CN111606921A - Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof - Google Patents

Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof Download PDF

Info

Publication number
CN111606921A
CN111606921A CN202010561358.7A CN202010561358A CN111606921A CN 111606921 A CN111606921 A CN 111606921A CN 202010561358 A CN202010561358 A CN 202010561358A CN 111606921 A CN111606921 A CN 111606921A
Authority
CN
China
Prior art keywords
dithiophene
benzo
reaction
compound according
molar ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010561358.7A
Other languages
Chinese (zh)
Inventor
秦瑜
李旭
刘海涛
张陆军
刘赣东
张淼淼
朱向珺
杨霞
梁雨涛
张淑芳
王金良
李玉宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry Henan Academy of Sciences Co Ltd
Original Assignee
Institute of Chemistry Henan Academy of Sciences Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry Henan Academy of Sciences Co Ltd filed Critical Institute of Chemistry Henan Academy of Sciences Co Ltd
Priority to CN202010561358.7A priority Critical patent/CN111606921A/en
Publication of CN111606921A publication Critical patent/CN111606921A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention provides a benzo [1,2-b:4,5-b']The dithiophene compound has a structure shown as a formula (I), wherein R1is-CnH2n+1And R is2is-Cn+2H2n+5And n is an even number of 1-20. The invention also provides a benzo [1,2-b:4,5-b']A process for the preparation of dithiophene compounds. In the compound system provided by the invention, pi electrons have a larger delocalization range, so that better pi-pi stacking among molecules can be realized, the charge transmission is facilitated, and the open-circuit voltage and the photoelectric conversion efficiency of the organic micromolecule solar cell based on the compound can be effectively improved. And the preparation method is simple and efficient and has high yield.
Figure DDA0002546406840000011

Description

Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a compound based on benzo [1,2-b:4,5-b' ] dithiophene and a preparation method thereof.
Background
The organic small molecule solar cell is one of the important research fields of the organic solar cell, which takes an organic small molecule material as an active material, and compared with a polymer material, the small molecule material has the following advantages: (1) the material has a determined structure and molecular weight, and does not have the problem of difference in material properties of different batches, (2) the design and regulation space of molecules is large, the synthesis is relatively simple, (3) the energy level and band gap are easy to effectively regulate and control, and (4) the carrier mobility is relatively high, see related documents: ZHao w, Qian D, Zhang S, et al, Fullere-free polymer solar cells with over 11% efficacy and excellent thermal stability Adv Mater,2016,28: 4734-; meanwhile, through continuous optimization of molecular structures in recent years, organic small-molecule solar cells have obtained materials with good light absorption and improved solubility, and meanwhile, the improvement of device processes has led to significant improvement of device efficiency of such materials, and has shown great development potential.
The synthesis of new donor materials is one of the important ways to improve the efficiency of the cell, the synthesis of materials with narrow band gaps is beneficial to better absorbing sunlight, and the main methods for reducing the band gaps of organic semiconductor materials are as follows: (1) utilizing intramolecular charge transfer between intramolecular donor-acceptor units, (2) reducing aromaticity of conjugated backbones, in view of this, many researchers have manipulated material energy levels by designing and synthesizing materials containing D-a units, and some researchers have designed and synthesized small molecule materials containing a-D-a and D1-a-D2-a-D1 for organic small molecule solar cells, see the relevant literature: lin Y, Li Y, Zhan X. Smallmolar organic semiconductors for high-efficiency organic photovoltiacs. chem Soc Rev,2012,41: 4245-.
Benzo [1,2-b:4,5-b' ] dithiophene (BDT) has received much attention as a synthesis intermediate because of its large conjugated system, good symmetry planarity and excellent charge transport properties, and has been used by researchers in the synthesis of organic photoelectric materials, see the relevant literature: zhou J, Zuo Y, Wan X, et al, solution-processed and high-performance organic cells using small molecules with a benzodithiophane unit.J Am Chem Soc,2013,135:8484-8487, therefore, the development of small molecule materials with D-A structure based on benzo [1,2-b:4,5-b' ] dithiophene (BDT) has important economic value and social significance.
Disclosure of Invention
In order to solve the defects, the invention provides a compound based on benzo [1,2-b:4,5-b '] dithiophene and a preparation method thereof, wherein pi electrons in a compound system have a larger delocalization range, so that pi-pi stacking among molecules can be better, charge transmission is facilitated, the open-circuit voltage and the photoelectric conversion efficiency of an organic micromolecule solar cell based on the compound can be effectively improved, and the method for preparing the compound of benzo [1,2-b:4,5-b' ] dithiophene is simple, efficient and high in yield.
The invention provides a compound based on benzo [1,2-b:4,5-b' ] dithiophene (BDT), which has a structure shown in a formula (I),
Figure BDA0002546406820000021
in the formula (I), R1is-CmH2m+1And R is2is-CnH2n+1Wherein n is m +2, and m is an even number selected from 2-20 natural numbers.
Preferably, said R is1Is selected from-C2H5、-C4H9or-C6H13Corresponding to said R2Is selected from-C4H9、-C6H13or-C8H17。
The second object of the present invention is to provide a method for preparing a benzo [1,2-b:4,5-b' ] dithiophene-based compound, comprising the steps of:
s1, uniformly dispersing thiophene in tetrahydrofuran in an inert gas atmosphere, adding n-butyl lithium at-78 ℃, uniformly mixing, adding alkyl bromide, uniformly mixing, heating to 60 ℃, reacting overnight, and quenching to obtain alkylthiophene;
s2, uniformly dispersing the alkylthiophene prepared in S1 in tetrahydrofuran in an inert gas atmosphere, adding n-butyllithium at 0 ℃, heating to 50 ℃, adding benzo [1,2-b:4,5-b '] dithiophene-4, 8-diketone, uniformly mixing, cooling to room temperature, continuously adding hydrochloric acid solution containing stannous chloride for reaction for 1.5-2 h, and carrying out quenching treatment to obtain alkylthienyl-benzo [1,2-b:4,5-b' ] dithiophene;
s3, uniformly dispersing alkylthienyl-benzo [1,2-b:4,5-b '] dithiophene prepared by S2 in tetrahydrofuran at-78 ℃ in an inert gas atmosphere, adding N-butyllithium for reaction for 2 hours, continuously adding N, N' -Dimethylformamide (DMF), mixing for reaction for 2.5 hours, and carrying out quenching treatment to prepare an aldehyde group substituted intermediate;
s4, uniformly dispersing the aldehyde group substituted intermediate prepared from the 3- (dicyanomethylene) indone and the S3 into chloroform in an inert gas atmosphere, and adding pyridine for reflux reaction overnight to obtain the compound based on benzo [1,2-b:4,5-b' ] dithiophene.
Preferably, in S1, the molar ratio of thiophene to brominated alkane is 1: 1.2.
Preferably, in S2, the molar ratio of the alkyl-thiophene to benzo [1,2-b:4,5-b' ] dithiophene-4, 8-dione is 3: 1.
Preferably, in S3, the molar ratio of alkylthienyl-benzo [1,2-b:4,5-b' ] dithiophene to dimethylformamide is 1: 10.
Preferably, in S4, the molar ratio of aldehyde substituted intermediate to 3- (dicyanomethylene) indolone is 1: 5.
Preferably, in S4, the molar ratio of the aldehyde substituted intermediate to pyridine is 1: 7.
The third purpose of the invention is to provide an application of the compound based on benzo [1,2-b:4,5-b' ] dithiophene in a solar cell.
Compared with the prior art, the invention has the following beneficial effects:
the derivative provided by the invention is based on benzo [1,2-b:4,5-b '] dithiophene (BDT), thiophene rings are introduced in the orthogonal direction of BDT units, and the obtained compound based on benzo [1,2-b:4,5-b' ] dithiophene has a larger delocalization range of pi electrons in the compound system, can enable better pi-pi stacking among molecules, is favorable for charge transmission, and simultaneously increases a conjugated structure, thereby effectively increasing the absorption of a spectrum.
By introducing the electron-withdrawing unit into the molecular structure, a push-pull electron structure (D-A) is formed in the molecule, and intramolecular charge transfer is formed, and the D-A structure adjusts the band gap of the molecule, so that the spectrum absorbs red shift, and the open-circuit voltage and the photoelectric conversion efficiency of the organic micromolecule solar cell based on the compound are improved.
The compound provided by the invention has the advantages of rich raw material sources, simple synthetic route and high yield.
Drawings
FIG. 1 is a hydrogen spectrum of the BMIBDT-ThEH compound prepared in example 1.
FIG. 2 is a hydrogen spectrum of the BMIBDT-ThBO compound obtained in example 2.
FIG. 3 is a hydrogen spectrum of the BMIBDT-ThHD compound obtained in example 3.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following embodiments are further described, but the present invention is not limited to the following embodiments.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The invention relates to a compound based on benzo [1,2-b:4,5-b' ] dithiophene, which is characterized in that the compound has a structure shown in a formula (I),
Figure BDA0002546406820000051
in the formula (I), R1is-CmH2m+1And R is2is-CnH2n+1Wherein n is m +2, and m is an even number selected from 2-20 natural numbers.
Specific examples of the benzo [1,2-b:4,5-b' ] dithiophene-based compounds of the present invention are shown below:
Figure BDA0002546406820000052
the reaction scheme of the preparation method of the benzo [1,2-b:4,5-b' ] dithiophene-based compound provided by the invention is as follows:
Figure BDA0002546406820000061
in the formulae (II) to (IV), R1is-CmH2m+1And R is2is-CnH2n+1In the formula (VI), R is Cm+nAnd (c) an alkyl group, wherein n is m +2, and m is an even number selected from 2-20 natural numbers.
Example 1
A compound based on benzo [1,2-b:4,5-b' ] dithiophene has a structure shown in formula (I),
Figure BDA0002546406820000071
the preparation method of the benzo [1,2-b:4,5-b' ] dithiophene-based compound comprises the following steps:
(1) synthesis of 2- (2-ethylhexyl) thiophene:
Figure BDA0002546406820000072
thiophene (5.00g,59.43mmol) was dissolved in 100mL of anhydrous THF under an argon atmosphere, cooled to-78 deg.C, n-butyllithium (65.37mmol,1.6M) was added dropwise, stirred for one hour, 2-ethylbromohexane (13.78g,71.32mmol) was added dropwise to the above solution, stirring was continued for one hour at-78 deg.C, heated to 60 deg.C and stirred overnight. The system was quenched with 20mL of cold water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, evaporated to dissolve under reduced pressure, and the crude product was analyzed by column chromatography to give a colorless oil (9.63g, yield: 82.4%);
(2) synthesis of 4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (BDTTT-EH):
Figure BDA0002546406820000081
2- (2-ethylhexyl) thiophene (3.48g,17.7mmol) was dissolved in 30mL of anhydrous THF under an argon atmosphere, stirred at 0 ℃ for fifteen minutes, n-butyllithium (1.6M,12.72mL,20.36mmol) was added dropwise, the system was heated to 50 ℃ and stirred for one hour, and then benzo [1,2-b:4,5-b']Adding dithiophene-4, 8-dione (1.3g,5.9mmol) into the reaction solution, stirring at 50 deg.C for one hour, cooling, and adding SnCl2·2H2O (10.65g,47.2mmol) in 10% hydrochloric acid solution (18.9mL) is added into the reaction system, stirred for 1.5 hours, then the reaction solution is poured into ice water, extracted by petroleum ether, the solvent is evaporated under reduced pressure after the organic phase is dried, and the crude product is purified by column chromatography to obtain light yellow oily matter (2.44g, yield: 71.2%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):7.65(d,J＝6.0Hz,2H),7.46(d,J＝5.6Hz,2H),7.30(d,J＝3.2Hz,2H),6.89(d,J＝3.2Hz,2H),2.86(d,J＝6.8Hz,4H),1.72–1.65(m,2H),1.47-1.26(br,16H),0.97-0.89(m,12H).
(3) synthesis of 4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene-2, 6-dicarboxaldehyde (BDTTT-EH-CHO):
Figure BDA0002546406820000082
under argon atmosphere, adding n-butyllithium (2.5M,2.28mL,5.7mmol) into BDTTT-EH (1.5g,2.59mmol) in anhydrous tetrahydrofuran (50mL) at-78 ℃, continuing to stir at the temperature for 1.5 hours, dropwise adding anhydrous DMF (2.0mL), continuing to stir the reaction system for 2.5 hours, quenching with an ammonium chloride solution after the reaction is finished, extracting with dichloromethane, drying an organic phase, evaporating the solvent under reduced pressure, and performing column chromatography on a crude product to obtain an orange-red solid (1.37g, yield: 86%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):10.1(s,2H),8.37(s,2H),7.34(d,J＝3.6Hz,2H),6.95(d,J＝3.6Hz,2H),2.89(d,J＝6.8Hz,4H),1.73-1.71(m,2H),1.69-1.24(br,16H),0.98-0.91(m,12H).13C NMR(100MHz,CDCl3)(ppm):184.78 147.53145.27 141.32 137.94 134.93 128.75 127.69 125.96 41.49 34.26 28.9 25.7 23.0314.18 10.89.
(4) synthesis of benzo [1,2-b:4,5-b' ] dithiophene-based Compound 1 (BMIBDT-ThEH):
Figure BDA0002546406820000091
BDTTT-EH-CHO (1.35g,2.04mmol), 3- (dicyanomethylene) indolone (1.97g,10.2mmol), pyridine (10mL) and chloroform (150mL) were added to a three-necked flask under an argon atmosphere, the system was heated to reflux overnight, after completion of the reaction, the reaction solution was poured into 150mL of methanol with cooling, and the resulting solid was filtered and washed with hot isopropanol to obtain a pure product (1.89g, yield: 94%).
1The H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):8.86(s,2H),8.72-8.70(m,2H),8.43(s,2H),8.0-7.98(m,2H),7.83-7.78(m,4H),7.44(d,J＝3.2Hz,2H),7.01(d,J＝3.2Hz,2H),2.93(d,J＝6.8Hz,4H),1.78-1.73(m,2H),1.54-1.26(br,16H),1.02-0.94(m,12H).13C NMR(100MHz,CDCl3)(ppm):194.01 147.78 144.52 140.77 137.65 137.16133.96 131.90 129.64 127.27 126.57 124.51 123.64 120.90 113.92 84.36 41.2234.20 28.73 25.56 23.03 14.02 10.80.
example 2
A compound based on benzo [1,2-b:4,5-b' ] dithiophene has a structure shown in formula (I),
Figure BDA0002546406820000101
the preparation method of the benzo [1,2-b:4,5-b' ] dithiophene-based compound comprises the following steps:
(1) synthesis of 2- (2-butyloctyl) thiophene:
Figure BDA0002546406820000102
thiophene (5.00g,59.43mmol) was dissolved in 100mL of anhydrous THF under argon atmosphere, cooled to-78 deg.C, n-butyllithium (65.37mmol,1.6M) was added dropwise, stirred for one hour, 2-butyl octyl bromide (17.78g,71.32mmol) was added dropwise to the above solution, stirred for one hour at-78 deg.C, heated to 60 deg.C and stirred overnight. The system was quenched with 20mL of cold water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, evaporated to dissolve under reduced pressure, and the crude product was analyzed by column chromatography to give a colorless oil (11.85g, yield: 79%);
(2) synthesis of 4, 8-bis (5- (2-butyloctyl) thienyl-2-) -benzodithiophene (BDTTT-BO):
Figure BDA0002546406820000111
2-(2-Butyloctyl) thiophene (5.16g,20.43mmol) was dissolved in 30mL of anhydrous THF, stirred at 0 ℃ for fifteen minutes, n-butyllithium (1.6M,9.4mL,23.5mmol) was added dropwise, and the system was heated to 50 ℃ and stirred for one hour, followed by benzo [1,2-b:4,5-b']Adding dithiophene-4, 8-dione (1.5g,6.8mmol) into the reaction solution, stirring at 50 deg.C for one hour, cooling, and adding SnCl2·2H2O (12.27g,54.4mmol) in 10% hydrochloric acid solution (21.8mL) is added into the reaction system, stirred for 1.5 hours, then the reaction solution is poured into ice water, extracted by petroleum ether, the solvent is evaporated under reduced pressure after the organic phase is dried, and the crude product is purified by column chromatography to obtain light yellow oily matter (3.24g, yield: 69%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):7.65(d,J＝6.0Hz,2H),7.46(d,J＝5.6Hz,2H),7.30(d,J＝3.2Hz,2H),6.89(d,J＝3.2Hz,2H),2.86(d,J＝6.8Hz,4H),1.79–1.72(m,2H),1.45-1.23(br,32H),0.94-0.85(m,12H).
(3) synthesis of 4, 8-bis (5- (2-butyloctyl) thienyl-2-) -benzodithiophene-2, 6-dicarboxaldehyde (BDTTT-BO-CHO):
Figure BDA0002546406820000112
under argon atmosphere, adding n-butyllithium (2.5M,1.66mL,4.14mmol) into BDTTT-BO (1.3g,1.88mmol) in anhydrous tetrahydrofuran (50mL) at-78 ℃, continuing to stir at the temperature for 1.5 hours, dropwise adding anhydrous DMF (1.45mL), continuing to stir the reaction system for 2.5 hours, quenching with an ammonium chloride solution after the reaction is finished, extracting with dichloromethane, drying an organic phase, evaporating the solvent under reduced pressure, and performing column chromatography on a crude product to obtain an orange solid (1.17g, yield: 84%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):10.1(s,2H),8.37(s,2H),7.34(d,J＝3.6Hz,2H),6.95(d,J＝3.6Hz,2H),2.88(d,J＝6.8Hz,4H),1.74-1.72(m,2H),1.57-1.26(br,32H),0.97-0.83(m,12H).13C NMR(100MHz,CDCl3)(ppm):184.75 147.52145.28 141.33 137.94 134.92 128.74 127.69 125.97 40.05 34.68 33.37 33.0029.69 28.87 26.63 23.03 22.70 14.19 14.15.
(4) synthesis of Compound 2 of benzo [1,2-b:4,5-b' ] dithiophene (BMIBDT-ThBO):
Figure BDA0002546406820000121
BDTTT-BO-CHO (0.82g,1.1mmol), 3- (dicyanomethylene) indolone (1.06g,5.5mmol), pyridine (5.5mL) and chloroform (100mL) were added to a three-necked flask under an argon atmosphere, the system was heated to reflux overnight, after the reaction was completed, the reaction solution was poured into 150mL of methanol under cooling, the obtained solid was filtered and washed with hot isopropanol to obtain a pure product (1.16g, yield: 96%).
1The H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):8.81(s,2H),8.68-8.67(m,2H),8.38(s,2H),8.0-7.98(m,2H),7.80-7.78(m,4H),7.44(d,J＝3.2Hz,2H),7.0(d,J＝3.2Hz,2H),2.93(d,J＝6.8Hz,4H),1.80-1.79(m,2H),1.48-1.26(br,32H),0.95-0.83(m,12H).13C NMR(100MHz,CDCl3)(ppm):194.00 147.72 144.51 140.72 137.64 137.17133.92 131.90 129.65 127.24 126.55 124.50 123.63 120.89 113.90 84.35 40.0434.65 33.34 33.00 29.65 28.85 26.60 23.00 22.69 14.14 14.10.
example 3
A compound based on benzo [1,2-b:4,5-b' ] dithiophene has a structure shown in formula (I),
Figure BDA0002546406820000131
the preparation method of the benzo [1,2-b:4,5-b' ] dithiophene-based compound comprises the following steps:
(1) synthesis of 2- (2-hexyldecyl) thiophene:
Figure BDA0002546406820000132
thiophene (5.00g,59.43mmol) was dissolved in 100mL of anhydrous THF under argon atmosphere, cooled to-78 deg.C, n-butyllithium (65.37mmol,1.6M) was added dropwise, stirred for one hour, 2-hexylbromodecane (21.77g,71.32mmol) was added dropwise to the above solution, stirring was continued for one hour at-78 deg.C, heated to 60 deg.C and stirred overnight. The system was quenched with 20mL of cold water, extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, evaporated to dissolve under reduced pressure, and the crude product was analyzed by column chromatography to give a colorless oil (14.48g, yield: 79%);
(2) synthesis of 4, 8-bis (5- (2-hexyldecyl) thienyl-2-) -benzodithiophene (BDTTT-HD):
Figure BDA0002546406820000133
2- (2-hexyldecyl) thiophene (9.52g,30.9mmol) was dissolved in 60mL of anhydrous THF under an argon atmosphere, stirred at 0 ℃ for fifteen minutes, n-butyllithium (1.6M,22.21mL,35.54mmol) was added dropwise, the system was heated to 50 ℃ and stirred for one hour, and then benzo [1,2-b:4,5-b']Dithiophene-4, 8-dione (2.27g,10.3mmol) was added to the reaction solution, stirring was continued at 50 ℃ for one hour, and after cooling, SnCl was added2·2H2O (18.6g,82.4mmol) in 10% hydrochloric acid solution (33mL) is added into the reaction system, the mixture is stirred for 1.5 hours, then the reaction solution is poured into ice water, petroleum ether is used for extraction, the solvent is evaporated under reduced pressure after the organic phase is dried, and the crude product is purified by column chromatography to obtain light yellow oily matter (5.86g, the yield: 70.9%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):7.65(d,J＝6.0Hz,2H),7.45(d,J＝5.6Hz,2H),7.30(d,J＝3.2Hz,2H),6.89(d,J＝3.2Hz,2H),2.86(d,J＝6.8Hz,4H),1.79–1.70(m,2H),1.44-1.30(br,48H),0.90-0.87(m,12H).
(3) synthesis of 4, 8-bis (5- (2-hexyldecyl) thienyl-2-) -benzodithiophene-2, 6-dicarboxaldehyde (BDTTT-HD-CHO):
Figure BDA0002546406820000141
under argon atmosphere, adding n-butyllithium (2.5M,1,96mL,4.91mmol) into BDTTT-HD (1.77g,2.23mmol) in anhydrous tetrahydrofuran (50mL) at-78 ℃, continuing to stir at the temperature for 1.5 hours, dropwise adding anhydrous DMF (1.72mL), continuing to stir the reaction system for 2.5 hours, quenching with an ammonium chloride solution after the reaction is finished, extracting with dichloromethane, drying an organic phase, evaporating the solvent under reduced pressure, and performing column chromatography on a crude product to obtain an orange solid (1.58g, yield: 82%);
1the H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):10.1(s,2H),8.37(s,2H),7.34(d,J＝3.6Hz,2H),6.94(d,J＝3.6Hz,2H),2.88(d,J＝6.8Hz,4H),1.74-1.71(m,2H),1.56-1.30(br,48H),0.97-0.85(m,12H).13C NMR(100MHz,CDCl3)(ppm):184.72 147.52145.28 141.33 137.94 134.93 134.12 128.74 127.69 125.96 40.07 34.68 33.3531.93 31.91 30.30 29.66 29.36 29.65 26.62 22.70 14.14.
(4) synthesis of benzo [1,2-b:4,5-b' ] dithiophene-based Compound 3 (BMIBDT-ThHD):
Figure BDA0002546406820000151
BDTTT-HD-CHO (1.5g,1.75mmol), 3- (dicyanomethylene) indolone (1.69g,8.73mmol), pyridine (8.75mL) and chloroform (130mL) were added to a three-necked flask under an argon atmosphere, the system was heated to reflux overnight, after the reaction was completed, the reaction solution was poured into 150mL of methanol with cooling, the obtained solid was filtered and washed with hot isopropanol to obtain a pure product (2.02g, yield: 95.5%).
1The H NMR spectrum analysis result is as follows:1H NMR(400MHz,CDCl3)(ppm):8.81(s,2H),8.71-8.69(m,2H),8.42(s,2H),8.0-7.98(m,2H),7.81-7.79(m,4H),7.45(d,J＝3.2Hz,2H),7.0(d,J＝3.2Hz,2H),2.93(d,J＝6.8Hz,4H),1.80-1.79(m,2H),1.42-1.26(br,48H),0.90-0.83(m,12H).13C NMR(100MHz,CDCl3)(ppm):194.00 147.71 144.50 140.73 137.65 137.18133.90 131.89 129.64 127.25 126.56 124.49 123.66 120.87 113.89 84.34 40.0634.66 33.34 31.92 31.91 30.29 29.65 29.36 29.64 26.60 22.69 14.10.
the above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of protection is not limited thereto. The equivalents and modifications of the present invention which may occur to those skilled in the art are within the scope of the present invention as defined by the appended claims.

Claims (9)

1. A compound based on benzo [1,2-b:4,5-b' ] dithiophene, characterized by having a structure as shown in formula (I),
Figure FDA0002546406810000011
in the formula (I), R1is-CmH2m+1And R is2is-CnH2n+1Wherein n is m +2, and m is an even number selected from 2-20 natural numbers.
2. Benzo [1,2-b:4,5-b ] based according to claim 1']A compound of dithiophene, wherein R is1Is selected from-C2H5、-C4H9or-C6H13Corresponding to said R2Is selected from-C4H9、-C6H13or-C8H17。
3. A process for the preparation of benzo [1,2-b:4,5-b' ] dithiophene-based compounds according to claim 1 or 2, characterized in that it comprises the following steps:
s1, uniformly dispersing thiophene in tetrahydrofuran in an inert gas atmosphere, adding n-butyl lithium at-78 ℃, uniformly mixing, adding alkyl bromide, uniformly mixing, heating to 60 ℃, reacting for 12 hours, and quenching to obtain alkylthiophene;
s2, uniformly dispersing the alkylthiophene prepared in S1 in tetrahydrofuran in an inert gas atmosphere, adding n-butyllithium at 0 ℃, heating to 50 ℃, adding benzo [1,2-b:4,5-b '] dithiophene-4, 8-diketone, uniformly mixing, cooling to room temperature, continuously adding hydrochloric acid solution containing stannous chloride for reaction for 1.5-2 h, and carrying out quenching treatment to obtain alkylthienyl-benzo [1,2-b:4,5-b' ] dithiophene;
s3, uniformly dispersing alkylthienyl-benzo [1,2-b:4,5-b' ] dithiophene prepared in S2 in tetrahydrofuran at-78 ℃ in an inert gas atmosphere, adding n-butyllithium for reaction for 2 hours, continuing adding dimethylformamide, mixing for reaction for 2.5 hours, and carrying out quenching treatment to prepare an aldehyde group substituted intermediate;
s4, uniformly dispersing the aldehyde group substituted intermediate prepared from the 3- (dicyanomethylene) indone and the S3 into chloroform in an inert gas atmosphere, and adding pyridine for reflux reaction overnight to obtain the compound based on benzo [1,2-b:4,5-b' ] dithiophene.
4. The method for preparing a benzo [1,2-b:4,5-b' ] dithiophene-based compound according to claim 3, wherein the molar ratio of thiophene to bromoalkane in S1 is 1: 1.2.
5. The method for preparing a benzo [1,2-b:4,5-b '] dithiophene-based compound according to claim 3, wherein the molar ratio of the alkyl-thiophene and benzo [1,2-b:4,5-b' ] dithiophene-4, 8-dione in S2 is 3: 1.
6. The method for preparing benzo [1,2-b:4,5-b ' ] dithiophene-based compound according to claim 3, wherein the molar ratio of alkylthienyl-benzo [1,2-b:4,5-b ' ] dithiophene to N, N ' -dimethylformamide in S3 is 1: 10.
7. The method for preparing benzo [1,2-b:4,5-b' ] dithiophene-based compound according to claim 3, wherein the molar ratio of the aldehyde-substituted intermediate to 3- (dicyanomethylene) indolone in S4 is 1: 5.
8. The method for preparing benzo [1,2-b:4,5-b' ] dithiophene-based compound according to claim 3, wherein the molar ratio of the aldehyde group substitution intermediate to pyridine in S4 is 1: 7.
9. Use of a benzo [1,2-b:4,5-b' ] dithiophene-based compound according to claim 1 or 2 in a solar cell.
CN202010561358.7A 2020-06-18 2020-06-18 Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof Pending CN111606921A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010561358.7A CN111606921A (en) 2020-06-18 2020-06-18 Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010561358.7A CN111606921A (en) 2020-06-18 2020-06-18 Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111606921A true CN111606921A (en) 2020-09-01

Family

ID=72198642

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010561358.7A Pending CN111606921A (en) 2020-06-18 2020-06-18 Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111606921A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943311A (en) * 2021-11-22 2022-01-18 北京航空航天大学 Preparation and application of novel non-fullerene micromolecule

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153189A (en) * 2015-07-20 2015-12-16 中国科学院化学研究所 Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof
WO2017191468A1 (en) * 2016-05-06 2017-11-09 Imperial Innovations Limited Non-fullerene electron acceptors

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153189A (en) * 2015-07-20 2015-12-16 中国科学院化学研究所 Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof
WO2017191468A1 (en) * 2016-05-06 2017-11-09 Imperial Innovations Limited Non-fullerene electron acceptors

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUE JIANG,ET AL.,: "Molecular electron-acceptors based on benzodithiophene for organic photovoltaics", 《TETRAHEDRON LETTERS》 *
中国化学会编著: "《化学学科发展报告》", 31 March 2018 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943311A (en) * 2021-11-22 2022-01-18 北京航空航天大学 Preparation and application of novel non-fullerene micromolecule

Similar Documents

Publication Publication Date Title
CN111647140B (en) Polymeric carbazole derivative cadmium complex and preparation method and application thereof
CN109666033B (en) Conjugated small molecule based on nona-fused heterocycle and preparation method and application thereof
CN108864137B (en) Receptor compound, preparation method and application thereof, and photovoltaic cell containing receptor compound
CN103261368A (en) Novel spirobifluorene compounds
CN108676000B (en) Photosensitive dye with D-D-pi-A structure and taking carbazole and triphenylamine as two-stage electron donors and preparation method and application thereof
CN109096313B (en) Preparation method of trimeric indenyl corrole-porphyrin-fullerene star-shaped compound
CN111393452B (en) Asymmetric thieno-indole nuclear small molecule receptor material and preparation method thereof
CN114195801A (en) Near-infrared organic photoelectric molecular material based on 3-alkoxy-4-cyanothiophene
CN112409323A (en) Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal
CN110452241B (en) Organic small-molecule non-fullerene acceptor material containing spirofluorene group and preparation method and application thereof
CN109912621B (en) Asymmetric naphthalene nucleus small molecule receptor material and preparation method and application thereof
CN111606921A (en) Compound based on benzo [1,2-b:4,5-b' ] dithiophene and preparation method thereof
CN110964040B (en) Benzoxadiazole-based acceptor material and preparation method and application thereof
CN108864143B (en) Asymmetric seven-element fused thiophene and preparation method and application thereof
CN113527285B (en) D-A-pi-A-D fluorescent compound and preparation method thereof
CN113773338B (en) Boron-containing organic free radical compound and preparation method and application thereof
CN109824691A (en) Liquid-crystal compounds and its preparation based on cyclopentadiene 1,4-Dithiapentalene -4- ketone
CN114249758A (en) Dimer based on five-membered aromatic heterocyclic BODIPY and preparation method thereof
CN111057008B (en) D-A type excited proton transfer high-efficiency fluorescent material and preparation method and application thereof
CN114316221A (en) Polythiophene and preparation method and application thereof
CN109776568B (en) Axisymmetric hexahydric bridged naphthalene nucleus micromolecule receptor material and preparation method and application thereof
CN112194612A (en) Synthesis method of photoelectric material intermediate N- (7-bromo-9, 9-dimethylfluorene-2-yl) carbazole
CN109749058B (en) Anthracene bithiophene imide polymer and preparation method and application thereof
CN115626911B (en) Trans-dithienylethylene derivative and preparation method and application thereof
CN111943965A (en) Pyridine imine derivative and 8-hydroxyquinoline derivative cadmium complex dye sensitizer and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination