【摘要】：含有異喹啉、二氫異喹啉骨架結(jié)構(gòu)的天然產(chǎn)物和藥物分子大都具有較好的生物活性。異喹啉類(lèi)化合物不僅是許多天然分子和合成小分子的亞結(jié)構(gòu)單元,同時(shí)也是生物堿全合成的重要中間體�；诖�,本論文主要研究通過(guò)多米諾反應(yīng)合成幾類(lèi)異喹啉骨架化合物。1.研究了CuI催化的鄰炔基苯甲醛與鄰氨基苯甲醇多米諾反應(yīng)構(gòu)筑了苯并VA嗪并異喹啉類(lèi)化合物,采用微波輻射加熱方式,相比傳統(tǒng)的油浴加熱方式,反應(yīng)時(shí)間短,操作簡(jiǎn)便,底物適應(yīng)性好,收率中等到良好。2.發(fā)展了兩種合成異喹啉類(lèi)化合物的方法。其一,在硝酸銀的催化下,利用NH4HCO3產(chǎn)生氨源的方法與鄰炔基苯甲醛發(fā)生串聯(lián)反應(yīng)合成異喹啉類(lèi)化合物。在該反應(yīng)的優(yōu)化條下進(jìn)行底物擴(kuò)展,均能以中等至良好的收率得到各種取代的異喹啉。其二,通過(guò)硝酸銀催化/N-N鍵直接斷裂的方法合成異喹啉化合物:鄰炔基苯甲醛與NH2NH2反應(yīng)得到腙,在硝酸銀的催化下發(fā)生成環(huán)反應(yīng),繼而在硝酸銀的作用下發(fā)生N-N斷裂而芳構(gòu)化生成異喹啉類(lèi)化合物。3.發(fā)展了一種基于同一1,3-偶極子底物通過(guò)不同條件得到兩種不同產(chǎn)物的[3+2]環(huán)加成反應(yīng)。鄰炔基苯甲醛在銀的催化下得到1,3-偶極中間體,然后與乙酰乙酸乙酯在DMF/Li2CO3和MeCN/K2CO3體系中,分別得到吡唑并異喹啉甲酯與吡唑并異喹啉乙酯化合物;并且,在DMF/Li2CO3反應(yīng)體系中,由于鋰離子在中間過(guò)渡態(tài)的絡(luò)合作用,得到了單一的反應(yīng)產(chǎn)物,產(chǎn)物的構(gòu)型通過(guò)X-ray單晶衍射得到了確證。
[Abstract]:Most natural products and drug molecules containing isoquinoline and dihydroisoquinoline skeleton have better biological activity. Isoquinoline compounds are not only substructural units of many natural molecules and synthetic small molecules, but also important intermediates for the total synthesis of alkaloids. Based on this, this paper mainly studied the synthesis of several isoquinoline skeleton compounds. 1 through domino reaction. CuI catalyzed domino reaction of o-alkynyl benzaldehyde with o-aminobenzyl methanol was studied in this paper. The benzo VA azide isoquinoline compounds were constructed by microwave irradiation. Compared with the traditional oil bath heating method, the reaction time was shorter and the operation was simple. The substrate has good adaptability and the yield is medium to good. 2. Two methods for the synthesis of isoquinoline compounds have been developed. First, isoquinoline compounds were synthesized by series reaction of o-alkynyl benzaldehyde with o-alkynyl benzaldehyde by using NH4HCO3 to produce ammonia under the catalysis of silver nitrate. When the substrate was expanded under the optimized strip, various substituted isoquinoline could be obtained in moderate to good yield. Secondly, isoquinoline compounds were synthesized by direct breaking of N-N bond catalyzed by silver nitrate: o-alkynyl benzaldehyde reacted with NH2NH2 to obtain Hydrazone, which formed a ring reaction under the catalysis of silver nitrate. Then N-N breaks under the action of silver nitrate and aromatization to form isoquinoline compounds. 3. A [32] cycloaddition reaction based on the same 1n 3- dipole substrate was developed to obtain two different products under different conditions. In the system of DMF/Li2CO3 and MeCN/K2CO3, pyrazolyl isoquinolinyl methyl ester and pyrazolium isoquinolinyl ethyl ester were obtained respectively, and in the system of DMF/Li2CO3, in the system of DMF/Li2CO3 reaction, the intermediate was obtained from o-alkynyl benzaldehyde under the catalysis of silver, and then with ethyl acetoacetate in the system of MeCN/K2CO3 and pyrazolyl isoquinolinyl methyl ester. Due to the complexation of lithium ions in the intermediate transition state, a single product was obtained. The configuration of the product was confirmed by X-ray single crystal diffraction.
【學(xué)位授予單位】：湖南科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O626.323

【參考文獻(xiàn)】

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1 高鵬;韓家軍;朱永明;張翠芬;李寧;;金屬鋰二次電池鋰負(fù)極改性[J];化學(xué)進(jìn)展;2009年Z2期

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本文編號(hào)：2256578