CN108864143B - 一种非对称七元稠合噻吩及其制备方法和应用 - Google Patents
一种非对称七元稠合噻吩及其制备方法和应用 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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Abstract
本发明涉及一种非对称七元稠合噻吩及其制备方法和应用,制备方法为:S1:将3‑溴‑6‑三甲基硅基‑二噻吩并[2,3‑b:2',3'‑d]噻吩先经烷基锂溴锂交换,再加频哪醇硼酸酯反应,制备6‑三甲基硅基‑3‑频哪醇酯基‑二噻吩并[2,3‑b:2',3'‑d]噻吩;S2:将S1的产物与5‑溴‑2‑三甲基硅基‑二噻吩并[3,2‑b:2',3'‑d]噻吩经Suzuki偶联制备2‑三甲基硅基‑5‑(6‑三甲基硅基‑二噻吩并[2,3‑b:2',3'‑d]噻吩‑3)二噻吩并[3,2‑b:2',3'‑d]噻吩;S3:将S2的产物经LDA去质子化、(PhSO2)2S硫代关环制备非对称并七噻吩。本发明的非对称七元稠合噻吩可以作为有机半导体材料在有机发光二极管、有机场效应晶体管和有机太阳能电池中应用。
Description
技术领域
本发明涉及一种非对称七元稠合噻吩及其制备方法和应用,属于有机化合物的制备技术领域。
背景技术
稠合噻吩类化合物是一类由噻吩单元通过芳环稠合形成的噻吩低聚物。目前,稠合噻吩类化合物作为有机半导体材料,已被应用于有机发光二极管、有机场效应晶体管和有机太阳能电池。基于并三噻吩合成的低聚噻吩(并四噻吩以及并五噻吩及其衍生物)已经在有机光电领域展现出诱人的应用前景。并七噻吩作为一类典型的稠合噻吩低聚物,具有多种形式的分子构型,如:螺旋型、牛角型以及线型等。相对于并三噻吩和并五噻吩,并七噻吩的共轭体系更大,有望展示出更加优异的光电性质。由于并七噻吩结构中S原子的位置异构和分子骨架异构,存在多种同分异构体,这些同分异构体可以表现出多种分子间作用力,而这些作用力的存在可能影响着分子间的堆积方式,进而影响着材料的光电性能。目前已报道的并七噻吩有直线型、螺旋型以及牛角型等对称结构分子。
直线型并七噻吩通过经BuLi溴锂交换TIPS基团保护制得 经LDA溴迁移制备再与(Bu3Sn)2S,Pd(PPh3)4在130℃反应24h,通过自身偶联制得该偶联产物经BuLi去质子化CuCl2关环制得
牛角型并七噻吩通过经LDA去质子化TMS基团保护,NBS溴代,LDA溴迁移制得在K3PO4,Pd[PtBu3]2作用下自身偶联制得该偶联产物经LDA去质子化,二苯磺酰硫醚((PhSO2)2S)关环制得
发明内容
本发明要解决的技术问题是:为解决现有技术中只有对称型并七噻吩同分异构体被合成的技术问题,提供一种新型的非对称七元稠合噻吩及其制备方法和应用,为非对称并七噻吩的发展奠定基础,以提供更多高性能的有机半导体材料。
本发明解决其技术问题所采用的技术方案是:
具体是:
将加入有机溶剂溶解后,在-70℃-90℃下保持搅拌10-20min;滴加入LDA,-70℃-90℃下反应;在惰性气体保护保护下加入(PhSO2)2S,升至室温反应;加入淬灭剂淬灭反应,反应后经后处理得
具体为:
优选地,所述碳酸盐为K2CO3、Na2CO3、CsCO3,所述有机溶剂为THF、甲苯或THF与甲苯的混合溶剂,反应温度为100-110℃,反应时间为8-14h,所述 四三苯基磷钯或醋酸钯、碳酸盐的摩尔比为1:1-3:0.003-0.01:1-5,有机溶剂与无氧水的体积比为2.5-5:1。
具体为:
优选地,所述烷基锂、频哪醇硼酸酯的摩尔比为1:2.1-2.5:1-1.5,所述有机溶剂为醚类溶剂,所述烷基锂为t-BuLi或n-BuLi,所述频哪醇硼酸酯为异丙醇频哪醇硼酸酯或联硼酸频哪醇酯,加入烷基锂后的反应时间为2-5h,加入频哪醇硼酸酯后的反应时间为8-14h。
本发明还提供一种非对称七元稠合噻吩作为有机半导体材料在有机发光二极管、有机场效应晶体管和有机太阳能电池中应用。
本发明非对称稠合七元噻吩的制备过程中,于两种不同结构的二噻吩并噻吩构筑模块的交叉偶联是关键步骤,采用常用的溴锂交换、氯化铜偶联会产生三种偶联产物,即两种自身偶联产物及一种交叉偶联产物,三种产物的溶解性及极性均非常接近,导致交叉偶联产物产率低且难以纯化。通过Negishi Coupling反应同样也出现了三种偶联产物,产率较低。通过多种尝试,最终获得最佳反应条件就是将非对称的制备成再通过Suzuki Coupling高效获得交叉偶联产物
本发明的有益效果是:
(1)本发明采用全新的方法来合成非对称七元稠合噻吩,将制备成再通过Suzuki Coupling高效获得交叉偶联产物避免了自身偶联产物副产物的产生,获得了较高收率,最终经LDA去质子化,二苯磺酰硫醚((PhSO2)2S)硫代关环制备双TMS取代的非对称并七噻吩。
(2)本发明制备的全新的非对称七元稠合噻吩可以作为作为有机半导体材料应用于有机发光二极管、有机场效应晶体管和有机太阳能电池中,具有优良的性能,在基底温度为室温时获得的性能为:迁移率为0.02cm2/V·s,阈值电压为-48V,开关比为105。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1为本发明实施例1所涉及化合物3的核磁共振氢谱图;
图2为本发明实施例1所涉及化合物3的核磁共振碳谱图;
图3为本发明实施例1所涉及化合物3的高分辨质谱图;
图4为本发明实施例1所涉及化合物3的红外光谱图;
图5为本发明实施例1所涉及化合物5的核磁共振氢谱图;
图6为本发明实施例1所涉及化合物5的核磁共振碳谱图;
图7为本发明实施例1所涉及化合物5的高分辨质谱图;
图8为本发明实施例1所涉及化合物5的红外光谱图;
图9为本发明实施例1所涉及化合物1的核磁共振氢谱图;
图10为本发明实施例1所涉及化合物1的核磁共振碳谱图;
图11为本发明实施例1所涉及化合物1的高分辨质谱图;
图12为本发明实施例1所涉及化合物1的红外光谱图。
具体实施方式
现在通过实施例对本发明作进一步详细的说明。
实施例1
本实施例提供一种双TMS取代的非对称并七噻吩的制备方法,包括如下步骤:
(1)6-三甲基硅基-3-频哪醇酯基-二噻吩并[2,3-b:2',3'-d]噻吩(3)的制备,反应方程式如下:
具体方法为:将化合物2(679mg,1.95mmol)加入到干燥的100mL Schlenk中,真空干燥0.5h,氩气保护下加入50mL无水***,充分搅拌使其溶解后,转入-78℃低温仪中保持搅拌10min;缓慢滴加t-BuLi(1.28M in Pentane,3.2mL,4.10mmol,2.1eq),-78℃反应2h;氩气保护下加入异丙醇频哪醇硼酸酯(0.47mL,2.34mmol,1.2eq),缓慢升至室温,搅拌10h。加入2mL CH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除去溶剂得粗品。经柱层析(硅胶:200-300目,淋洗液:PE,后用EA:PE=1:10)分离得化合物灰白色固体(6399mg),产率:52%,Mp:156.7-158.5℃。1H NMR(400MHz,CDCl3):7.73(s,1H),7.43(s,1H),1.37(s,12H),0.37(s,9H);13C NMR(100MHz,CDCl3)δ: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)2-三甲基硅基-5-(6-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩-3)二噻吩并[3,2-b:2',3'-d]噻吩的制备(5),反应方程式如下:
具体方法为:将化合物3(157mg,0.4mmol),化合物4(138mg,0.4mmol,1.0eq),Pd(PPh3)4(1.4mg,0.0012mmol,0.003eq),K2CO3(138mg,1.0mmol,2.5eq)加入到干燥的25mLSchlenk中,真空干燥0.5h,加入10mL无水THF,0.4mL无氧水,105℃反应10h。除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经柱层析(硅胶:300-400目,干法上样,淋洗液:PE)分离得白色固体化合物5(132mg),产率:66%,Mp:275.8-277.8℃。1H NMR(400MHz,CDCl3,δ):7.71(s,1H),7.67(s,1H),7.46(s,1H),7.42(s,1H),0.40(s,18H);13CNMR(100MHz,CDCl3,δ):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)双TMS取代的非对称并七噻吩(1)的制备,反应方程式如下:
将化合物5(59mg,0.11mmol)加入到干燥100mL Schlenk中,真干燥1.0h,加入35mL无水Et2O,充分搅拌使其溶解,转入-78℃低温仪中保持搅拌10min;滴加入LDA(0.43mmol,4.0eq),-78℃反应2h,在氩气保护下迅速加入干燥(PhSO2)2S(38mg,0.12mmol,1.05eq),缓慢升至室温,反应10h。低温下加入2mL CH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经PTLC纯化得白色固体化合物1(19mg),产率:32%,Mp:>300℃。1H NMR(400MHz,CDCl3,δ):7.42(s,2H),0.41(s,18H);13C NMR(100MHz,CDCl3,δ):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;found563.9143。
双TMS取代的非对称并七噻吩(1)在基底温度为室温时获得的性能为:迁移率为0.02cm2/V·s,阈值电压为-48V,开关比为105,具有优良的性能,可以作为作为有机半导体材料应用于有机发光二极管、有机场效应晶体管和有机太阳能电池中。
实施例2
本实施例提供一种双TMS取代的非对称并七噻吩的制备方法,包括如下步骤:
(1)6-三甲基硅基-3-频哪醇酯基-二噻吩并[2,3-b:2',3'-d]噻吩(3)的制备,反应方程式如下:
具体方法为:将化合物2(678mg,1.95mmol)加入到干燥的100mL Schlenk中,真空干燥0.5h,氩气保护下加入50mL无水***,充分搅拌使其溶解后,转入-70℃低温仪中保持搅拌10min;缓慢滴加n-BuLi(1.28M in Pentane,3.81mL,4.88mmol,2.5eq),-70℃反应2h;氩气保护下加入联硼酸频哪醇酯(0.39mL,1.95mmol,1eq),缓慢升至室温,搅拌8h。加入2mLCH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除去溶剂得粗品。经柱层析(硅胶:200-300目,淋洗液:PE,后用EA:PE=1:10)分离得化合物灰白色固体(6450mg),产率:52.4%,Mp:156.6-158.5℃。
(2)2-三甲基硅基-5-(6-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩-3)二噻吩并[3,2-b:2',3'-d]噻吩的制备(5),反应方程式如下:
具体方法为:将化合物3(158mg,0.4mmol),化合物4(414mg,1.2mmol,3.0eq),醋酸钯(1.4mg,0.0012mmol,0.003eq),Na2CO3(0.4mmol,1eq)加入到干燥的25mLSchlenk中,真空干燥0.5h,加入10mL无水甲苯,0.2mL无氧水,100℃反应14h。除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经柱层析(硅胶:300-400目,干法上样,淋洗液:PE)分离得白色固体化合物5(122mg),产率:61%,Mp:275.7-277.8℃。
(3)双TMS取代的非对称并七噻吩(1)的制备,反应方程式如下:
将化合物5(58mg,0.11mmol)加入到干燥100mL Schlenk中,真干燥1.0h,加入35mL无水Et2O,充分搅拌使其溶解,转入-70℃低温仪中保持搅拌10min;滴加入LDA(0.22mmol,2.0eq),-70℃反应2h,在氩气保护下迅速加入干燥(PhSO2)2S(43.4mg,0.14mmol,1.2eq),缓慢升至室温,反应8h。低温下加入2mL CH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经PTLC纯化得白色固体化合物1(20mg),产率:34%,Mp:>300℃。
实施例3
本实施例提供一种双TMS取代的非对称并七噻吩的制备方法,包括如下步骤:
(1)6-三甲基硅基-3-频哪醇酯基-二噻吩并[2,3-b:2',3'-d]噻吩(3)的制备,反应方程式如下:
具体方法为:将化合物2(679mg,1.95mmol)加入到干燥的100mL Schlenk中,真空干燥0.5h,氩气保护下加入50mL无水***,充分搅拌使其溶解后,转入-90℃低温仪中保持搅拌20min;缓慢滴加t-BuLi(1.28M in Pentane,3.2mL,4.10mmol,2.1eq),-90℃反应5h;氩气保护下加入异丙醇频哪醇硼酸酯(0.59mL,2.93mmol,1.5eq),缓慢升至室温,搅拌14h。加入2mL CH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除去溶剂得粗品。经柱层析(硅胶:200-300目,淋洗液:PE,后用EA:PE=1:10)分离得化合物灰白色固体(6998mg),产率:57%,Mp:156.5-158.5℃。
(2)2-三甲基硅基-5-(6-三甲基硅基-二噻吩并[2,3-b:2',3'-d]噻吩-3)二噻吩并[3,2-b:2',3'-d]噻吩的制备(5),反应方程式如下:
具体方法为:将化合物3(157mg,0.4mmol),化合物4(138mg,0.4mmol,1.0eq),Pd(PPh3)4(4.67mg,0.004mmol,0.01eq),CsCO3(2.0mmol,5eq)加入到干燥的25mL Schlenk中,真空干燥0.5h,加入10mL无水THF与甲苯的混合溶剂(体积比1:1),0.4mL无氧水,110℃反应8h。除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经柱层析(硅胶:300-400目,干法上样,淋洗液:PE)分离得白色固体化合物5(141mg),产率:71%,Mp:275.7-277.8℃。
(3)双TMS取代的非对称并七噻吩(1)的制备,反应方程式如下:
将化合物5(58mg,0.11mmol)加入到干燥100mL Schlenk中,真干燥1.0h,加入35mL无水Et2O,充分搅拌使其溶解,转入-90℃低温仪中保持搅拌20min;滴加入LDA(0.43mmol,4.0eq),-90℃反应5h,在氩气保护下迅速加入干燥(PhSO2)2S(36mg,0.11mmol,1.0eq),缓慢升至室温,反应14h。低温下加入2mL CH3OH淬灭反应,除出溶剂,加入30mL饱和NaHCO3溶液,用4×15mL CH2Cl2萃取水相,合并有机相,用3×15mL H2O洗涤有机相,无水MgSO4充分干燥、过滤、除出溶剂得粗品。粗品经PTLC纯化得白色固体化合物1(17mg),产率:29%,Mp:>300℃。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (10)
3.根据权利要求2所述的制备方法,其特征在于,所述碳酸盐为K2CO3、Na2CO3、CsCO3,所述有机溶剂为THF、甲苯或THF与甲苯的混合溶剂,反应温度为100-110℃,反应时间为8-14h。
10.权利要求7所述的非对称七元稠合噻吩作为有机半导体材料在有机发光二极管、有机场效应晶体管和有机太阳能电池中应用。
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