chloride is added in round-bottomed flask, 25mL bis- is added Chloromethanes, at 0 DEG C by 1.9939g3- secondary amine thiophene and 11mL dichloromethane solution and 5.71mL triethylamine and 40mL dichloromethane Alkane solution is successively added dropwise in round-bottomed flask, and stirring reacts 12h at room temperature, obtained solution is first evaporated under reduced pressure, layer is passed through Analyse column purification, eluant ethyl acetate: the ratio of petroleum ether is 1:8, obtains compound (VIII), compound by vacuum distillation Quality be 515.7mg, yield 9.7%；Its chemical equation is as follows:
(2) 515.7mg compound (VIII) and 393.5mg lawesson reagent are added in round-bottomed flask, it is right starts degassing Continuously three times 10mL ortho-xylene, stirring, in 60 DEG C of reaction 3h is added in inflated with nitrogen afterwards.Obtained solution is first evaporated under reduced pressure, By column chromatography, the ratio of eluant dichloromethane and petroleum ether is 1:3, obtains compound (IX) by vacuum distillation, The quality of compound is 223.1mg, yield 46.0%；Its chemical equation is as follows:
(3) 223.1mg compound (IX), 430.1mg copper nanoparticle are added in round-bottomed flask, start to deaerate and then fills Then continuously three times 9mL dimethyl sulfoxide (DMSO) is added in nitrogen, then 620.0mg perfluor butyl iodide is added in stirring, 120 DEG C of reaction 4h.Obtained solution is first evaporated under reduced pressure, column chromatography, eluant dichloromethane and petroleum ether are then passed through Ratio be 1:5, can be obtained compound (X) by vacuum distillation, the quality of compound is 96mg, yield 29%；It is changed It is as follows to learn reaction equation:
Fig. 8 is compound (X's)1H NMR spectra can prove the compound of synthesis for knot by hydrogen nuclear magnetic resonance spectrogram Structure (X)；Fig. 9 is the ultraviolet absorption curve figure of compound (X), can learn that the compound (X) of synthesis is maximum by the spectrogram and inhale Receipts wavelength is 557nm, is located at visible-range；Figure 10 is the cyclic voltammetry curve figure of compound (X), is calculated by curve The lumo energy of compound (VI) is -3.92eV, and HOMO energy level is -5.51eV.

Claims (10)

1. a kind of perfluoro butyl substituted compound, which is characterized in that its general formula of the chemical structure such as formula (III), (VI) or (X) institute Show:
Wherein, R is the branched paraffin or linear paraffin of 8~16 C.
2. perfluoro butyl substituted compound according to claim 1, which is characterized in that the R is isooctane base.
3. the preparation method of perfluoro butyl substituted compound described in claim 1, which comprises the steps of:
For leading to formula (III), the steps include:
S1. under nitrogen protection, potassium tert-butoxide and solvent are added in the reaction vessel and stirs, then sequentially adds cyano thiophene Pheno, dimethyl succinate tert-amyl alcohol solution continue stirring and are reacted, post-treated after the reaction was completed to obtain compound (I)；
S2. under nitrogen protection, compound (I), potassium carbonate and crown ether -6 18- are added into reaction vessel, solvent is then added And stir, it is eventually adding brominated alkanes and is reacted, processing obtains compound (II) after the reaction was completed；
S3. under nitrogen protection, compound (II), copper nanoparticle are added into reaction vessel, solvent is then added and stirs, most Perfluor butyl iodide is added afterwards to be reacted, processing obtains compound (III) after the reaction was completed；
For leading to formula (VI), the steps include:
S1. isatin, 2- indolone and hydrochloric acid are added into reaction vessel, stirring solvent is then added and is reacted, after reaction Reason obtains compound (IV)；
S2. under nitrogen protection, compound (IV) and potassium carbonate are added into reaction vessel, solvent is then added and stirs, most Brominated alkanes are added afterwards to be reacted, processing obtains compound (V) after the reaction was completed；
S3. under nitrogen protection, compound (V), copper nanoparticle are added into reaction vessel, solvent is then added and stirs, most Perfluor butyl iodide is added afterwards to be reacted, processing obtains compound (VI) after the reaction was completed；
For leading to formula (X), the steps include:
S1. under nitrogen protection, cuprous iodide, potassium carbonate are added into reaction vessel, is then added and solvent and stirs, finally plus Enter 3 bromo thiophene, 2- isobutyryl cyclohexanone and amino alkane to be reacted, is handled after the reaction was completed, continuously add oxalyl Chlorine, triethylamine and solvent are reacted, and processing obtains compound (VIII) after the reaction was completed；
S2. under nitrogen protection, compound (VIII) and lawesson reagent are added into reaction vessel, be then added stirring solvent into Row reaction, processing obtains compound (IX) after the reaction was completed；
S3. under nitrogen protection, compound (IX), copper nanoparticle are added into reaction vessel, solvent is then added and stirs, most Perfluor butyl iodide is added afterwards to be reacted, processing obtains compound (X) after the reaction was completed.
4. preparation method according to claim 3, which is characterized in that the reaction molar concentration of the compound (II) is 0.04~0.05mol/L.
5. preparation method according to claim 3, which is characterized in that the compound (II), perfluor butyl iodide and receive Rice copper powder molar ratio is 1:4:15.
6. preparation method according to claim 3, which is characterized in that the reaction molar concentration of the compound (V) is 0.05~0.06mol/L.
7. preparation method according to claim 3, which is characterized in that the compound (V), perfluor butyl iodide and nanometer Copper powder molar ratio is 1:8:25.
8. preparation method according to claim 3, which is characterized in that the reaction molar concentration of the compound (IX) is 0.05~0.06mol/L.
9. preparation method according to claim 3, which is characterized in that the compound (IX), perfluor butyl iodide and receive Rice copper powder molar ratio is 1:4:15.
10. perfluoro butyl substituted compound as claimed in claim 1 or 2 is preparing organic semiconducting materials or organic effect crystal Application in pipe or organic solar battery material.
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