本文選題：磺酰肼 + 自由基串聯(lián)環(huán)化�。� 參考：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：砜和硫醚化合物大量存在于天然產(chǎn)物和藥物分子中,另外在作為合成中間體也具有廣泛的應(yīng)用。近年來發(fā)展的磺酰肼作為硫醚化試劑,由于其一般是固體,具有對水不敏感、操作簡單、無難聞氣味等優(yōu)點,通過形成S-C鍵來得到硫醚,進(jìn)而能夠與各種有機化合物反應(yīng)。然而與磺酰肼發(fā)生眾多的反應(yīng)類型相比,N-羥基磺酰胺發(fā)生的反應(yīng)類型則較少,尤其是作為砜基化試劑。此外N-羥基磺酰胺作為硫醚化試劑則還未有報道。為了拓展磺酰肼作為硫醚化試劑在有機反應(yīng)中的應(yīng)用,以及發(fā)展N-羥基磺酰胺作為一種前所未有新型的硫醚化試劑和作為砜基化試劑在關(guān)環(huán)反應(yīng)中的應(yīng)用,本文進(jìn)行下面四個工作的探討。本文發(fā)展了磺酰肼作為硫醚化試劑與N-芳基丙烯酰胺在廉價碘催化下的自由基串聯(lián)環(huán)化反應(yīng),選擇性地給出3-硫甲基氧化吲哚和3-硫基-3,4-二氫喹啉-2(1H)-酮。初步的機理研究表明,在早期階段磺酰肼基本上在碘催化下已經(jīng)完全分解為硫代磺酸酯和二硫醚;在后一個階段,這兩個中間體進(jìn)一步在碘催化下與N-芳基丙烯酰胺進(jìn)行自由基串聯(lián)硫醚化/環(huán)化反應(yīng)。利用磺酰肼作為親電硫試劑,本文發(fā)展了氧化吲哚與磺酰肼在碘催化下的5-位硫醚化反應(yīng),選擇性合成了一系列五元和六元雜環(huán)與磺酰肼進(jìn)行硫醚化反應(yīng)。該反應(yīng)具有高度化學(xué)區(qū)域選擇性,以及反應(yīng)綠色,其產(chǎn)生的水和氮氣對環(huán)境友好。本文發(fā)展了 N-羥基磺酰胺在有機合成中的一種新應(yīng)用,即它作為硫醚化試劑與芳香化合物經(jīng)過S=O和S-N鍵的斷裂得到硫醚化合物。在10 mol%的碘和30 mol%的N-羥基丁二酰亞胺的催化下,一系列N-羥基芳基磺酰胺快速地與吲哚,7-氮雜吲哚,N-甲基吡咯或2-萘酚以高度區(qū)域選擇性以及中等到優(yōu)秀的產(chǎn)率構(gòu)建結(jié)構(gòu)多樣化的硫醚。初步的機理研究表明,N-羥基芳基磺酰胺首先分解為亞磺酸,后再與芳香化合物經(jīng)過硫醚化而得到最終產(chǎn)物。利用N-羥基磺酰胺作為砜基化試劑,本文進(jìn)一步發(fā)展了 N-羥基磺酰胺與N-芳基丙烯酰胺以及芳甲酰基甲基丙烯酰亞胺,在廉價硝酸銀和過硫酸鉀共同催化下的自由基串聯(lián)砜基化/環(huán)化反應(yīng),得到一系列結(jié)構(gòu)多樣化的氧化吲哚和異喹啉-1,3(2H,4H)-二酮。
[Abstract]:Sulfone and sulfide compounds are abundant in natural products and drug molecules, and are also widely used as synthetic intermediates. Sulfonyl hydrazide, as a sulfidizing reagent developed in recent years, is generally solid, which has the advantages of being insensitive to water, simple to operate, no smell and so on. The sulfides can be obtained by forming S-C bond, which can react with various organic compounds. However, the reaction types of N-hydroxysulfonamide are less than those of sulfonyl hydrazide, especially as sulfone group reagents. In addition, N-hydroxysulfonamide as a sulfidation reagent has not been reported. In order to expand the application of sulfonyl hydrazide as a sulfidizing reagent in organic reactions, and to develop the application of N-hydroxysulfonamide as an unprecedented new sulfidizing reagent and as sulfone group reagent in the cyclization reaction, This article carries on the following four work discussion. In this paper, a series cyclization reaction of sulfonyl hydrazide with N-aryl acrylamide catalyzed by cheap iodine has been developed. The reaction of 3-thiomethyl oxoindole and 3-thio-4-dihydroquinoline-2 (1H) -one has been selectively given. Preliminary mechanism studies show that sulfonyl hydrazide has been completely decomposed into thiosulfonate and disulfide in the early stage under the catalysis of iodine, while in the latter stage, the sulfonyl hydrazine has been completely decomposed into thiosulfonate and disulfide. The two intermediates were further reacted with N-aryl acrylamide by radical series sulfation / cyclization catalyzed by iodine. Using sulfonyl hydrazine as an electrophilic sulfur reagent, the 5-position sulfidization reaction of indoles and sulfonyl hydrazides catalyzed by iodine was developed. A series of five-member and six-member heterocycles were selectively synthesized for sulfidation with sulfonyl hydrazide. The reaction is highly chemically regioselective and green, and produces water and nitrogen that are environmentally friendly. In this paper, a new application of N-hydroxysulfonamide in organic synthesis has been developed, that is, it is used as a sulfidizing reagent and the aromatic compounds are broken down by Sino and S-N bonds to form sulfides. Catalyzed by 10 mol% iodine and 30 mol% N-hydroxysuccinimide, A series of N-hydroxy-aryl sulfonamide was rapidly constructed with indole 7-azindole-N-methylpyrrole or 2-naphthol with high regioselectivity and intermediate to excellent yields. The preliminary mechanism study shows that N-hydroxy-aryl sulfonamide is first decomposed into sulfonic acid and then sulfided with aromatic compounds to obtain the final product. Using N-hydroxysulfonamide as sulfone, N-hydroxysulfonamide, N-aryl acrylamide and aryl methacrylamide were further developed. A series of oxyindole and isoquinoline -1H _ 3 (2H _ 4H) -diketone were synthesized by series sulfone / cyclization of free radical catalyzed by cheap silver nitrate and potassium persulfate.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.25

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本文編號：2100736