【摘要】：近年來雜環(huán)稠合多環(huán)芳香族化合物的合成與應(yīng)用受到人們?cè)絹碓蕉嗟年P(guān)注,它們?cè)谟袡C(jī)半導(dǎo)體器件中的應(yīng)用引起人們廣泛的興趣,如在有機(jī)場(chǎng)效應(yīng)晶體管、有機(jī)光伏電池等領(lǐng)域中的應(yīng)用。雜環(huán)稠合多環(huán)芳香族化合物具有場(chǎng)效應(yīng)晶體管遷移率高,電流開關(guān)比大,溶解性好的優(yōu)點(diǎn)。鑒于雜環(huán)稠合多環(huán)芳香族化合物具有良好的光電性能,我們就設(shè)計(jì)并完合成了一系列雜環(huán)并苯并菲類化合物。這類化合物的特點(diǎn)是都以苯并菲為母核,且均擁有C3-非對(duì)稱結(jié)構(gòu),其中雜原子包括O,N,S。以苯并菲為母核合成的一系列化合物都擁有比較大的共軛體系。論文的第一部分是C3-非對(duì)稱三呋喃/三噻吩并苯并菲其衍生物的合成研究。關(guān)鍵前驅(qū)物2,6,11-三鹵代-3,7,10-三甲氧基苯并菲是以鄰溴苯甲醚或鄰氯苯甲醚為原料,在濃硫酸為催化劑和氯化鐵為氧化劑作用下,通過三聚生成非對(duì)稱苯并菲類化合物2,6,11-三鹵代-3,7,10-三甲氧基苯并菲;對(duì)于C3-非對(duì)稱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為原料,三溴化硼脫去甲基生成2,6,11-三溴代-3,7,10-三羥基苯并菲,用醋酐保護(hù)酚羥基得到的酰化產(chǎn)物與一系列炔烴進(jìn)行鈀催化Sonogashira偶聯(lián)反應(yīng),其產(chǎn)物在碳酸銫的作用下關(guān)環(huán)得到;而C3-非對(duì)稱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發(fā),經(jīng)三溴化硼脫去甲基形成2,6,11-三氯代-3,7,10-三羥基苯并菲,與三氟甲磺酸酐轉(zhuǎn)換成磺酸酯后和一系列炔烴通過鈀催化Sonogashira偶聯(lián)反應(yīng),其產(chǎn)物最后在九水合硫化鈉存在下關(guān)環(huán)得到目標(biāo)產(chǎn)物。論文的第二部分是以2,6,11-三溴-3,7,10-三甲氧基苯并菲為原料合成一系列的異三聚咔唑/異三聚二苯并呋喃/異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與鄰甲氧基苯硼酸在Pd132的作用下進(jìn)行Suzuki偶聯(lián)得到具有六個(gè)甲氧基的中間體,然后在三溴化硼作用下脫去甲基得到聯(lián)苯結(jié)構(gòu)的六個(gè)酚羥基化合物,將酚羥基化合物與三氟甲磺酸酐反應(yīng)得到磺酸酯后與一系列的苯胺類化合物進(jìn)行Buchwald-Hartwig反應(yīng)得到異三聚咔唑類化合物;(2)以2,6,11-三溴-3,7,10-三甲氧基苯并菲為原料與鄰氯苯硼酸在催化劑Pd132的作用下進(jìn)行Suzuki偶聯(lián),接著在三溴化硼作用下脫去甲氧基,最后關(guān)環(huán)得到異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為原料,首先用三溴化脫去甲基保護(hù)基,接著與鄰氟苯腈在碳酸銫存在下醚化,其產(chǎn)物在Pd(OAc)2/K2C03體系下進(jìn)行C-H活化作用,生成三氰基取代的異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為原料與鄰氟苯硼酸在Pd132催化下發(fā)生Suzuki偶聯(lián)反應(yīng),然后三溴化硼脫去甲基生成3,7,10-三(2-氟苯基)-2,6,11-三羥基苯并菲,再與三氟甲磺酸酐發(fā)生磺化反應(yīng),磺化產(chǎn)物再與巰基丙酸乙酯發(fā)生反應(yīng),最后用叔丁醇鉀關(guān)環(huán)得到異三聚二苯并噻吩。
[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.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626

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本文編號(hào)：2198722