官能化二硫化物的相轉(zhuǎn)移催化制備及還原研究
發(fā)布時間：2019-06-03 13:26
【摘要】：二硫化物在有機(jī)合成和生物體中具有重要的地位,生物體內(nèi)二硫化物與巰基的可逆相互轉(zhuǎn)化使得基于二硫化物的可生物降解材料在化學(xué)傳感器、前體藥物、水凝膠和納米材料等領(lǐng)域廣泛應(yīng)用。本論文研究了通過相轉(zhuǎn)移催化合成官能化二硫化物中各種反應(yīng)條件的影響和相轉(zhuǎn)移催化機(jī)理,利用相轉(zhuǎn)移催化合成了雙(羥基十一烷基)二硫化物和聚烷基二硫化物,并使用不同的還原劑對雙(羥基十一烷基)二硫化物進(jìn)行還原,探討了DTT在不同溶劑體系中還原二硫化物的能力,提出了DTT還原二硫化物的反應(yīng)機(jī)理,主要研究結(jié)論包括:1、通過對相轉(zhuǎn)移催化合成烷基二硫化物過程中反應(yīng)溫度、反應(yīng)時間、物料比等因素的研究,第I步反應(yīng)中硫磺與硫化鈉的配比決定了生成二硫根的反應(yīng)平衡,決定了反應(yīng)完畢后單硫根、二硫根和三硫根離子的濃度。2、相轉(zhuǎn)移催化合成烷基二硫化物的第II步反應(yīng)中,三種硫根離子與雙十二烷基二甲基銨離子的結(jié)合能力順序?yàn)?單硫根二硫根三硫根;相轉(zhuǎn)移催化制備二硫化物過程中,硫根離子的濃度及其與相轉(zhuǎn)移活性離子的結(jié)合能力決定了哪種離子能夠被轉(zhuǎn)移并生成相應(yīng)的產(chǎn)物。3、利用相轉(zhuǎn)移催化反應(yīng),通過控制優(yōu)化的反應(yīng)條件,可以制得純度很高的雙(羥基十一烷基)二硫化物;此外,調(diào)節(jié)Na2S2和1,10-二溴癸烷的摩爾比,在適當(dāng)?shù)姆磻?yīng)條件下可以制備聚癸烷基二硫化物,這種聚合物為無色透明的聚合物。4、在雙(羥基十一烷基)二硫化物的還原反應(yīng)中,使用硼氫化鈉作為還原劑可實(shí)現(xiàn)的還原比例為70%;使用Zn-乙酸體系可以實(shí)現(xiàn)還原率為80%,但易造成羥基的酯化反應(yīng);Zn-HCl體系的還原率為53%;三丁基膦基本上未發(fā)現(xiàn)還原活性。5、DTT還原雙(羥基十一烷基)二硫化物與溶劑性質(zhì)密切相關(guān)。在THF為主溶劑的體系中,隨著質(zhì)子性溶劑(水、甲醇)含量的增加,還原率越來越高,最高達(dá)到95.6%;在二氯甲烷為主溶劑體系中,當(dāng)完全無水時,還原反應(yīng)不能發(fā)生,而水含量僅為0.05%時,還原率可達(dá)到73.6%,然后隨著水含量的增加而還原率降低。6、從反應(yīng)機(jī)理來看,堿性條件下,二硫蘇糖醇的兩個巰基電離為硫離子,這種硫離子作為親核試劑對二硫鍵中的硫原子進(jìn)攻,在水、甲醇等質(zhì)子性溶劑的促進(jìn)作用下,使得二硫鍵斷裂,形成硫離子;而二硫蘇糖醇的兩個硫原子閉環(huán)被氧化。
[Abstract]:Disulfide plays an important role in organic synthesis and organisms. The reversible transformation of disulfide and sulfhydryl groups in organisms makes disulfide-based biodegradable materials in chemical sensors, precursor drugs, Hydrogel and nanomaterials are widely used in the field of hydrogel and nanomaterials. In this paper, the effects of reaction conditions and the mechanism of phase transfer catalysis on the synthesis of functionalized disulfide by phase transfer catalysis were studied, and bis (hydroxyundecyl) disulfide and polyalkyl disulfide were synthesized by phase transfer catalysis. The ability of DTT to reduce disulfide in different solvent systems was discussed by using different reductants. The reaction mechanism of DTT reduction of disulfide was put forward. The main conclusions are as follows: 1. By studying the reaction temperature, reaction time and material ratio in the synthesis of alkyl disulfide by phase transfer catalysis, the reaction equilibrium of the formation of disulfide is determined by the ratio of sulfur to sodium sulfide in the first step. The concentration of monosulfide, disulfide and trisulfide ions after the reaction was determined. 2. In the second step of the synthesis of alkyl disulfide by phase transfer catalysis, The order of binding ability of three sulfur ions to dialkyl dimethyl ammonium ion is as follows: monosulfide disulfide trisulfide; In the process of phase transfer catalysis to prepare disulfide, the concentration of sulfur ion and its binding ability to phase transfer active ion determine which ion can be transferred and form the corresponding product. 3, using phase transfer catalytic reaction, By controlling the optimized reaction conditions, the bis (hydroxyundecyl) disulfide with high purity can be prepared. In addition, polydecyl disulfide can be prepared by adjusting the molar ratio of Na2S2 to 1, 10-dibromodecane under appropriate reaction conditions, which is a colorless and transparent polymer. 4, In the reduction reaction of bis (hydroxyundecyl) disulfide, the reduction ratio can be realized by using sodium borohydrate as reductant. The reduction rate of Zn- acetic acid system is 80%, but it is easy to cause the esterification of hydroxyl group, and the reduction rate of Zn-HCl system is 53%. The reduction activity of tributylphosphine was basically not found. 5, the reduction of bis (hydroxyundecyl) disulfide by DTT was closely related to the properties of solvent. In the system of THF as the main solvent, with the increase of the content of protonic solvent (water, methanol), the reduction rate is higher and higher, the highest is 95.6%. In the main solvent system of dichloromethane, when there is no water, the reduction reaction can not occur, and when the water content is only 0.05%, the reduction rate can reach 73.6%, and then the reduction rate decreases with the increase of water content. From the point of view of reaction mechanism, two sulfhydryl groups of dithiothreitol were ionized into sulfur ions under alkaline conditions, which were used as nucleophilic reagents to attack sulfur atoms in disulfide bonds, promoted by protonic solvents such as water and methanol. The disulfide bond is broken and sulfur ion is formed. The two sulfur atoms of dithiothreitol are oxidized in closed loop.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
本文編號：2491962
[Abstract]:Disulfide plays an important role in organic synthesis and organisms. The reversible transformation of disulfide and sulfhydryl groups in organisms makes disulfide-based biodegradable materials in chemical sensors, precursor drugs, Hydrogel and nanomaterials are widely used in the field of hydrogel and nanomaterials. In this paper, the effects of reaction conditions and the mechanism of phase transfer catalysis on the synthesis of functionalized disulfide by phase transfer catalysis were studied, and bis (hydroxyundecyl) disulfide and polyalkyl disulfide were synthesized by phase transfer catalysis. The ability of DTT to reduce disulfide in different solvent systems was discussed by using different reductants. The reaction mechanism of DTT reduction of disulfide was put forward. The main conclusions are as follows: 1. By studying the reaction temperature, reaction time and material ratio in the synthesis of alkyl disulfide by phase transfer catalysis, the reaction equilibrium of the formation of disulfide is determined by the ratio of sulfur to sodium sulfide in the first step. The concentration of monosulfide, disulfide and trisulfide ions after the reaction was determined. 2. In the second step of the synthesis of alkyl disulfide by phase transfer catalysis, The order of binding ability of three sulfur ions to dialkyl dimethyl ammonium ion is as follows: monosulfide disulfide trisulfide; In the process of phase transfer catalysis to prepare disulfide, the concentration of sulfur ion and its binding ability to phase transfer active ion determine which ion can be transferred and form the corresponding product. 3, using phase transfer catalytic reaction, By controlling the optimized reaction conditions, the bis (hydroxyundecyl) disulfide with high purity can be prepared. In addition, polydecyl disulfide can be prepared by adjusting the molar ratio of Na2S2 to 1, 10-dibromodecane under appropriate reaction conditions, which is a colorless and transparent polymer. 4, In the reduction reaction of bis (hydroxyundecyl) disulfide, the reduction ratio can be realized by using sodium borohydrate as reductant. The reduction rate of Zn- acetic acid system is 80%, but it is easy to cause the esterification of hydroxyl group, and the reduction rate of Zn-HCl system is 53%. The reduction activity of tributylphosphine was basically not found. 5, the reduction of bis (hydroxyundecyl) disulfide by DTT was closely related to the properties of solvent. In the system of THF as the main solvent, with the increase of the content of protonic solvent (water, methanol), the reduction rate is higher and higher, the highest is 95.6%. In the main solvent system of dichloromethane, when there is no water, the reduction reaction can not occur, and when the water content is only 0.05%, the reduction rate can reach 73.6%, and then the reduction rate decreases with the increase of water content. From the point of view of reaction mechanism, two sulfhydryl groups of dithiothreitol were ionized into sulfur ions under alkaline conditions, which were used as nucleophilic reagents to attack sulfur atoms in disulfide bonds, promoted by protonic solvents such as water and methanol. The disulfide bond is broken and sulfur ion is formed. The two sulfur atoms of dithiothreitol are oxidized in closed loop.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 李春鴿;趙爽;李俊杰;尹玉姬;;含巰基/二硫鍵聚合物生物材料[J];化學(xué)進(jìn)展;2013年01期
2 李新芳,王學(xué)業(yè),文小紅,龍清平,劉萬強(qiáng),譚援強(qiáng),李建軍;有機(jī)二硫化物極壓添加劑結(jié)構(gòu)與潤滑性能的理論研究[J];摩擦學(xué)學(xué)報(bào);2005年01期
，本文編號：2491962
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