CN107522720B - Diselenopheno [2,3-b:3',2' -d ] thiophene and preparation method thereof - Google Patents

Diselenopheno [2,3-b:3',2' -d ] thiophene and preparation method thereof Download PDF

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CN107522720B
CN107522720B CN201710619837.8A CN201710619837A CN107522720B CN 107522720 B CN107522720 B CN 107522720B CN 201710619837 A CN201710619837 A CN 201710619837A CN 107522720 B CN107522720 B CN 107522720B
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thiophene
diselenopheno
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李春丽
王�华
吴龙龙
徐婉
方茂鸿
单震
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Henan University
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    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
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Abstract

The invention relates to diselenopheno [2,3-b:3',2' -d ] thiophene and a preparation method thereof, belonging to the technical field of heterocyclic compounds. The diselenopheno [2,3-b:3',2' -d ] thiophene has a structure shown as a formula (1). The diselenopheno [2,3-b:3',2' -d ] thiophene is a novel organic functional material and a construction module of selenothiophene, and lays a foundation for development of organic semiconductor materials with excellent semiconductor performance and construction of selenothiophene.

Description

Diselenopheno [2,3-b:3',2' -d ] thiophene and preparation method thereof
Technical Field
The invention relates to diselenopheno [2,3-b:3',2' -d ] thiophene and a preparation method thereof, belonging to the technical field of heterocyclic compounds.
Background
Thiophene derivatives have attracted extensive attention in the field of organic field effect transistors due to their excellent photoelectric properties, and research on the internal relation and rule between the structure and performance of thiophene derivatives has made remarkable progress. However, since thiophene derivatives are limited in their own structure such as relatively small radius of S atom, low polarizability, etc., further improvement of their performance is under serious examination. The selenium atom has the characteristic of easy polarization and easy electron supply, so that the selenophene derivative has stronger Se.Se interaction between molecules, and the selenophene derivative is reflected on an organic semiconductor material to ensure that the material shows excellent performance. Replacement of part of the sulfur atoms in the bithiophene system with selenium atoms may improve the material arrangement and improve the material properties, such as field effect mobility (1.1 cm) of compound 22V.s) is Compound 1(0.5 cm)2V · s) (k. yamada, t. okamoto, k. kudoh, a. wakamiya, s. Yamaguchi, j. takeya. appl. phys. lett.2007,90,072102 (1-3)). Replacing part of sulfur atoms in the thiophene system with selenium atoms is an effective way to develop organic semiconductor materials with excellent performance.
Figure BDA0001361428000000011
Disclosure of Invention
The invention aims to provide diselenopheno [2,3-b:3',2' -d ] thiophene, which lays a foundation for development of organic semiconductor materials with excellent semiconductor performance and construction of selenothiophene helicene.
The second purpose of the invention is to provide a preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene.
In order to achieve the purpose, the technical scheme of the invention is as follows:
diselenopheno [2,3-b:3',2' -d ] thiophene, having the structure shown in formula (1),
Figure BDA0001361428000000012
the preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene comprises the following steps:
dissolving a compound 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene shown as a formula (2) in an organic solvent, adding trifluoroacetic acid to react for 0.5-1 h, and then quenching to obtain the compound,
Figure BDA0001361428000000021
the preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene is simple and feasible, and the yield of the obtained diselenopheno [2,3-b:3',2' -d ] thiophene is high and can reach 77%.
The organic solvent is trichloromethane or dichloromethane.
The molar ratio of the 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene to the trifluoroacetic acid is 1: 5-10.
10-30 ml of organic solvent is added to every 0.2 mmol of 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene.
The quenching is water quenching or sodium bicarbonate solution quenching.
The sodium bicarbonate solution is a sodium bicarbonate aqueous solution.
The preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene further comprises the following steps: and adding water to wash the reaction solution obtained after quenching, and then separating an aqueous phase and an organic phase.
The preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene also comprises the steps of extracting the separated water phase with trichloromethane and combining the organic phases.
The preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene also comprises the steps of washing, drying, filtering and removing the solvent from the combined organic phase to obtain a crude diselenopheno [2,3-b:3',2' -d ] thiophene product.
The combined organic phases are washed with water, saturated sodium bicarbonate solution and water respectively.
The drying is drying with anhydrous magnesium sulfate.
The 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene is prepared by a preparation method comprising the following steps:
adding 5,5 '-bis (trimethylsilyl) -3,3' -bis selenophene shown as a formula (3) into anhydrous ether under the protection of inert gas, then adding n-BuLi at 0 ℃, reacting for 2h at 0 ℃, and then adding (PhSO) at-78 ℃ under the protection of argon2)2S, raising the temperature to-55 ℃ again, keeping the reaction for 2h, slowly raising the temperature to room temperature, stirring overnight, adding CH at low temperature3Quenching OH, and then separating, washing and drying to obtain the product;
Figure BDA0001361428000000031
the 5,5 '-bis (trimethylsilyl) -3,3' -bisselenophene is prepared by the following steps:
dissolving a compound 4-bromo-2-trimethylsilyl-selenophene shown as a formula (4) in anhydrous ether under the protection of inert gas, cooling to-78 ℃, stirring for 30min, adding n-BuLi under the protection of argon, reacting for 2h at-78 ℃, and then adding CuCl under the protection of argon2Heating to-55 deg.C for reaction for 2h, heating to room temperature, stirring overnight, adding CH3Quenching OH, and then separating, washing and drying to obtain the product;
Figure BDA0001361428000000032
the diselenopheno [2,3-b:3',2' -d ] thiophene is a novel organic functional material and a construction module of selenothiophene, and lays a foundation for development of organic semiconductor materials with excellent semiconductor performance and construction of selenothiophene.
The preparation method of the diselenopheno [2,3-b:3',2' -d ] thiophene is simple and feasible, is suitable for batch production, and the yield of the obtained diselenopheno [2,3-b:3',2' -d ] thiophene is high and can reach 77%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound (3) obtained in example 1;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the compound (3) obtained in example 1;
FIG. 3 is a mass spectrum of the compound (3) obtained in example 1;
FIG. 4 is an infrared spectrum of the compound (3) obtained in example 1;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the compound (2) obtained in example 2;
FIG. 6 is a nuclear magnetic resonance carbon spectrum of the compound (2) obtained in example 2;
FIG. 7 is a mass spectrum of the compound (2) obtained in example 2;
FIG. 8 is an infrared spectrum of the compound (2) obtained in example 2;
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the compound (1) obtained in example 3;
FIG. 10 is a nuclear magnetic resonance carbon spectrum of the compound (1) obtained in example 3;
FIG. 11 is a mass spectrum of the compound (1) obtained in example 3;
FIG. 12 is a high-resolution mass spectrum of the compound (1) obtained in example 3;
FIG. 13 is an infrared spectrum of the compound (1) obtained in example 3.
Detailed Description
Examples
The diselenopheno [2,3-b:3',2' -d ] thiophene of the embodiment has the structure shown in the formula (1),
Figure BDA0001361428000000041
the synthetic route of the diselenopheno [2,3-b:3',2' -d ] thiophene of the embodiment is as follows,
Figure BDA0001361428000000042
the preparation method of diselenopheno [2,3-b:3',2' -d ] thiophene in this example includes the following steps:
1) preparation of 5,5 '-bis (trimethylsilyl) -3,3' -bisselenophene (3):
vacuum-drying 250mL Schlenk bottle for 0.5h, adding 0.65g (2.29mmol) of 4-bromo-2-trimethylsilyl-selenophene (4) under the protection of argon gas, adding 50mL of anhydrous ether under the protection of argon gas, stirring to completely dissolve the compound (4), cooling to-78 ℃, and stirring for 30 min; under the protection of argon, n-BuLi (1.0mL, 2.5M in hexane,11.73mmol,1.0equiv) was added dropwise, and the reaction was maintained at-78 ℃ for 2 h. Then 3.19g of dry CuCl were added under argon protection2(23.45mmol2.0equiv), heating to-55 deg.C for reaction for 2h, slowly heating to room temperature and stirring overnight. Adding a few drops of CH at low temperature3The reaction was quenched with OH, the reaction was transferred to a 250mL separatory funnel, the aqueous phase was separated and 3X 15mLCH was used2Cl2The aqueous phase was extracted and the organic phases were combined. The organic phase was washed with 15mL of water, 15mL of saturated sodium bicarbonate solution, and 15mL of water, and then with anhydrous MgSO4Drying, filtration and removal of the solvent gave 2.73g of crude product. The crude product was purified by column chromatography (silica gel: 300-400 mesh, eluent: petroleum ether) to give 2.1g of the compound (3) (pale yellow solid), yield: 89% and Mp of 68-69 ℃.1H NMR (CDCl3,400MHz)δ(ppm)8.28(s,2H),7.76(s,2H),0.35(s,18H),13C NMR(CDCl3, 100MHz):δ148.6,142.3,136.5,129.9,0.3.MS(EI,70eV):m/z)405.96(90)[M+], 390.81(100)[M+-15].HRMS(DART-Positive)m/z:[M+H]+calcd for C14H23Se2Si2406.9663；found 406.9662.IR(KBr):3124,3026,2947,2892cm-1. NMR Hydrogen spectrum of Compound (3), NMRThe carbon spectrogram, the mass spectrogram and the infrared spectrogram are respectively shown in figures 1-4.
2) Preparation of 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene (2):
0.2100g of the compound 5,5 '-bis (trimethylsilyl) -3,3' -bisselenophene (3) (0.54mmol) obtained in step 1) are added into a 100mL Shlenk bottle, vacuum drying is carried out for 0.5h, 20mL of anhydrous ether is added under the protection of argon, the temperature is reduced to 0 ℃, n-BuLi (0.47mL,2.4M in hexane,1.14mmol,2.1equiv) is added for reaction for 2h at 0 ℃, the temperature is adjusted to-78 ℃, 0.1739g (PhSO) is added under the protection of argon2)2S (1.02equiv), heating to-55 ℃ and keeping the reaction for 2h, slowly heating to room temperature and stirring overnight. Adding a few drops of CH at low temperature3The reaction was quenched with OH, transferred to a 125mL separatory funnel, and washed with 3X 15mLCH2Cl2The aqueous phase was extracted and the organic phases were combined. The organic phase was washed with 15mL of water, 15mL of saturated sodium bicarbonate solution, and 15mL of water, and then with anhydrous MgSO4Drying, filtering and removing the solvent to obtain 0.29g of crude product. The crude product was separated by column chromatography (silica gel: 300-400 mesh, eluent: petroleum ether) to give 0.1900g of the compound (2), yield: 84 percent and Mp of 76-78 ℃.1H NMR(CDCl3,300MHz)δ(ppm)7.76(s,2H),0.36(s,18H),13C NMR(CDCl3, 75MHz):δ150.6,143.7,143.5,127.8,0.2.MS(EI,70eV):m/z)435.92(100)[M+], 420.91(95)[M+-15].HRMS(DART-Positive)m/z:[M+H]+calcd for C14H21SSe2Si2436.9232；found 436.9229.IR(KBr):3037,2956,2894cm-1. The NMR hydrogen spectrum, NMR carbon spectrum, mass spectrum and IR spectrum of the compound (2) are shown in FIGS. 5-8.
3) Preparation of diselenopheno [2,3-b:3',2' -d ] thiophene (1):
0.0873g (0.2009mmol) of the 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d) obtained in step 2) was added]Thiophene (2) dissolved in 10mL of CHCl3To this solution, 0.07mL of trifluoroacetic acid (TFA) (1.0045 mmol,5equiv) was added, the reaction was carried out at room temperature for 1 hour, the thin layer plate followed the disappearance of the starting material, a few drops of water were added to the system to quench the reaction, the reaction solution was transferred to a 125mL separatory funnel, 15mL of water was added thereto and washed, shaken,after standing and separating, the aqueous phase was extracted with 3X 10mL of dichloromethane, and the organic phases were combined. The combined organic phases were washed with 15mL of water, 15mL of saturated sodium bicarbonate solution, 15mL of water, and anhydrous MgSO4Drying, filtering and removing the solvent to obtain a crude product: 0.0624g, and the crude product was purified by column chromatography to give compound (1)0.0450g, yield: 77%, Mp: 126-.1H NMR(CDCl3,400MHz)δ(ppm)7.98(d,J＝5.6Hz, 2H),7.63(d,J＝5.6Hz,2H).13C NMR(CDCl3,100MHz):δ141.8,138.6,131.3, 121.6.MS(EI,70eV):m/z)291.68(50)[M+].HRMS(DART-Positive)m/z:[M+H]+calcd for C8H5SSe2292.8437；found 292.8434.IR(KBr):3089,2919,2854,1418 cm-1. The NMR hydrogen spectrum, NMR carbon spectrum, mass spectrum, high-resolution mass spectrum and IR spectrum of the compound (1) are shown in FIGS. 9-13.

Claims (5)

1. A method for preparing diselenopheno [2,3-b:3',2' -d ] thiophene is characterized by comprising the following steps:
dissolving a compound 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene shown as a formula (2) in an organic solvent, adding trifluoroacetic acid to react for 0.5-1.5 h at room temperature, and then quenching to obtain the compound,
Figure FDA0002115946290000011
the organic solvent is trichloromethane or dichloromethane;
the molar ratio of the 2, 5-bis (trimethylsilyl) diselenopheno [2,3-b:3',2' -d ] thiophene to the trifluoroacetic acid is 1: 5-10;
the quenching is water quenching or sodium bicarbonate solution quenching;
the diselenopheno [2,3-b:3',2' -d ] thiophene has the structure shown in the formula (1),
Figure FDA0002115946290000012
2. the method of claim 1 for preparing diselenopheno [2,3-b:3',2' -d ] thiophene, further comprising the steps of: and adding water to wash the reaction solution obtained after quenching, and then separating an aqueous phase and an organic phase.
3. The method of claim 2 further comprising extracting the separated aqueous phase with chloroform and combining the organic phases.
4. The method of claim 3, further comprising washing, drying, filtering, and removing the solvent from the combined organic phase to obtain a crude diselenopheno [2,3-b:3',2' -d ] thiophene.
5. A process according to claim 4, wherein the washing of the combined organic phases is with water, a saturated sodium bicarbonate solution, water.
CN201710619837.8A 2017-07-26 2017-07-26 Diselenopheno [2,3-b:3',2' -d ] thiophene and preparation method thereof Active CN107522720B (en)

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二硒吩并[2,3-b:3`,2`-d ]硒吩（噻吩）（DSS/DST）及其螺烯化衍生物的制备;吴龙龙;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20170315;第I页化合物11，第17-18页合成路线图1-33，第14页1.22文字描述内容，第3页合成路线图1-5 *

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