二茂铁基吡唑啉衍生物的合成及其性质研究
发布时间：2018-10-30 14:56
【摘要】：本论文结合了二茂铁和吡唑啉杂环化合物的双重特性,将二茂铁基引入吡唑啉化合物中,设计合成了一些新型的二茂铁基吡唑啉衍生物,并对目标化合物进行了结构表征、紫外和荧光活性测试,对目标化合物的电化学性质也进行了研究。这对二茂铁基吡唑啉类杂环化合物的合成及其应用研究都具有极为重要的理论意义和现实意义。本论文的主要工作:1.以4种苯乙酮衍生物和苯肼为原料合成4种苯乙酮苯腙,在微波条件下经Vilsmeier-Haack反应生成中间体4种4-甲酰基吡唑。然后二茂铁与乙酰氯在AlCl3的催化下生成1,1'-二茂铁二乙酮,将其分别与4-甲酰基吡唑为反应原料,以NaOH溶液为催化剂,添加四丁基溴化铵相转移催化剂,在微波条件下合成4种二茂铁双酰烯吡唑衍生物3a-3d。经工艺优化,各目标化合物产率均在84%左右。同样反应条件下,以乙酰基二茂铁和4-甲酰基吡唑合成4种二茂铁单酰烯吡唑衍生物3e-3h。2.以1,1'-二茂铁二乙酮为原料,加入10%的NaClO溶液生成1,1'-二茂铁二乙酸,然后在浓硫酸条件下与甲醇生成1,1'-二茂铁双甲酸甲酯,再与80%的水合肼合成1,1'-二茂铁双甲酰肼,将其分别与4种4-甲酰基吡唑在无水乙醇中,以冰乙酸为催化剂,在微波条件下合成4种二茂铁双酰腙吡唑衍生物4a-4d。经工艺优化,各目标化合物产率均在85%以上。3.以合成的二茂铁双酰烯吡唑衍生物3a-3d为原料与氨基硫脲在乙醇溶液中加入NaOH,微波辐射下回流制得目标化合物5a-5d。经工艺优化,各目标化合物产率均在83%以上。同样反应条件下,以二茂铁单酰烯吡唑衍生物3e-3h合成目标化合物5e-5h。所有目标化合物的结构都经元素分析,1H NMR,IR和MS得以确认。4.各目标化合物的紫外光谱测试显示:二茂铁酰烯吡唑衍生物3a-3h,二茂铁双酰腙吡唑衍生物4a-4d和二茂铁基吡唑啉衍生物5a-5h均在280nm和360nm附近有吸收峰,但各化合物吸收强度却各不相同。各目标化合物的荧光光谱测试显示:二茂铁酰烯吡唑衍生物3a-3h在465nm附近有最大荧光发射,二茂铁双酰腙吡唑衍生物4a-4d在380nm左右有最大荧光发射。二茂铁吡唑啉衍生物5a-5h在390nm左右有最大荧光发射。各目标化合物的CV测试显示:化合物3e-3h和5e-5h均在0.5~0.8v范围内出现了二茂铁的氧化还原峰。
[Abstract]:Based on the double properties of ferrocene and pyrazoline heterocyclic compounds, some novel ferrocenyl pyrazoline derivatives were designed and synthesized by introducing ferrocene into pyrazoline compounds, and the structure of the target compounds was characterized. The electrochemical properties of the target compounds were also studied by UV and fluorescence assay. This is of great theoretical and practical significance for the synthesis and application of ferrocenyl pyrazoline heterocyclic compounds. The main work of this paper: 1. Four kinds of acetophenone phenylhydrazone were synthesized from four acetophenone derivatives and phenylhydrazine. Four kinds of 4-formyl pyrazole were synthesized by Vilsmeier-Haack reaction under microwave condition. Then ferrocene and acetyl chloride, catalyzed by AlCl3, were used as catalyst to form 1 ~ (-1) -ferrocene diethyl ketone, respectively, and 4-formyl pyrazole was used as raw material, and NaOH solution was used as catalyst, and then tetraDing Ji ammonium bromide phase transfer catalyst was added. Four ferrocene dienopyrazole derivatives 3a-3d were synthesized under microwave irradiation. The yield of each target compound is about 84%. Under the same reaction conditions, four ferrocenylenopyrazole derivatives 3e-3h.2were synthesized from acetylferrocene and 4-formylpyrazole. In this paper, 1 ~ (1) C ~ (-1) -ferrocene diethyl ketone was added into 10% NaClO solution to form 1H ~ (1 +) -ferrocene diacetic acid, and then to form 1 ~ (-1) ~ (-1) -ferrocene diformate methyl ester with methanol under concentrated sulfuric acid condition. Four ferrocene diacylhydrazole derivatives (4a-4d) were synthesized with 4 kinds of 4-formyl pyrazole in anhydrous ethanol under microwave irradiation using acetic acid as catalyst and 80% hydrazine hydrate. The yield of each target compound is more than 85%. The synthetic ferrocene diacylenopyrazole derivative 3a-3d was used as raw material and thiosemicarbazone was added in ethanol solution under NaOH, microwave irradiation to obtain the target compound for 5a-5 d. The yield of each target compound is over 83%. The target compound 5e-5 h was synthesized from ferrocenyl pyrazole derivative 3e-3h under the same reaction conditions. The structures of all the target compounds were confirmed by elemental analysis, 1 H NMR,IR and 4. 4% MS. UV spectra of the target compounds showed that ferrocenylenopyrazole derivatives 3a-3h, ferrocenylhydrazone pyrazole derivatives 4a-4d and ferrocenyl pyrazoline derivatives 5a-5h had absorption peaks near 280nm and 360nm. However, the absorption intensity of each compound is different. The fluorescence spectra of the target compounds showed that the maximum fluorescence emission of ferrocenylenopyrazole derivative (3a-3h) was near 465nm, and that of ferrocene diacylhydrazole derivative (4a-4d) was about 380nm. Ferrocene pyrazoline derivative 5a-5h has the largest fluorescence emission around 390nm. The CV test of each target compound showed that the redox peaks of ferrocene appeared in the range of 0.5 ~ 0.8v for both 3e-3h and 5e-5h.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O627.81;O626.21
，
本文编号：2300321
[Abstract]:Based on the double properties of ferrocene and pyrazoline heterocyclic compounds, some novel ferrocenyl pyrazoline derivatives were designed and synthesized by introducing ferrocene into pyrazoline compounds, and the structure of the target compounds was characterized. The electrochemical properties of the target compounds were also studied by UV and fluorescence assay. This is of great theoretical and practical significance for the synthesis and application of ferrocenyl pyrazoline heterocyclic compounds. The main work of this paper: 1. Four kinds of acetophenone phenylhydrazone were synthesized from four acetophenone derivatives and phenylhydrazine. Four kinds of 4-formyl pyrazole were synthesized by Vilsmeier-Haack reaction under microwave condition. Then ferrocene and acetyl chloride, catalyzed by AlCl3, were used as catalyst to form 1 ~ (-1) -ferrocene diethyl ketone, respectively, and 4-formyl pyrazole was used as raw material, and NaOH solution was used as catalyst, and then tetraDing Ji ammonium bromide phase transfer catalyst was added. Four ferrocene dienopyrazole derivatives 3a-3d were synthesized under microwave irradiation. The yield of each target compound is about 84%. Under the same reaction conditions, four ferrocenylenopyrazole derivatives 3e-3h.2were synthesized from acetylferrocene and 4-formylpyrazole. In this paper, 1 ~ (1) C ~ (-1) -ferrocene diethyl ketone was added into 10% NaClO solution to form 1H ~ (1 +) -ferrocene diacetic acid, and then to form 1 ~ (-1) ~ (-1) -ferrocene diformate methyl ester with methanol under concentrated sulfuric acid condition. Four ferrocene diacylhydrazole derivatives (4a-4d) were synthesized with 4 kinds of 4-formyl pyrazole in anhydrous ethanol under microwave irradiation using acetic acid as catalyst and 80% hydrazine hydrate. The yield of each target compound is more than 85%. The synthetic ferrocene diacylenopyrazole derivative 3a-3d was used as raw material and thiosemicarbazone was added in ethanol solution under NaOH, microwave irradiation to obtain the target compound for 5a-5 d. The yield of each target compound is over 83%. The target compound 5e-5 h was synthesized from ferrocenyl pyrazole derivative 3e-3h under the same reaction conditions. The structures of all the target compounds were confirmed by elemental analysis, 1 H NMR,IR and 4. 4% MS. UV spectra of the target compounds showed that ferrocenylenopyrazole derivatives 3a-3h, ferrocenylhydrazone pyrazole derivatives 4a-4d and ferrocenyl pyrazoline derivatives 5a-5h had absorption peaks near 280nm and 360nm. However, the absorption intensity of each compound is different. The fluorescence spectra of the target compounds showed that the maximum fluorescence emission of ferrocenylenopyrazole derivative (3a-3h) was near 465nm, and that of ferrocene diacylhydrazole derivative (4a-4d) was about 380nm. Ferrocene pyrazoline derivative 5a-5h has the largest fluorescence emission around 390nm. The CV test of each target compound showed that the redox peaks of ferrocene appeared in the range of 0.5 ~ 0.8v for both 3e-3h and 5e-5h.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O627.81;O626.21
，
本文编号：2300321
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