CN110606858B - Preparation method of thiophene organic semiconductor material intermediate - Google Patents
Preparation method of thiophene organic semiconductor material intermediate Download PDFInfo
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- CN110606858B CN110606858B CN201910952514.XA CN201910952514A CN110606858B CN 110606858 B CN110606858 B CN 110606858B CN 201910952514 A CN201910952514 A CN 201910952514A CN 110606858 B CN110606858 B CN 110606858B
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000004065 semiconductor Substances 0.000 title claims abstract description 18
- 229930192474 thiophene Natural products 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- -1 2-ethylhexyl Chemical group 0.000 claims abstract description 13
- BDQANEJJDSLTKJ-UHFFFAOYSA-N dichloro-(2-ethylhexyl)-octylsilane Chemical compound CCCCCCCC[Si](Cl)(Cl)CC(CC)CCCC BDQANEJJDSLTKJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- KBRZCEVRNLKHAZ-UHFFFAOYSA-N 3-bromo-2-(3-bromothiophen-2-yl)thiophene Chemical compound C1=CSC(C2=C(C=CS2)Br)=C1Br KBRZCEVRNLKHAZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- MENYRYNFSIBDQN-UHFFFAOYSA-N 5,5-dibromoimidazolidine-2,4-dione Chemical compound BrC1(Br)NC(=O)NC1=O MENYRYNFSIBDQN-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000002140 halogenating effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005051 trimethylchlorosilane Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MOMHMPZSZNZLAK-UHFFFAOYSA-N 3,5-dibromo-2-(3,5-dibromothiophen-2-yl)thiophene Chemical group S1C(Br)=CC(Br)=C1C1=C(Br)C=C(Br)S1 MOMHMPZSZNZLAK-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- 208000020564 Eye injury Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZKCVPMCCGPMMBH-UHFFFAOYSA-N [4-bromo-5-(3-bromo-5-trimethylsilylthiophen-2-yl)thiophen-2-yl]-trimethylsilane Chemical compound S1C([Si](C)(C)C)=CC(Br)=C1C1=C(Br)C=C([Si](C)(C)C)S1 ZKCVPMCCGPMMBH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000152 severe skin burn Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The application relates to a preparation method of a thiophene organic semiconductor material intermediate, which comprises the following steps: (1) reacting 2, 2' -bithiophene with a halogenating agent to obtain tetrahalo-substituted bithiophene; (2) selectively removing halogen at the ortho position of the bithiophene substituted by tetrahalo to obtain bithiophene substituted by m-dihalogen; and (3) under the protection of inert atmosphere and in the presence of a catalyst, reacting meta-dihalogen substituted bithiophene with dichloro (2-ethylhexyl) octylsilane to synthesize the target product 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] dithiophene. The preparation method of the thiophene organic semiconductor material intermediate has simple process, does not use substances with serious corrosiveness or toxicity, does not need further reaction treatment on the intermediate 3,3 '-dibromo-2, 2' -bithiophene, and can react with dichloro (2-ethylhexyl) octyl silane to synthesize the target product.
Description
Technical Field
The application relates to the technical field of organic chemical synthesis. In particular to a preparation method of a thiophene organic semiconductor material intermediate.
Background
4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] dithiophene is an organic semiconductor material and is most widely used in organic photovoltaics (e.g., solar cells) and photodiodes. Polymers formed from 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] dithiophene have excellent solubility in organic solvents and excellent film-forming properties, and exhibit high energy conversion efficiency for use in organic photovoltaic devices, such as solar cells.
With respect to the synthesis of 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b ' ] dithiophene, a method for synthesizing 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b ' ] dithiophene by reacting compound a with compound b to obtain 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b ' ] dithiophene has been reported in Japan Mitsubishi chemical Co., Ltd. patent CN 104350082A. The specific synthetic route disclosed in this patent document is as follows:
the first step is as follows:
the second step is that:
the third step:
as shown above, compound b is dichloro (2-ethylhexyl) octylsilane, and compound a is 3,3 ' -dibromo-5, 5 ' -bis (trimethylsilyl) -2,2 ' -bithiophene. The compound a is synthesized according to the report of patent WO2010136353A1, and is synthesized by reacting 3,3 '-dibromo-2, 2' -bithiophene with trimethylchlorosilane under the action of butyl lithium. In the prior art patent CN104350082A, the synthesis route of 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b ' ] dithiophene is long, especially the preparation process of the compound a is firstly synthesized by reacting 3,3 ' -dibromo-2, 2 ' -bithiophene with trimethylchlorosilane under the action of butyllithium, and then the obtained compound a is reacted with the compound b to obtain the target product. In addition, trimethylchlorosilane, which is a highly flammable liquid and vapor, may corrode metals, be poisoned by inhalation or swallowing, be harmful to skin contact, cause severe skin burns and eye injuries, and may cause damage to the respiratory system, is required in the synthesis of compound a.
For this reason, there is a continuing need in the art to develop a process for preparing thiophene-based organic semiconductor material intermediates that is simplified in process and does not use highly corrosive or toxic substances.
Disclosure of Invention
The present application aims to provide a method for preparing an intermediate of thiophene organic semiconductor materials, which has a simplified process and does not use trimethylchlorosilane, so as to solve the technical problems in the prior art. In the synthesis method described herein, 2' -bithiophene is used as a starting material to synthesize tetrahalo-substituted bithiophene; then selectively removing halogen at the ortho position of the bithiophene substituted by the tetrahalogen to obtain bithiophene substituted by the meta-dihalogen; then the bithiophene substituted by m-dihalogen and dichloro (2-ethylhexyl) octylsilane are reacted to synthesize the target product 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] dithiophene.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a method for preparing a thiophene-based organic semiconductor material intermediate, characterized in that the method comprises the steps of:
(1) reacting 2, 2' -bithiophene with a halogenating agent to obtain a tetrahalo-substituted bithiophene;
(2) selectively removing halogen at the ortho position of the bithiophene substituted by tetrahalo to obtain bithiophene substituted by m-dihalogen; and
(3) under the protection of inert atmosphere and in the presence of catalyst, meta-dihalogen substituted bithiophene reacts with dichloro (2-ethylhexyl) octylsilane to synthesize the target product 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] bithiophene.
In one embodiment of the first aspect, the halogenating agent comprises dibromohydantoin.
In one embodiment of the first aspect, in step (1), 2' -bithiophene is reacted with a halogenating agent in a mixed solvent comprising chloroform and acetic acid.
In one embodiment of the first aspect, selectively removing the halogen ortho to the tetrahalo-substituted bithiophene in step (2) comprises reacting the tetrahalo-substituted bithiophene with a metal under acidic conditions.
In one embodiment of the first aspect, the metal comprises zinc.
In one embodiment of the first aspect, the acidic condition is provided by a mixture of hydrochloric acid and glacial acetic acid.
In one embodiment of the first aspect, in step (3), the catalyst is n-butyllithium.
In one embodiment of the first aspect, in step (3), dichloro (2-ethylhexyl) octylsilane is in excess relative to meta-dihalogen-substituted bithiophene on a molar basis.
In one embodiment of the first aspect, the tetrahalo-substituted bithiophene is 3,3 ' 5,5 ' -tetrabromo-2, 2 ' -bithiophene.
In one embodiment of the first aspect, the meta-dihalogen-substituted bithiophene is 3,3 '-dibromo-2, 2' -bithiophene.
Compared with the prior art, the preparation method of the thiophene organic semiconductor material intermediate has the advantages that the process is simplified, and no severely corrosive or toxic substance is used. The preparation method of the thiophene organic semiconductor material intermediate is an optimized process, 3,3 '-dibromo-2, 2' -bithiophene does not need further reaction treatment, and can react with dichloro (2-ethylhexyl) octyl silane to synthesize a target product, so that the process is simple and saves materials.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations that can include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from a lower value to an upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical or other property (e.g., molecular weight, melt index, etc.) is stated to be from 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and sub ranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are expressly enumerated. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms as well.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the exclusion of any doubt, all compositions herein using the terms "comprising", "including", or "having" may include any additional additive, adjuvant, or compound, unless explicitly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In a specific embodiment, the invention provides a preparation method of 4- (2-ethylhexyl) -4-octyl-4-silicon-based [3,2-b:4,5-b' ] dithiophene, which has a simple process and saves materials. The specific synthetic routes described herein are shown below:
examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
This example relates to the synthesis of 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] dithiophene. The synthetic route and experimental operation of this example are as follows.
The first step is as follows:
the reaction equation is as follows:
proportioning materials:
the operation process is as follows:
2, 2' -bithiophene, chloroform and acetic acid in the weights shown in the above table were added to a 2L flask, and stirred to dissolve at room temperature (20-30 ℃ C.). Then 378g of dibromohydantoin is added for four times, the addition is completed in 30min, and the exothermic temperature of the reaction rises to 40-45 ℃. After reacting for 1h, heating to 45-50 ℃, reacting for 18h, and separating out white solids, sampling and controlling the white solids in a middle control mode (the middle control is 1, and the main content is more than or equal to 90%). Concentrating the reaction solution to about 0.8L, adding 600ml of ethanol, stirring, cooling with ice water, performing suction filtration, washing with 400ml of ethanol slurry once, washing with 400ml of methanol slurry once, performing suction drying to obtain 319g of wet product (the central control is 2, the main content is more than or equal to 98%), and drying at 60 ℃ to obtain 262g of white-like solid, wherein the molar yield is 90.6%.
The second step:
the reaction equation is as follows:
material proportioning:
the operation process is as follows:
3,3 ' 5,5 ' -tetrabromo-2, 2 ' -bithiophene in the weight indicated in the above table, ethanol, water, glacial acetic acid and hydrochloric acid were added to a 5L flask, and heated to 74 ℃ for reflux. Then, adding zinc powder by 6 times, adding for 1.5h, refluxing for 1h after adding, and sampling (the center control is 1, and the main content is more than or equal to 80%). Filtering while hot, concentrating the filtrate to 700g, adding 500g water, stirring, cooling with ice water, and filtering to obtain light green wet product (center control 2, main content greater than or equal to 85%). Then, adding 600ml of dichloromethane, washing twice with 300ml of x 2 water, drying 40g of anhydrous sodium sulfate, performing suction filtration, concentrating to obtain 162g of crude product, adding 450ml of ethanol, performing reflux dissolution, cooling for crystallization, cooling with ice water, performing suction filtration, leaching once with 200ml of ethanol, performing suction filtration to obtain 132g of wet product (the central control is 3, the main content is more than or equal to 99%), and drying at 60 ℃ to obtain 110g of 3,3 '-dibromo-2, 2' -bithiophene, wherein the molar yield is 62%.
The third step:
the reaction equation is as follows:
proportioning materials:
the operation process comprises the following steps:
magnesium and two iodine pellets in the weight shown in the above table were charged into a 2L flask, and the nitrogen gas was replaced three times. Then, 10ml of THF solution of bromo-isooctane is dripped at room temperature, stirring is carried out for 10min, the iodine color disappears, the reaction is initiated, the heat is released to 35 ℃, the solution is dripped continuously at room temperature for 1 hour and 40 minutes, the temperature is at 37 ℃, stirring is carried out continuously for 1 hour to obtain the Grignard reagent, and sampling is carried out (center control is 1, the content of raw materials is less than or equal to 1%). The grignard reagent was added dropwise to a THF solution of n-octyltrichlorosilane, dropwise at room temperature, and dropwise addition was completed within 2.5 h. After dripping, reacting for 16h at room temperature, sampling (central control 2, main content is more than or equal to 50%), performing suction filtration, washing a filter cake once by using normal hexane, concentrating and drying filtrate, adding 300ml of normal hexane, stirring uniformly, filtering, washing the filter cake once by using 100ml of normal hexane, and concentrating and drying to obtain 150g of oily matter. Rectifying, and collecting 60g of fractions at 96-103 ℃ (the central control is 3, and the main content is more than or equal to 96%).
The fourth step:
the reaction equation is as follows:
material proportioning:
the operation process comprises the following steps:
the 5L reaction flask was replaced with nitrogen three times, then THF 3150ml was added and the dry ice ethanol was cooled to-30 ℃. Then 215ml of n-butyllithium is added, the temperature of dry ice ethanol is reduced to-71 ℃, 630ml of tetrahydrofuran solution of 3,3 '-dibromo-2, 2' -bithiophene is added dropwise, and the solution is dripped out for 1 hour. After the dripping is finished, continuously stirring for 2h at the temperature of between 70 ℃ below zero and 75 ℃ below zero, and sampling (the central control is 1, and the content of the raw materials is less than or equal to 4 percent). Dripping a THF solution of dichloro (2-ethylhexyl) octyl silane for 50min, and maintaining the temperature at-65 to-75 ℃ for 2 h. Then, the temperature is naturally raised to the room temperature overnight, the reaction is carried out for 15h, a sample is taken (the central control is 2, the main content is more than or equal to 70 percent), and 500g of ammonium chloride (the mass ratio is 10 percent) aqueous solution is added. Concentrating under reduced pressure below 45 deg.C until there is no organic solvent, adding n-hexane 500ml, stirring, separating water layer, washing organic layer with 200ml 2 water twice, drying with anhydrous sodium sulfate 75g, vacuum filtering, concentrating to obtain 95g oily substance, purifying with aluminum peroxide (1.4kg) column, and eluting with n-hexane to obtain 23g pale yellow oily substance (center control 3, main content not less than 96%).
The embodiments described above are presented to enable a person having ordinary skill in the art to make and use the present application. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (8)
1. A preparation method of a thiophene organic semiconductor material intermediate is characterized by comprising the following steps:
(1) reacting 2, 2' -bithiophene with dibromohydantoin in a mixed solvent containing chloroform and acetic acid to obtain tetrahalo-substituted bithiophene;
(2) selectively removing halogen at the ortho position of the bithiophene substituted by tetrahalogen to obtain bithiophene substituted by m-dihalogen; and
(3) under the protection of inert atmosphere and in the presence of catalyst, meta-dihalogen substituted bithiophene reacts with dichloro (2-ethylhexyl) octylsilane to synthesize the target product 4- (2-ethylhexyl) -4-octyl-4-silyl [3,2-b:4,5-b' ] bithiophene.
2. The method for producing a thiophene organic semiconductor material intermediate according to claim 1, wherein selectively dehalogenating an ortho position to said tetrahalo-substituted bithiophene in step (2) comprises reacting said tetrahalo-substituted bithiophene with a metal under acidic conditions.
3. The method of claim 2, wherein the metal comprises zinc.
4. The method of preparing a thiophene organic semiconductor material intermediate according to claim 2, wherein the acidic conditions are provided by a mixture of hydrochloric acid and glacial acetic acid.
5. The method for producing a thiophene organic semiconductor material intermediate according to claim 2, wherein in step (3), said catalyst is n-butyllithium.
6. The method for producing a thiophene organic semiconductor material intermediate according to claim 2, wherein dichloro (2-ethylhexyl) octylsilane is in excess relative to meta-dihalo-substituted bithiophene in step (3) on a molar basis.
7. The method for producing a thiophene organic semiconductor material intermediate according to any one of claims 1-6, wherein said tetrahalo-substituted bithiophene is 3,3 ', 5 ' -tetrabromo-2, 2 ' -bithiophene.
8. The method for producing the thiophene organic semiconductor material intermediate according to any one of claims 1-6, wherein said meta-dihalogen-substituted bithiophene is 3,3 '-dibromo-2, 2' -bithiophene.
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