【摘要】：本論文結(jié)合了二茂鐵和吡唑啉雜環(huán)化合物的雙重特性,將二茂鐵基引入吡唑啉化合物中,設(shè)計合成了一些新型的二茂鐵基吡唑啉衍生物,并對目標(biāo)化合物進行了結(jié)構(gòu)表征、紫外和熒光活性測試,對目標(biāo)化合物的電化學(xué)性質(zhì)也進行了研究。這對二茂鐵基吡唑啉類雜環(huán)化合物的合成及其應(yīng)用研究都具有極為重要的理論意義和現(xiàn)實意義。本論文的主要工作:1.以4種苯乙酮衍生物和苯肼為原料合成4種苯乙酮苯腙,在微波條件下經(jīng)Vilsmeier-Haack反應(yīng)生成中間體4種4-甲酰基吡唑。然后二茂鐵與乙酰氯在AlCl3的催化下生成1,1'-二茂鐵二乙酮,將其分別與4-甲�；吝驗榉磻�(yīng)原料,以NaOH溶液為催化劑,添加四丁基溴化銨相轉(zhuǎn)移催化劑,在微波條件下合成4種二茂鐵雙酰烯吡唑衍生物3a-3d。經(jīng)工藝優(yōu)化,各目標(biāo)化合物產(chǎn)率均在84%左右。同樣反應(yīng)條件下,以乙酰基二茂鐵和4-甲�；吝蚝铣�4種二茂鐵單酰烯吡唑衍生物3e-3h。2.以1,1'-二茂鐵二乙酮為原料,加入10%的NaClO溶液生成1,1'-二茂鐵二乙酸,然后在濃硫酸條件下與甲醇生成1,1'-二茂鐵雙甲酸甲酯,再與80%的水合肼合成1,1'-二茂鐵雙甲酰肼,將其分別與4種4-甲�；吝蛟跓o水乙醇中,以冰乙酸為催化劑,在微波條件下合成4種二茂鐵雙酰腙吡唑衍生物4a-4d。經(jīng)工藝優(yōu)化,各目標(biāo)化合物產(chǎn)率均在85%以上。3.以合成的二茂鐵雙酰烯吡唑衍生物3a-3d為原料與氨基硫脲在乙醇溶液中加入NaOH,微波輻射下回流制得目標(biāo)化合物5a-5d。經(jīng)工藝優(yōu)化,各目標(biāo)化合物產(chǎn)率均在83%以上。同樣反應(yīng)條件下,以二茂鐵單酰烯吡唑衍生物3e-3h合成目標(biāo)化合物5e-5h。所有目標(biāo)化合物的結(jié)構(gòu)都經(jīng)元素分析,1H NMR,IR和MS得以確認(rèn)。4.各目標(biāo)化合物的紫外光譜測試顯示:二茂鐵酰烯吡唑衍生物3a-3h,二茂鐵雙酰腙吡唑衍生物4a-4d和二茂鐵基吡唑啉衍生物5a-5h均在280nm和360nm附近有吸收峰,但各化合物吸收強度卻各不相同。各目標(biāo)化合物的熒光光譜測試顯示:二茂鐵酰烯吡唑衍生物3a-3h在465nm附近有最大熒光發(fā)射,二茂鐵雙酰腙吡唑衍生物4a-4d在380nm左右有最大熒光發(fā)射。二茂鐵吡唑啉衍生物5a-5h在390nm左右有最大熒光發(fā)射。各目標(biāo)化合物的CV測試顯示:化合物3e-3h和5e-5h均在0.5~0.8v范圍內(nèi)出現(xiàn)了二茂鐵的氧化還原峰。
[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.
【學(xué)位授予單位】：石河子大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O627.81;O626.21
，

本文編號：2300321