CN110183452B - Perfluorobutyl substituted compound and preparation method and application thereof - Google Patents

Perfluorobutyl substituted compound and preparation method and application thereof Download PDF

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CN110183452B
CN110183452B CN201910406735.7A CN201910406735A CN110183452B CN 110183452 B CN110183452 B CN 110183452B CN 201910406735 A CN201910406735 A CN 201910406735A CN 110183452 B CN110183452 B CN 110183452B
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岳晚
徐玉淳
王亚洲
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Sun Yat Sen University
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Abstract

The invention discloses a perfluorobutyl substituted compound and a preparation method and application thereof; the compound is a perfluorobutyl substituted compound of dithiophene pyrrolopyrrole-dione, isoindigo and thiophene isoindigo, the chemical structural formulas of the compounds are respectively shown as formulas (III), (VI) and (X), wherein R is branched chain alkane or straight chain alkane with 8-16 carbon atoms, the compound has good solubility, and the yield of each step is higher than 10%. Compared with compounds which are not substituted by fluoroalkyl, the compound has better air stability, the LUMO and HOMO energy levels of the compound are reduced, the electron injection and transmission are facilitated, and the maximum absorption wavelength of the compound is in the visible light field and has potential application prospects in the fields of Organic Field Effect Transistors (OFETs) and organic solar cells (OPVs).

Description

Perfluorobutyl substituted compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic semiconductor synthesis, and particularly relates to a perfluorobutyl substituted compound and a preparation method and application thereof.
Background
The materials such as pyrrolopyrrole diketones, isoindigo and derivatives thereof are organic semiconductor materials widely applied at present. The good planarity of the pyrrolopyrrole diketones, the isoindigo and the derivatives thereof can enhance the electron transmission thereof, so the pyrrolopyrrole diketones, the isoindigo and the derivatives thereof can be widely applied to Organic Field Effect Transistors (OFETs) and organic photovoltaic cells (OPVs). However, the compounds still have a plurality of problems in n-type semiconductor materials, such as energy level mismatch, and low solubility and stability.
At present, in the prior art, a side group is usually introduced on an aromatic ring or an aromatic heterocycle to modify pyrrolopyrrole dione and isoindigo, however, a halogenated compound is often required to be generated firstly, and then a final target product is generated through a coupling reaction, so that the problems of complicated reaction steps, low reaction yield and generation of polluting or toxic by-products exist; therefore, it is urgent to find a simple and efficient synthetic method with relatively high yield.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel, stable and good-solubility perfluorobutyl substituent.
The second purpose of the invention is to provide a preparation method of the perfluorobutyl substituent.
The above object of the present invention is achieved by the following technical solutions:
a perfluorobutyl substituted compound has a chemical structural general formula shown in formula (III), (VI) or (X):
Figure GDA0002541930940000021
wherein R is branched chain alkane or straight chain alkane with 8-16C.
The full compound has good solubility by introducing branched chain alkane or straight chain alkane with 8-16 carbon atoms as a side group; by carrying out perfluorobutyl substitution, the fluoroalkyl compound can effectively reduce the LUMO energy level and the HOMO energy level of the fluoroalkyl compound due to the strong electron withdrawing property of fluorine atoms, and the molecular arrangement mode can be changed through a fluoroalkyl chain, so that water oxygen molecules are prevented from entering, the air stability of the fluoroalkyl compound is improved, the injection and transmission of electrons are facilitated, and the maximum absorption wavelength is in the visible light field.
Preferably, R is isooctyl.
A process for the preparation of said compound (III), comprising the steps of:
s1, under the protection of nitrogen, adding potassium tert-butoxide and a solvent into a reaction vessel, stirring, then sequentially adding a cyanothiophene and dimethyl succinate tert-amyl alcohol solution, continuously stirring for reaction, and carrying out aftertreatment after the reaction is finished to obtain a compound (I); the chemical reaction equation is as follows:
Figure GDA0002541930940000022
s2, under the protection of nitrogen, adding the compound (I), potassium carbonate and 18-crown-6 into a reaction vessel, then adding a solvent and stirring, finally adding bromoalkane for reaction, and carrying out post-treatment after the reaction is finished to obtain a compound (II); the chemical reaction equation is as follows:
Figure GDA0002541930940000031
s3, under the protection of nitrogen, adding the compound (II) and the nano copper powder into a reaction container, then adding a solvent, stirring, finally adding perfluoroiodobutane to react, and carrying out post-treatment after the reaction is finished to obtain a compound (III); the chemical reaction equation is as follows:
Figure GDA0002541930940000032
preferably, the solvent of S1 is t-amyl alcohol.
Preferably, the reaction molar concentration of the 2-cyanothiophene described in S1 is 1mol/L to 1.1mol/L, such as 1mol/L, 1.05mol/L or 1.1 mol/L.
Preferably, the molar ratio of the 2-cyanothiophene, the dimethyl succinate and the potassium tert-butoxide in S1 is 3:1: 3.15.
Preferably, the reaction of S1 is carried out at 90-110 ℃ for 7-9 h, for example at 110 ℃ for 8 h.
Preferably, the post-reaction treatment of S1 is adding methanol and water at 80 ℃ and continuing stirring for 45min, cooling to room temperature and adding hydrochloric acid and methanol and stirring for 45min, and finally filtering and washing the filter residue with methanol to obtain a solid product.
Preferably, the solvent of S2 is DMF.
Preferably, the reaction molar concentration of the compound (I) in S2 is 0.1-0.3 mol/L, such as 0.1mol/L, 0.2mol/L or 0.3 mol/L.
Preferably, the molar ratio of the compound (I) described in S2, the bromoalkane, the potassium carbonate and the 18-crown-6 is 1:4:5: 4.
Preferably, the reaction of S2 is carried out at 80-120 ℃ for 4-24 h, for example, at 120 ℃ for 24 h.
Preferably, the post-treatment of S2 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1:3.
Preferably, the solvent of S3 is DMSO.
Preferably, the reaction molar concentration of the compound (II) in S3 is 0.04-0.05 mol/L, such as 0.04mol/L or 0.05 mol/L.
Preferably, the mole ratio of the compound (II) in S3, the perfluoroiodobutane and the nano copper powder is 1:4: 15.
Preferably, the reaction of S3 is carried out at 80-120 ℃ for 2-5 h, for example, at 120 ℃ for 4 h.
Preferably, the post-treatment of S3 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1: 5.
A process for the preparation of said compound (VI), comprising the steps of:
s1, adding isatin, 2-indolone and hydrochloric acid into a reaction vessel, then adding a solvent, stirring, reacting, and carrying out post-reaction treatment to obtain a compound (IV); the chemical reaction equation is as follows:
Figure GDA0002541930940000041
s2, adding a compound (IV) and potassium carbonate into a reaction container under the protection of nitrogen, then adding a solvent and stirring, finally adding bromoalkane for reaction, and carrying out post-treatment after the reaction is finished to obtain a compound (V); the chemical reaction equation is as follows:
Figure GDA0002541930940000042
s3, under the protection of nitrogen, adding the compound (V) and the nano copper powder into a reaction container, then adding a solvent, stirring, finally adding perfluoroiodobutane to react, and carrying out post-treatment after the reaction is finished to obtain a compound (VI); the chemical reaction equation is as follows:
Figure GDA0002541930940000043
preferably, the solvent of S1 is acetic acid.
Preferably, the reaction molar concentration of isatin at S1 is 0.1mol/L to 0.2mol/L, such as 0.1mol/L, 0.15mol/L or 0.2 mol/L.
Preferably, the molar ratio of isatin to 2-indolone of S1 is 1:1.
Preferably, the concentration of the hydrochloric acid solution of S1 is 1mL/150 mL.
Preferably, the reaction of S1 is carried out at 100-120 ℃ for 3-12h, for example at 115 ℃ for 5 h.
Preferably, the post-reaction treatment of S1 is to cool the reaction solution and filter, and wash the filter residue with cold methanol, water, sodium bicarbonate solution and pentane to obtain solid product
Preferably, the solvent of S2 is DMF.
Preferably, the reaction molar concentration of the compound (IV) in S2 is 0.1-0.3 mol/L, such as 0.1mol/L, 0.2mol/L or 0.3 mol/L.
Preferably, the molar ratio of the compound (IV) described in S2, the alkyl bromide and the potassium carbonate is 1:2.5: 10.
Preferably, the reaction of S2 is carried out at 80-120 ℃ for 4-24 h, for example, at 110 ℃ for 24 h.
Preferably, the post-treatment of S2 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1:3.
Preferably, the solvent of S3 is DMSO.
Preferably, the reaction molar concentration of the compound (V) in S3 is 0.05-0.06 mol/L, such as 0.05mol/L or 0.06 mol/L.
Preferably, the molar ratio of the compound (V) in S3, the perfluoroiodobutane and the nano copper powder is 1:8: 25.
Preferably, the reaction of S3 is carried out at 80-120 ℃ for 2-6 h, for example, at 120 ℃ for 5 h.
Preferably, the post-treatment of S3 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1: 5.
A process for the preparation of said compound (X), comprising the steps of:
s1, under the protection of nitrogen, adding cuprous iodide and potassium carbonate into a reaction vessel, then adding a solvent and stirring, finally adding 3-bromothiophene, 2-isobutyrylcyclohexanone and aminoalkane for reaction, after the reaction is finished, treating, adding a reaction solution and triethylamine into oxalyl chloride, and after the reaction is finished, treating to obtain a compound (VIII); the chemical reaction equation is as follows:
Figure GDA0002541930940000051
s2, adding the compound (VIII) and a Lawson reagent into a reaction vessel under the protection of nitrogen, then adding a solvent, stirring, reacting, and carrying out post-treatment after the reaction to obtain a compound (IX); the chemical reaction equation is as follows:
Figure GDA0002541930940000061
s3, under the protection of nitrogen, adding the compound (IX) and the nano copper powder into a reaction container, then adding a solvent, stirring, finally adding perfluoroiodobutane to react, and carrying out post-treatment after the reaction is finished to obtain a compound (X); the chemical reaction equation is as follows:
Figure GDA0002541930940000062
preferably, the first step solvent of S1 is DMF.
Preferably, the reaction molar concentration of the 3-bromothiophene described in S1 is 2mol/L to 2.5mol/L, such as 2mol/L or 2.5 mol/L.
Preferably, the molar ratio of the 3-bromothiophene, isooctylamine, cuprous iodide, 2-isobutyrylcyclohexanone and potassium carbonate in S1 is: 20:30:1:4:4.
Preferably, the reaction of S1 is carried out at 100-120 ℃ for 3-12h, for example, at 120 ℃ for 4 h.
Preferably, the first step of the reaction described in S1 is to distill the solution after the reaction is finished under reduced pressure and then to purify it rapidly by a chromatographic column, and the eluent is dichloromethane.
Preferably, the second-step solvent of S1 is dichloromethane.
Preferably, the reaction molar concentration of the 3-secondary aminothiophene of S1 is 0.2-0.3 mol/L, such as 0.2mol/L, 0.25mol/L or 0.3 mol/L.
Preferably, the molar ratio of the 3-secondary aminothiophene, oxalyl chloride and triethylamine in S1 is 1:1.35: 4.5.
Preferably, the reaction of S1 is a reaction at 10-25 ℃ for 8-12h, for example at 25 ℃ for 12 h.
Preferably, the post-reaction treatment of S1 is to distill the solution after the end of the reaction under reduced pressure and then purify the solution through a chromatographic column, wherein the eluent is ethyl acetate: and 1:8 of petroleum ether.
Preferably, the solvent of S2 is o-xylene.
Preferably, the reaction molar concentration of the compound (VIII) in S2 is 0.1-0.3 mol/L, such as 0.1mol/L, 0.2mol/L or 0.3 mol/L.
Preferably, the molar ratio of the compound (VIII) described in S2 to the lawson reagent is 2: 1.
Preferably, the reaction of S2 is carried out at 50-60 ℃ for 2-4 h, for example, at 60 ℃ for 2 h.
Preferably, the post-treatment of S2 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1:3.
Preferably, the solvent of S3 is DMSO.
Preferably, the compound (IX) of S3 is reacted at a molar concentration of 0.05 to 0.06mol/L, such as 0.05mol/L or 0.06 mol/L.
Preferably, the mole ratio of the compound (IX) in S3, the perfluoroiodobutane and the nano copper powder is 1:4: 15.
Preferably, the reaction of S3 is carried out at 80-120 ℃ for 2-6 h, for example, at 120 ℃ for 3 h.
Preferably, the post-treatment of S3 is to distill the solution after the reaction under reduced pressure and then purify the solution by a chromatographic column, wherein the ratio of dichloromethane to petroleum ether is 1: 6.
According to the perfluorobutyl substituent of the dithiophene pyrrolopyrrole-dione, isoindigo and thiophene isoindigo, the compound has good solubility by introducing branched-chain alkane or straight-chain alkane with 8-16 carbon atoms as a side group; compared with a compound without perfluoroalkyl substitution, the compound has better air stability, the LUMO energy level of the compound is reduced, the injection and the transmission of electrons are facilitated, and the maximum absorption wavelength of the compound is in the visible light field and has potential application prospect in the fields of Organic Field Effect Transistors (OFET) and organic solar cells (OPV).
Therefore, the invention also protects the application of the perfluorobutyl substitutes of the dithiophene pyrrolopyrrole dione, isoindigo and thiophene isoindigo in the preparation of organic semiconductor materials or organic field effect transistors or organic solar cell materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) the dithiophene pyrrolopyrrole diketone, the isoindigo and the perfluorobutyl substituent of the thiofuran isoindigo are synthesized by the method, have good solubility and are easy to dissolve in organic solvents such as dichloromethane, normal hexane and the like. Compared with a compound which is not substituted by perfluoroalkyl, the F-H bond is formed between the fluoroalkyl chain and the alkyl chain, so that the entry of water and oxygen molecules is prevented, the compound has better air stability, the LUMO and HOMO energy levels of the compound are reduced, the injection and transmission of electrons are facilitated, and the maximum absorption wavelength of the compound is in the visible light field and has potential application prospect in the fields of Organic Field Effect Transistors (OFET) and organic solar cells (OPV).
(2) The perfluorobutyl substitutes of the dithienophenepyrrolopyrrole dione, isoindigo and thienylisoindigo have the advantages of simple synthesis method, low cost and relatively high yield, eliminates the harm of using heavy metal catalysts, reduces the generation of toxic by-products and is beneficial to purification.
Drawings
FIG. 1 is a chemical reaction equation for the preparation of perfluorobutyl substituents of dithienophenepyrrolopyrrole diones, isoindigo and thienylisoindigo of the present invention.
FIG. 2 is a drawing showing the preparation of Compound (III) in example 11H NMR spectrum.
FIG. 3 is a UV absorption curve of compound (III) in example 1.
FIG. 4 is a cyclic voltammogram of the compound (III) in example 1.
FIG. 5 is a drawing showing the preparation of Compound (VI) in example 21H NMR spectrum.
FIG. 6 is a UV absorption curve of Compound (VI) in example 2.
FIG. 7 is a cyclic voltammogram of compound (VI) in example 2.
FIG. 8 is a drawing showing the preparation of Compound (X) in example 31H NMR spectrum.
FIG. 9 is a UV absorption curve of Compound (X) in example 3.
FIG. 10 is a cyclic voltammogram of the compound (X) in example 3.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The invention adopts AVANCE III 400M type liquid nuclear magnetic resonance spectrometer manufactured by Bruker company of Switzerland to detect products to obtain 1H NMR and 13C NMR spectrograms, and solvents are deuterated chloroform (CDCl3) and deuterated dichloromethane (CD)2Cl2) Tetramethylsilane (TMS) was used as an internal standard. The experiment was characterized using a solariX mass analysis flight mass spectrometer (Maldi-TOF) from Bruker, SwitzerlandMolecular weight, ultraviolet absorption spectrum of the product was measured by using UV-3600 type ultraviolet-visible spectrophotometer of Shimadzu corporation, a quartz cuvette of 1X 1cm was used as a sample cell, and CHI620E electrochemical analyzer of Shanghai Chenghua apparatus Co.
The chemical reaction equation for the preparation of perfluorobutyl substituents of dithienopyrrolopyrrole diones, isoindigo and thienylisoindigo in the following embodiment of the invention is shown in FIG. 1. Wherein R is a branched or straight chain alkane of 8-16C, such as isooctyl.
Example 1
A preparation method of perfluorobutyl substituent of pyrrolopyrroledione comprises the following steps:
(1) 29g of potassium tert-butoxide are added to a three-necked round-bottomed flask, degassed initially and then flushed with nitrogen three times in succession, followed by 179mL of tert-amyl alcohol and stirring for 2h at 110 ℃. Then 20mL of 3-cyanothiophene was added dropwise with stirring for 45min, and 9.4mL of dimethyl succinate and 29mL of tert-amyl alcohol solution were added dropwise with stirring via a dropping funnel and stirring was continued for 3 h. After the reaction solution was cooled to 80 ℃, 108mL of methanol and 29mL of deionized water were added and stirred for 45min, and after the solution was cooled to room temperature, 57mL of hydrochloric acid and 287mL of methanol were added and stirred for 45 min. Filtering the treated reaction solution, washing the filter residue by using 72mL of methanol to obtain a compound (I), wherein the mass of the obtained compound is 9.54g, and the yield is 16.3%; the chemical reaction equation is as follows:
Figure GDA0002541930940000091
(2) 1.024g of Compound (I), 2.7642g of potassium carbonate and 4.2991g of 18-crown ether 6 were charged in a round-bottom flask, initially degassed and then purged with nitrogen three times in succession, then 20mL of N, N-Dimethylformamide (DMF) were added, stirred and then 2.84mL of bromoisooctane were added and reacted at 120 ℃ for 12 hours. Distilling the obtained solution under reduced pressure, purifying with chromatography column at the ratio of dichloromethane to petroleum ether of 1:3 to obtain compound (II) with a mass of about 1.52g and a yield of 72%; the chemical reaction equation is as follows:
Figure GDA0002541930940000092
(3) 50mg of compound (II) and 90.9mg of copper nanopowder were added to a round-bottomed flask, initially degassed and then charged with nitrogen gas three times in succession, then 2mL of dimethyl sulfoxide (DMSO) was added, stirred, and then 132mg of perfluoroiodobutane was added and reacted at 120 ℃ for 3 hours. Distilling the obtained solution under reduced pressure, purifying with chromatography column at the ratio of dichloromethane to petroleum ether of 1:5 to obtain compound (III) with mass of about 10.2mg and yield of 14.4%; the chemical reaction equation is as follows:
Figure GDA0002541930940000101
FIG. 2 is a drawing showing a method for producing the compound (III)1H NMR spectrum, and the synthesized compound can be proved to be the structure (III) through a nuclear magnetic resonance hydrogen spectrum; FIG. 3 is a graph showing the ultraviolet absorption spectrum of compound (III), from which it can be seen that the maximum absorption wavelength of the synthesized compound (III) is 551nm, which is in the visible light range; FIG. 4 is a cyclic voltammogram of the compound (III), and the LUMO level of the compound (III) is-3.30 eV and the HOMO level is-5.24 eV.
Example 2
A preparation method of perfluorobutyl substituent of isoindigo comprises the following steps:
(1) 3.7754g of isatin, 3.4472g of 2-indolone and 1mL of hydrochloric acid are added into a round-bottom flask, then 150mL of acetic acid is added, stirring is carried out, and reaction is carried out for 12 hours at 115 ℃; filtering the reacted solution, and washing filter residue by using methanol, water, a sodium bicarbonate solution and pentane to obtain a solid compound (IV), wherein the mass of the compound is 4.8537g, and the yield is 79%; the chemical reaction equation is as follows:
Figure GDA0002541930940000102
(2) 1.5g of Compound (IV) and 7.905g of potassium carbonate were charged in a round-bottomed flask, initially degassed and then purged with nitrogen three times in succession, then 30ml of N-Dimethylformamide (DMF) was added, stirred, and then 2.76g of bromoisooctane was added and reacted at 100 ℃ for 24 hours. Distilling the obtained solution under reduced pressure, purifying by a chromatographic column, eluting with dichloromethane and petroleum ether at a ratio of 1:3, and distilling under reduced pressure to obtain compound (V), wherein the mass of the compound is 2.56g, and the yield is 92%; the chemical reaction equation is as follows:
Figure GDA0002541930940000111
(3) 50mg of compound (V) and 163.4mg of copper nanopowder were added to a round-bottomed flask, initially degassed and then charged with nitrogen gas three times in succession, then 2mL of dimethyl sulfoxide (DMSO) was added, stirred, and then 284.8mg of perfluoroiodobutane was added and reacted at 120 ℃ for 5 hours. Distilling the obtained solution under reduced pressure, purifying with chromatography column at a ratio of dichloromethane to petroleum ether of 1:5 to obtain compound (VI) with mass of 18mg and yield of 26%; the chemical reaction equation is as follows:
Figure GDA0002541930940000112
FIG. 5 is a drawing of Compound (VI)1H NMR spectrum, and the synthesized compound can be proved to be the structure (VI) through nuclear magnetic resonance hydrogen spectrum; FIG. 6 is a graph showing the ultraviolet absorption spectrum of compound (VI), from which it can be seen that the synthesized compound (VI) has a maximum absorption wavelength of 500nm in the visible light range; FIG. 7 is a cyclic voltammogram of compound (VI), which was calculated from the curve to give compound (VI) having a LUMO level of-3.69 eV and a HOMO level of-5.53 eV.
Example 3
A preparation method of perfluorobutyl substituent of thiophene isoindigo comprises the following steps:
(1) adding 0.2g of cuprous iodide and 5.6g of potassium carbonate into a round-bottom flask, beginning degassing, then introducing nitrogen, continuing for three times, then adding 10mL of N-Dimethylformamide (DMF), stirring, then adding 2mL of 3-bromothiophene, 5mL of isooctylamine and 0.74g of 2-isobutyrylcyclohexanone, reacting for 12 hours at 120 ℃, distilling the obtained solution under reduced pressure, then passing through a flash chromatography column, and eluting with dichloromethane to obtain 3-secondary aminothiophene; adding 0.75mL of oxalyl chloride into a round-bottom flask, adding 25mL of dichloromethane, adding 1.9939g of 3-secondary aminothiophene and 11mL of dichloromethane solution and 5.71mL of triethylamine and 40mL of dichloromethane solution at 0 ℃ into the round-bottom flask in sequence dropwise, stirring, reacting at room temperature for 12h, distilling the obtained solution under reduced pressure, purifying by a chromatographic column, and eluting with ethyl acetate: the ratio of petroleum ether is 1:8, and the compound (VIII) is obtained by reduced pressure distillation, the mass of the compound is 515.7mg, and the yield is 9.7%; the chemical reaction equation is as follows:
Figure GDA0002541930940000121
(2) 515.7mg of Compound (VIII) and 393.5mg of Lawson's reagent were added to a round-bottomed flask, initially degassed and then purged with nitrogen three times in succession, 10mL of o-xylene was added, stirred and reacted at 60 ℃ for 3 hours. Distilling the obtained solution under reduced pressure, purifying with chromatography column at the ratio of dichloromethane to petroleum ether of 1:3, and distilling under reduced pressure to obtain compound (IX) with mass of 223.1mg and yield of 46.0%; the chemical reaction equation is as follows:
Figure GDA0002541930940000122
(3) 223.1mg of compound (IX), 430.1mg of copper nanopowder was added to the round bottom flask, degassing was started and then nitrogen gas was charged, three times in succession, then 9mL of dimethyl sulfoxide (DMSO) was added, stirring was performed, then 620.0mg of perfluoroiodobutane was added, and reaction was carried out at 120 ℃ for 4 h. Distilling the obtained solution under reduced pressure, purifying with chromatography column at a ratio of dichloromethane to petroleum ether of 1:5 to obtain compound (X) with mass of 96mg and yield of 29%; the chemical reaction equation is as follows:
Figure GDA0002541930940000131
FIG. 8 is a drawing showing a scheme for preparing a compound (X)1H NMR spectrum, and the synthesized compound can be proved to be the structure (X) by a nuclear magnetic resonance hydrogen spectrum; FIG. 9 is a graph showing an ultraviolet absorption spectrum of compound (X), from which it can be seen that the maximum absorption wavelength of the synthesized compound (X) is 557nm, which is in the visible light range; FIG. 10 is a cyclic voltammogram of compound (X), and the LUMO level of compound (VI) was-3.92 eV and the HOMO level was-5.51 eV as calculated from the graph.

Claims (4)

1. A preparation method of a perfluorobutyl substituted compound is characterized by comprising the following steps:
s1, under the protection of nitrogen, adding cuprous iodide and potassium carbonate into a reaction vessel, then adding a solvent and stirring, finally adding 3-bromothiophene, 2-isobutyrylcyclohexanone and aminoalkane for reaction, after the reaction is finished, treating, continuously adding oxalyl chloride, triethylamine and the solvent for reaction, and after the reaction is finished, treating to obtain a compound (VIII), wherein the chemical reaction equation is as follows:
Figure FDA0002933119500000011
s2, adding the compound (VIII) and a Lawson reagent into a reaction vessel under the protection of nitrogen, then adding a solvent, stirring, reacting, and processing after the reaction is finished to obtain a compound (IX), wherein the chemical reaction equation is as follows:
Figure FDA0002933119500000012
s3, under the protection of nitrogen, adding the compound (IX) and the nano copper powder into a reaction container, then adding a solvent, stirring, finally adding perfluoroiodobutane to react, and after the reaction is finished, carrying out treatment to obtain a perfluorobutyl substituted compound (X), wherein the chemical reaction equation is as follows:
Figure FDA0002933119500000013
wherein R is alkane with 8-16C.
2. The process for preparing a perfluorobutyl-substituted compound according to claim 1, wherein R is isooctyl.
3. The process for producing a perfluorobutyl-substituted compound according to claim 1, wherein the reaction molar concentration of the compound (IX) is 0.05 to 0.06 mol/L.
4. The method for preparing a perfluorobutyl-substituted compound according to claim 1, wherein the molar ratio of the compound (IX), perfluoroiodobutane and the nano-copper powder is 1:4: 15.
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