CN108864143B - Asymmetric seven-element fused thiophene and preparation method and application thereof - Google Patents
Asymmetric seven-element fused thiophene and preparation method and application thereof Download PDFInfo
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229930192474 thiophene Natural products 0.000 title claims abstract description 16
- -1 lithium alkyl bromide Chemical class 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 8
- 230000005669 field effect Effects 0.000 claims abstract description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004327 boric acid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical group B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical group [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 1
- VGWBXRXNERKBSJ-UHFFFAOYSA-N dithieno[2,3-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2SC=C1 VGWBXRXNERKBSJ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 3
- 238000010537 deprotonation reaction Methods 0.000 abstract description 2
- FPBIZKVBSICZCB-UHFFFAOYSA-N (3-bromodithieno[3,2-a:3',2'-d]thiophen-6-yl)-trimethylsilane Chemical compound BrC1=CSC2=C1SC1=C2C=C([Si](C)(C)C)S1 FPBIZKVBSICZCB-UHFFFAOYSA-N 0.000 abstract 1
- 230000005595 deprotonation Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- 239000012043 crude product Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 229940125898 compound 5 Drugs 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 7
- 229940126214 compound 3 Drugs 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000006880 cross-coupling reaction Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 150000003577 thiophenes Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- KYOIPUDHYRWSFO-UHFFFAOYSA-N [Br].[Li] Chemical group [Br].[Li] KYOIPUDHYRWSFO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HKNRNTYTYUWGLN-UHFFFAOYSA-N dithieno[3,2-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2C=CS1 HKNRNTYTYUWGLN-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—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 four or more hetero rings
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- 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
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Abstract
The invention relates to an asymmetric seven-element fused thiophene and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1: 3-bromo-6-trimethylsilyl-dithieno [2,3-b:2',3' -d]Thiophene is firstly exchanged by lithium alkyl bromide and then reacted with pinacol boric acid ester to prepare 6-trimethylsilyl-3-pinacol ester-dithieno [2,3-b:2',3' -d]Thiophene; s2: reacting the product of S1 with 5-bromo-2-trimethylsilyl-dithieno [3,2-b:2',3' -d]Preparation of 2-trimethylsilyl-5- (6-trimethylsilyl-dithieno [2,3-b:2',3' -d ] thiophene by Suzuki coupling]Thiophene-3) dithieno [3,2-b:2',3' -d]Thiophene; s3: deprotonation of the product of S2 by LDA, (PhSO)2)2S-thio ring closure is used for preparing unsymmetrical heptathiophene. The asymmetric seven-element fused thiophene can be used as an organic semiconductor material to be applied to organic light-emitting diodes, organic field effect transistors and organic solar cells.
Description
Technical Field
The invention relates to an asymmetric seven-element fused thiophene and a preparation method and application thereof, belonging to the technical field of preparation of organic compounds.
Background
Fused thiophenes are a class of thiophene oligomers formed by the fusion of thiophene units through aromatic rings. At present, fused thiophene compounds have been applied to organic light emitting diodes, organic field effect transistors, and organic solar cells as organic semiconductor materials. Oligothiophenes (tetrachiophenes and pentachiophenes and derivatives thereof) synthesized based on the benzotrithiophene have shown attractive application prospects in the field of organic optoelectronics. Heptathiophenes, as a typical class of fused thiophene oligomers, have various forms of molecular configuration, such as: spiral, horn, and wire types, etc. Compared with the conjugated system of the bitrothiophene and the pentachiophene, the conjugated system of the heptathiophene is larger, and the more excellent photoelectric property is expected to be displayed. Due to position isomerism and molecular skeleton isomerism of an S atom in a heptathiophene structure, various isomers exist, the isomers can show various intermolecular acting forces, and the existence of the acting forces can influence the intermolecular accumulation mode and further influence the photoelectric performance of the material. The reported heptathiophene has linear, spiral and horn symmetric molecules.
Straight-chain heptathiophene through
Prepared by exchanging BuLi lithium bromide for TIPS group protection
Preparation by LDA bromine transfer
Then with (Bu)3Sn)2S，Pd(PPh3)4Reacting at 130 ℃ for 24h, and preparing the product by self-coupling
The coupled product is deprotonated CuCl by BuLi2By closing the ring to obtain
Spiro-heptathiophene through
Preparation by NBS bromination and LDA bromine migration
Exchange of CuCl by n-BuLi lithium bromide2Prepared by self-coupling under the action of
The coupling product was deprotonated by LDA and diphenylsulfonyl sulfide ((PhSO)2)2S) ring closure to obtain
Ox horn heptathiophene through
Is prepared by the protection of deprotonated TMS group by LDA, NBS bromination and LDA bromine migration
At K3PO4，Pd[PtBu3]2Prepared by self-coupling under the action of
The coupling product was deprotonated by LDA and diphenylsulfonyl sulfide ((PhSO)2)2S) ring closure to obtain
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problem that only symmetric heptathiophene isomers are synthesized in the prior art, a novel asymmetric heptathiophene fused thiophene, a preparation method and application thereof are provided, a foundation is laid for the development of the asymmetric heptathiophene, and more high-performance organic semiconductor materials are provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an asymmetric seven-membered fused thiophene having the structure:
wherein TMS is trimethylsilyl, and the preparation method of the asymmetric seven-element fused thiophene comprises the following steps:
the method comprises the following steps:
will be provided with
Adding organic solvent for dissolving, and stirring at-70 deg.C to 90 deg.C for 10-20 min; LDA is added dropwise to react at-70 ℃ to 90 ℃; adding (PhSO) under the protection of inert gas2)2S, heating to room temperature for reaction; adding quenching agent to quench reaction, and performing post-treatment after the reaction to obtain
Preferably, the
LDA、(PhSO2)2The molar ratio of S is 1:2-4:1-1.2, the reaction time after LDA is added is 2-5h, and (PhSO) is added2)2The reaction time after S is 8-14 h.
Wherein, an intermediate compound for preparing asymmetric seven-membered fused thiophene
The preparation method comprises the following steps:
the method specifically comprises the following steps:
in that
Adding organic solvent and oxygen-free water into tetratriphenylphosphine palladium or palladium acetate and carbonate, heating for reaction, and post-treating after reaction to obtain
Preferably, the carbonate is K2CO3、Na2CO3、CsCO3The organic solvent is THF, toluene or a mixed solvent of THF and toluene, the reaction temperature is 100-110 ℃, the reaction time is 8-14h, and the organic solvent is
The molar ratio of the tetrakistriphenylphosphine palladium or palladium acetate to the carbonate is 1:1-3:0.003-0.01:1-5, and the volume ratio of the organic solvent to the oxygen-free water is 2.5-5: 1.
Further, the
The preparation method comprises the following steps:
the method specifically comprises the following steps:
will be provided with
Adding an organic solvent for dissolving under the protection of inert gas, and keeping stirring at-70-90 ℃ for 10-20 min; dropping alkyl lithium to react at-70-90 deg.c; adding pinacol boric acid ester under the protection of inert gas, and slowly heating to room temperature for reaction; adding quenching agent to quench the reaction, and treating to obtain
Preferably, the
The molar ratio of the alkyl lithium to the pinacol borate is 1:2.1-2.5:1-1.5, the organic solvent is an ether solvent, the alkyl lithium is t-BuLi or n-BuLi, the pinacol borate is isopropanol pinacol borate or diboron pinacol ester, the reaction time after the alkyl lithium is added is 2-5 hours, and the reaction time after the pinacol borate is added is 8-14 hours.
The invention also provides application of the asymmetric seven-element fused thiophene as an organic semiconductor material in organic light-emitting diodes, organic field effect transistors and organic solar cells.
In the process for preparing the asymmetric fused heptathiophene of the invention
The cross coupling of two dithienothiophene building modules with different structures is a key step, three coupling products, namely two self-coupling products and one cross-coupling product, can be generated by adopting common bromine-lithium exchange and copper chloride coupling, and the solubility and polarity of the three products are very close to each other, so that the cross-coupling product is low in yield and difficult to purify. Three coupled products were also present via Negishi Coupling reaction, with lower yields. Through various attempts, the optimal reaction conditions are finally obtainedThat is, will be asymmetric
Is prepared into
Then efficiently obtaining a cross-Coupling product by Suzuki Coupling
The invention has the beneficial effects that:
(1) the invention adopts a brand new method to synthesize the asymmetric seven-element fused thiophene
Is prepared into
Then efficiently obtaining a cross-Coupling product by Suzuki Coupling
Avoids the generation of self-coupling product by-products, obtains higher yield, and finally obtains diphenyl sulfonyl sulfide ((PhSO) through LDA deprotonation2)2S) preparing asymmetric heptathiophene substituted by double TMS through a thio-ring.
(2) The novel asymmetric seven-element fused thiophene prepared by the invention can be used as an organic semiconductor material to be applied to organic light-emitting diodes, organic field effect transistors and organic solar cells, has excellent performance, and can obtain the following performances when the substrate temperature is room temperature: mobility of 0.02cm2A threshold voltage of-48V and a switching ratio of 105。
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of Compound 3 according to example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of Compound 3 according to example 1 of the present invention;
FIG. 3 is a high-resolution mass spectrum of Compound 3 according to example 1 of the present invention;
FIG. 4 is a chart of an infrared spectrum of compound 3 according to example 1 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of Compound 5 according to example 1 of the present invention;
FIG. 6 is a nuclear magnetic resonance carbon spectrum of Compound 5 according to example 1 of the present invention;
FIG. 7 is a high-resolution mass spectrum of Compound 5 according to example 1 of the present invention;
FIG. 8 is a chart of an infrared spectrum of Compound 5 according to example 1 of the present invention;
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of Compound 1 according to example 1 of the present invention;
FIG. 10 shows a nuclear magnetic resonance carbon spectrum of Compound 1 according to example 1 of the present invention;
FIG. 11 is a high-resolution mass spectrum of Compound 1 according to example 1 of the present invention;
FIG. 12 is an infrared spectrum of Compound 1 according to example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail by way of examples.
Example 1
The embodiment provides a preparation method of bis-TMS substituted asymmetric heptathiophene, which comprises the following steps:
(1) preparation of 6-trimethylsilyl-3-pinacol ester-dithieno [2,3-b:2',3' -d ] thiophene (3), the reaction equation is as follows:
the specific method comprises the following steps: adding compound 2(679mg,1.95mmol) into dried 100mL Schlenk, vacuum drying for 0.5h, adding 50mL anhydrous diethyl ether under the protection of argon, stirring thoroughly to dissolve, transferring into a low temperature instrument at-78 deg.C, and stirring for 10 min; t-BuLi (1.28M in Pentane,3.2mL,4.10mmol,2.1eq) was slowly added dropwise) Reacting at-78 ℃ for 2 h; isopropanol pinacol borate (0.47mL,2.34mmol,1.2eq) was added under argon, the mixture was allowed to warm to room temperature slowly and stirred for 10 h. 2mL of CH was added3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The compound was isolated by column chromatography (silica gel: 200 mesh, 300 mesh, eluent: PE, and then EA: PE: 1:10) as an off-white solid (6399mg), yield: 52%, Mp:156.7-158.5 ℃. 1H NMR (400MHz, CDCl)3):7.73(s,1H),7.43(s,1H),1.37(s,12H),0.37(s,9H)；13C NMR(100MHz,CDCl3):147.62,145.17,144.59,135.93,129.96,124.71,84.18,24.89,-0.09；IR(KBr):2978，1504，1357，1320，1258，1137，975，831cm-1；HRMS(MALDI_DHB)m/z calcd for[C17H23BO2S3Si]394.0722,found 394.0719。
(2) Preparation of 2-trimethylsilyl-5- (6-trimethylsilyl-dithieno [2,3-b:2',3' -d ] thiophene-3) dithieno [3,2-b:2',3' -d ] thiophene (5) according to the following reaction equation:
the specific method comprises the following steps: compound 3(157mg,0.4mmol), compound 4(138mg,0.4mmol,1.0eq), Pd (PPh)3)4(1.4mg,0.0012mmol,0.003eq)，K2CO3(138mg,1.0mmol,2.5eq) was added to a dry 25mL Schlenk, dried under vacuum for 0.5h, 10mL anhydrous THF, 0.4mL anhydrous water, and reacted at 105 ℃ for 10 h. The solvent was removed and 30mL of saturated NaHCO was added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was separated by column chromatography (silica gel: 300-400 mesh, dry-loading, eluent: PE) to give the compound 5(132mg) as a white solid in a yield of 66% and Mp at 275.8-277.8 ℃. 1H NMR (400MHz, CDCl3,):7.71(s, 1)H),7.67(s,1H),7.46(s,1H),7.42(s,1H),0.40(s,18H)；13C NMR(100MHz,CDCl3,):145.73,143.99,143.34,143.15,140.28,139.81,135.91,130.41,129.14,128.68,126.72,124.60,121.52,121.06,-0.10,-0.15；IR(KBr):3086,2955,2896,1408,2348,1250,992,834,758cm-1；HRMS(MALDI_DHB)m/z calcd for[C22H23S6Si2]534.9662；found 534.9655。
(3) Preparation of bis-TMS substituted unsymmetrical heptathiophenes (1), the reaction equation is as follows:
compound 5(59mg,0.11mmol) was added to dry 100mL Schlenk, dried for 1.0h, and 35mL of anhydrous Et was added2O, fully stirring to dissolve the O, and transferring the O into a low-temperature instrument at the temperature of minus 78 ℃ to keep stirring for 10 min; LDA (0.43mmol,4.0eq) is added dropwise, the mixture reacts for 2 hours at 78 ℃, and drying (PhSO) is added rapidly under the protection of argon2)2S (38mg,0.12mmol,1.05eq), was slowly warmed to room temperature and reacted for 10 h. 2mL of CH was added at low temperature3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was purified by PTLC to give compound 1(19mg) as a white solid, yield: 32%, Mp:>300℃。1H NMR(400MHz,CDCl3,):7.42(s,2H),0.41(s,18H)；13C NMR(100MHz,CDCl3,):145.84,143.05,142.36,142.26,140.41,138.68,138.33,136.42,132.41,132.30,131.89,131.48,129.37,129.30,126.63,124.19,-0.08；IR(KBr):2955,2923,2852,1466,1372,1249,992,835,756cm-1；HRMS(MALDI_CLA)m/z calcd for[C22H20S7Si2]563.9148；found 563.9143。
the properties obtained for the bis-TMS substituted asymmetric heptathiophene (1) at substrate temperature at room temperature were: mobility of 0.02cm2A threshold voltage of-48V and a switching ratio of 105Has excellent performance, canThe organic semiconductor material is used as an organic semiconductor material in organic light-emitting diodes, organic field effect transistors and organic solar cells.
Example 2
The embodiment provides a preparation method of bis-TMS substituted asymmetric heptathiophene, which comprises the following steps:
(1) preparation of 6-trimethylsilyl-3-pinacol ester-dithieno [2,3-b:2',3' -d ] thiophene (3), the reaction equation is as follows:
the specific method comprises the following steps: adding the compound 2(678mg,1.95mmol) into a dry 100mL Schlenk, vacuum-drying for 0.5h, adding 50mL of anhydrous ether under the protection of argon, fully stirring to dissolve, and then transferring into a low temperature instrument at-70 ℃ to keep stirring for 10 min; slowly adding n-BuLi (1.28M in Pentane,3.81mL,4.88mmol,2.5eq) dropwise, and reacting for 2h at-70 ℃; pinacol diboron (0.39mL,1.95mmol,1eq) was added under argon, warmed slowly to room temperature and stirred for 8 h. 2mL of CH was added3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. After column chromatography (silica gel: 200 meshes, 300 meshes, eluent: PE, EA: PE: 1:10), the compound was isolated as an off-white solid (6450mg), with a yield of 52.4% and a Mp of 156.6-158.5 ℃.
(2) Preparation of 2-trimethylsilyl-5- (6-trimethylsilyl-dithieno [2,3-b:2',3' -d ] thiophene-3) dithieno [3,2-b:2',3' -d ] thiophene (5) according to the following reaction equation:
the specific method comprises the following steps: compound 3(158mg,0.4mmol), compound 4(414mg,1.2mmol,3.0eq), palladium acetate (1.4mg,0.0012mmol,0.003eq), Na2CO3(0.4mmol,1eq) was added to dry 25mL of a Schlenk, dried under vacuum for 0.5h, 10mL of anhydrous toluene, 0.2mL of anhydrous water, and reacted at 100 ℃ for 14 h. The solvent was removed and 30mL of saturated NaHCO was added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was separated by column chromatography (silica gel: 300-400 mesh, dry-loading, eluent: PE) to give the compound 5(122mg) as a white solid in a yield of 61% and Mp:275.7-277.8 ℃.
(3) Preparation of bis-TMS substituted unsymmetrical heptathiophenes (1), the reaction equation is as follows:
compound 5(58mg,0.11mmol) was added to dry 100mL Schlenk, dried for 1.0h, and 35mL of anhydrous Et was added2O, fully stirring to dissolve the O, and transferring the O into a low temperature instrument at the temperature of 70 ℃ below zero to keep stirring for 10 min; LDA (0.22mmol,2.0eq) is added dropwise, reaction is carried out at 70 ℃ for 2h, and drying (PhSO) is added rapidly under the protection of argon2)2S (43.4mg,0.14mmol,1.2eq), was slowly warmed to room temperature and reacted for 8 h. 2mL of CH was added at low temperature3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was purified by PTLC to give compound 1(20mg) as a white solid, yield: 34%, Mp:>300℃。
example 3
The embodiment provides a preparation method of bis-TMS substituted asymmetric heptathiophene, which comprises the following steps:
(1) preparation of 6-trimethylsilyl-3-pinacol ester-dithieno [2,3-b:2',3' -d ] thiophene (3), the reaction equation is as follows:
the specific method comprises the following steps: adding compound 2(679mg,1.95mmol) into dried 100mL Schlenk, vacuum drying for 0.5h, adding 50mL anhydrous diethyl ether under the protection of argon, stirring thoroughly to dissolve, transferring into a-90 deg.C cryostat, and stirring for 20 min; slowly adding t-BuLi (1.28M in Pentane,3.2mL,4.10mmol,2.1eq) dropwise, and reacting for 5h at 90 ℃; isopropanol pinacol borate (0.59mL,2.93mmol,1.5eq) was added under argon, the mixture was allowed to warm to room temperature slowly and stirred for 14 h. 2mL of CH was added3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The compound was isolated by column chromatography (silica gel: 200 meshes, 300 meshes, eluent: PE, and then EA: PE: 1:10) as an off-white solid (6998mg), yield: 57%, Mp:156.5-158.5 ℃.
(2) Preparation of 2-trimethylsilyl-5- (6-trimethylsilyl-dithieno [2,3-b:2',3' -d ] thiophene-3) dithieno [3,2-b:2',3' -d ] thiophene (5) according to the following reaction equation:
the specific method comprises the following steps: compound 3(157mg,0.4mmol), compound 4(138mg,0.4mmol,1.0eq), Pd (PPh)3)4(4.67mg,0.004mmol,0.01eq)，CsCO3(2.0mmol,5eq) was added to a dry 25mL Schlenk, dried under vacuum for 0.5h, and reacted with 10mL of a mixed solvent of anhydrous THF and toluene (volume ratio 1:1), 0.4mL of anhydrous water, at 110 ℃ for 8 h. The solvent was removed and 30mL of saturated NaHCO was added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was separated by column chromatography (silica gel: 300-400 mesh, dry-loading, eluent: PE) to give white solid compound 5(141mg), yield: 71%, Mp:275.7-277.8℃。
(3) Preparation of bis-TMS substituted unsymmetrical heptathiophenes (1), the reaction equation is as follows:
compound 5(58mg,0.11mmol) was added to dry 100mL Schlenk, dried for 1.0h, and 35mL of anhydrous Et was added2O, fully stirring to dissolve the O, and transferring the O into a low temperature instrument at the temperature of 90 ℃ below zero to keep stirring for 20 min; LDA (0.43mmol,4.0eq) is added dropwise, the mixture reacts at 90 ℃ for 5 hours, and the mixture is rapidly added with dry (PhSO) under the protection of argon2)2S (36mg,0.11mmol,1.0eq), was slowly warmed to room temperature and reacted for 14 h. 2mL of CH was added at low temperature3The reaction was quenched with OH, the solvent removed, and 30mL of saturated NaHCO added3Solution with 4X 15mL CH2Cl2The aqueous phase was extracted, the organic phases combined and washed with 3X 15mL of H2O washing the organic phase, anhydrous MgSO4Fully drying, filtering and removing the solvent to obtain a crude product. The crude product was purified by PTLC to give compound 1(17mg) as a white solid, yield: 29%, Mp:>300℃。
in light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An intermediate compound for preparing asymmetric seven-membered fused thiophene, which is characterized in that the structural formula is shown in the specification
Wherein TMS is trimethylsilyl.
2. A process for the preparation of an intermediate compound as claimed in claim 1, comprising the steps of:
in that
Adding organic solvent and oxygen-free water into tetratriphenylphosphine palladium or palladium acetate and carbonate, heating for reaction, and post-treating after reaction to obtain
3. The method according to claim 2, wherein the carbonate is K2CO3、Na2CO3、CsCO3The organic solvent is THF, toluene or a mixed solvent of THF and toluene, the reaction temperature is 100-110 ℃, and the reaction time is 8-14 h.
4. The method of claim 2 or 3, wherein the method comprises
The molar ratio of the tetrakistriphenylphosphine palladium or palladium acetate to the carbonate is 1:1-3:0.003-0.01:1-5, and the volume ratio of the organic solvent to the oxygen-free water is 2.5-5: 1.
5. The method of claim 2 or 3, further comprising
The preparation method comprises the following steps:
will be provided with
Adding an organic solvent for dissolving under the protection of inert gas, and keeping stirring at-70-90 ℃ for 10-20 min; dropping alkyl lithium to react at-70-90 deg.c; adding under the protection of inert gasSlowly raising the temperature of pinacol boric acid ester to room temperature for reaction; adding quenching agent to quench the reaction, and treating to obtain
6. The method of claim 5, wherein the step of applying the coating comprises applying a coating to the substrate
The molar ratio of the alkyl lithium to the pinacol borate is 1:2.1-2.5:1-1.5, the organic solvent is an ether solvent, the alkyl lithium is t-BuLi or n-BuLi, the pinacol borate is isopropanol pinacol borate or diboron pinacol ester, the reaction time after the alkyl lithium is added is 2-5 hours, and the reaction time after the pinacol borate is added is 8-14 hours.
7. An asymmetric seven-membered fused thiophene characterized by the structure:
wherein TMS is trimethylsilyl.
8. A method for producing an asymmetric seven-membered fused thiophene according to claim 7, comprising the steps of:
will be provided with
Adding organic solvent for dissolving, and stirring at-70 deg.C to 90 deg.C for 10-20 min; LDA is added dropwise to react at-70 ℃ to 90 ℃; adding (PhSO) under the protection of inert gas2)2S, heating to room temperature for reaction; adding quenching agent to quench reaction, and performing post-treatment after the reaction to obtain
9. According toThe method of claim 8, wherein the step of preparing the composition is carried out in the presence of a catalyst
LDA、(PhSO2)2The molar ratio of S is 1:2-4:1-1.2, the reaction time after LDA is added is 2-5h, and (PhSO) is added2)2The reaction time after S is 8-14 h.
10. The asymmetric seven-membered fused thiophene according to claim 7, as an organic semiconductor material, for use in organic light emitting diodes, organic field effect transistors and organic solar cells.
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