C3-非对称杂环并苯并菲及其衍生物的合成与研究

发布时间：2018-08-23 10:06

【摘要】：近年来杂环稠合多环芳香族化合物的合成与应用受到人们越来越多的关注,它们在有机半导体器件中的应用引起人们广泛的兴趣,如在有机场效应晶体管、有机光伏电池等领域中的应用。杂环稠合多环芳香族化合物具有场效应晶体管迁移率高,电流开关比大,溶解性好的优点。鉴于杂环稠合多环芳香族化合物具有良好的光电性能,我们就设计并完合成了一系列杂环并苯并菲类化合物。这类化合物的特点是都以苯并菲为母核,且均拥有C3-非对称结构,其中杂原子包括O,N,S。以苯并菲为母核合成的一系列化合物都拥有比较大的共轭体系。论文的第一部分是C3-非对称三呋喃/三噻吩并苯并菲其衍生物的合成研究。关键前驱物2,6,11-三卤代-3,7,10-三甲氧基苯并菲是以邻溴苯甲醚或邻氯苯甲醚为原料,在浓硫酸为催化剂和氯化铁为氧化剂作用下,通过三聚生成非对称苯并菲类化合物2,6,11-三卤代-3,7,10-三甲氧基苯并菲;对于C3-非对称苯并菲并呋喃及其衍生物的合成,以2,6,11-三溴代-3,7,10-三甲氧基苯并菲为原料,三溴化硼脱去甲基生成2,6,11-三溴代-3,7,10-三羟基苯并菲,用醋酐保护酚羟基得到的酰化产物与一系列炔烃进行钯催化Sonogashira偶联反应,其产物在碳酸铯的作用下关环得到;而C3-非对称苯并菲并噻吩及其衍生物是以2,6,11-三氯代-3,7,10-三甲氧基苯并菲出发,经三溴化硼脱去甲基形成2,6,11-三氯代-3,7,10-三羟基苯并菲,与三氟甲磺酸酐转换成磺酸酯后和一系列炔烃通过钯催化Sonogashira偶联反应,其产物最后在九水合硫化钠存在下关环得到目标产物。论文的第二部分是以2,6,11-三溴-3,7,10-三甲氧基苯并菲为原料合成一系列的异三聚咔唑/异三聚二苯并呋喃/异三聚二苯并噻吩衍生物。(1)以2,6,11-三溴-3,7,10-三甲氧基苯并菲与邻甲氧基苯硼酸在Pd132的作用下进行Suzuki偶联得到具有六个甲氧基的中间体,然后在三溴化硼作用下脱去甲基得到联苯结构的六个酚羟基化合物,将酚羟基化合物与三氟甲磺酸酐反应得到磺酸酯后与一系列的苯胺类化合物进行Buchwald-Hartwig反应得到异三聚咔唑类化合物;(2)以2,6,11-三溴-3,7,10-三甲氧基苯并菲为原料与邻氯苯硼酸在催化剂Pd132的作用下进行Suzuki偶联,接着在三溴化硼作用下脱去甲氧基,最后关环得到异三聚二苯并呋喃化合物。或者以2,6,11-三溴-3,7,10-三甲氧基苯并菲为原料,首先用三溴化脱去甲基保护基,接着与邻氟苯腈在碳酸铯存在下醚化,其产物在Pd(OAc)2/K2C03体系下进行C-H活化作用,生成三氰基取代的异三聚二苯并呋喃衍生物;(3)以2,6,11-三溴-3,7,10-三甲氧基苯并菲为原料与邻氟苯硼酸在Pd132催化下发生Suzuki偶联反应,然后三溴化硼脱去甲基生成3,7,10-三(2-氟苯基)-2,6,11-三羟基苯并菲,再与三氟甲磺酸酐发生磺化反应,磺化产物再与巯基丙酸乙酯发生反应,最后用叔丁醇钾关环得到异三聚二苯并噻吩。
[Abstract]:In recent years, more and more attention has been paid to the synthesis and application of heterocyclic polycyclic aromatic compounds. Their applications in organic semiconductor devices have attracted widespread interest, such as in the presence of airfield effect transistors. Organic photovoltaic cells and other applications in the field. Heterocyclic polycyclic aromatic compounds have the advantages of high mobility, high current switching ratio and good solubility. A series of heterocyclic phenanthrene compounds have been designed and synthesized in view of their good optoelectronic properties. The characteristic of these compounds is that all of them have a C _ 3-asymmetric structure, and all of them have C _ 3-asymmetric structure. A series of compounds synthesized with Benzo phenanthrene as parent nucleus all have relatively large conjugated systems. The first part of this paper is about the synthesis of C _ 3-asymmetric trifuran / trithiophene phenanthrene derivatives. The key precursor, 2O6, 11- trihalogen-3-trimethoxybenzofen, was prepared from o-bromophenyl ether or o-chlorophenyl ether with concentrated sulfuric acid as catalyst and ferric chloride as oxidant. Asymmetric benzophenanthrene 2o 6n 11- trihalogenated -3 haloanilo-10 trimethoxy benzophenanthrene was synthesized by trimerization, and the synthesis of C 3 asymmetric benzophenanthroline furan and its derivatives was carried out by means of 2 '611- tribromo-trimethoxybenzophenanthene (TMEB), which was used as raw material for the synthesis of C3- asymmetric benzofuran and its derivatives, and was used as the raw material for the synthesis of C3- asymmetric benzofuran. The demethylation of boron tribromoxide (BBS) was carried out to form 2n 6n 11- tribromo-3H 710-trihydroxy benzofen. Palladium catalyzed Sonogashira coupling reaction of acylated products from phenolic hydroxyl groups protected by acetic anhydride with a series of alkynes was carried out, and the products were obtained in the ring under the action of cesium carbonate. C _ 3- asymmetric benzophenothiophene and its derivatives were prepared by the demethylation of boron tribromoxide to form 2 ~ (611) -trichlorophenyl -7 ~ (10) -trihydroxy benzophenanthrene, and their derivatives were obtained by the demethylation of boron tribromoxide (B _ (3). After conversion from trifluoromethyl sulfonic anhydride to sulfonic acid ester, a series of alkynes were coupled with a series of alkynes through palladium catalyzed Sonogashira coupling reaction. Finally, the target product was obtained in the presence of sodium sulfide nine-hydrate. The second part of the thesis is the synthesis of a series of isotripolycarbazole / isotripolybenzofuran / isotripolydibenzothiophene derivatives from 2O6O6-TIBROMO-3BROMO-710TIMETHYXYBENZHENYL. (1) using 2O6O6-TIBROMO-3710- TIMETHYLBENE and o-TYDROXYBENE as raw materials. The intermediates with six methoxy groups were obtained by Suzuki coupling of methoxy phenylboric acid with the action of Pd132. Six phenolic hydroxyl compounds with biphenyl structure were obtained by demethylation with boron tribromide. The phenolic hydroxyl compounds reacted with trifluoromethyl sulfonic anhydride to obtain sulfonates and then reacted with a series of anilines to obtain isotripolycarbazole compounds. (2) using 2O6O6-tribromo-3-trimethoxybenzophenanthrene as raw material and o-chlorobenzene boron as the raw material, iso-tripolycarbazole compounds were obtained by the reaction of phenolic hydroxyl compounds with trifluoromethyl sulfonic anhydride. Acid was coupled by Suzuki under the action of catalyst Pd132. Then the methoxy group was removed under the action of boron tribromide, and finally the iso-tripolybenzofuran compound was obtained by closing the ring. In addition, the product was activated by C-H in the presence of cesium carbonate, and demethylated with tribrominated benzophenanthroline, which was used as a raw material for the removal of methyl protection group by tribromination, and the product was activated by C-H in the presence of cesium carbonate, and the product was activated by C-H in the presence of cesium carbonate. A tricyano-substituted isotripolydibenzofuran derivative was synthesized. (3) Suzuki coupling reaction took place with o-fluoroborate boric acid under the catalysis of Pd132. Then the tribromoboron demethylated to form 3o 7N 10 tris (2 fluorophenyl) -2N 611 trihydroxy benzophenanthrene, then sulfonated with trifluoromethyl sulfonic anhydride, and then the sulfonation product reacts with ethyl mercaptopropionate. Finally, isotrimeric dibenzothiophene was obtained by closing the ring of potassium tert-butanol.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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