本文選題：有機硅格氏試劑 + 六甲基磷酰三胺　； 參考：《山東大學》2017年碩士論文

【摘要】：與碳原子相比,硅原子既具有相似性,又具其獨特性。碳的格氏試劑是有機化學中至關(guān)重要的中間體,另外,關(guān)于硅金屬鍵的研究中缺乏硅鎂鍵的報道,因此我們提出了以氯硅烷、鎂為原料制備有機硅格氏試劑的研究思路。我們以帶有不同烷基的氯硅烷、鎂屑為原料,六甲基磷酰三胺(HMPA)等為溶劑,成功制備了四種帶有不同烷基的有機硅格氏試劑,分別是三甲硅基氯化鎂、二甲基苯基氯化鎂、甲基二苯基硅基氯化鎂、三苯基硅基氯化鎂。我們不僅得到了各個反應的最佳反應溫度、反應物配比、催化劑等,還對各產(chǎn)物進行了1 HNMR、29SiNMR表征。通過冷卻有機硅格氏試劑,我們發(fā)現(xiàn)產(chǎn)物中產(chǎn)生了無色透明針狀晶體,對得到的晶體進行測試,得知配合物分子式為MgCl2·2HMPA。通過所得晶體結(jié)構(gòu),我們推測有機硅格氏試劑中也可能存在類似碳格氏試劑中的Schlenk平衡。該晶體的得出進一步驗證了有機硅格氏試劑的產(chǎn)生。羥烴基二硅氧烷是合成高性能有機硅改性聚氨酯材料及有機硅改性聚脲等材料的重要原材料。1,3-雙(γ-羥丙基)-1,1,3,3-四甲基二硅氧烷是羥烴基封端劑中應用較多的一種,其主要制備方法有硅氫加成法和有機金屬合成法,但是硅氫加成法需要羥基保護,反應步驟繁瑣,有機金屬合成法對操作要求高,不適于工業(yè)生產(chǎn)。我們用新的合成方法成功制備了 1,3-雙(丫-羥丙基)-1,1,3,3-四甲基二硅氧烷。我們通過乙酸烯丙酯與二甲基氫氯硅烷發(fā)生硅氫加成反應生成碳官能硅基羧酸酯,該羧酸酯在酸性條件下水解后通過簡單提純便可直接得到1,3-雙(γ-羥丙基)四甲基二硅氧烷。該方法步驟簡單、操作方便,并且反應中副反應少,產(chǎn)物收率高且純度高。
[Abstract]:Compared with carbon atoms, silicon atoms have both similarity and uniqueness. Grignard reagent of carbon is an important intermediate in organic chemistry. In addition, there is no report of silicon and magnesium bond in the study of silicon metal bond. Therefore, we put forward the research idea of preparing organic silicon Grignard reagent using chlorosilane and magnesium as raw material. Four organosilyl Grignard reagents with different alkyl groups were successfully prepared by using chlorosilane with different alkyl groups, magnesium chips as raw materials, hexamethylphosphoryltriamine (HMPA) as solvent, trimethylsilyl magnesium chloride and dimethyl phenyl magnesium chloride, respectively. Methyl diphenylsilyl magnesium chloride, triphenylsilyl magnesium chloride. Not only the optimum reaction temperature, reactant ratio and catalyst were obtained, but also the products were characterized by 1HNMR-29Si NMR. By cooling the organosilicon Grignard reagent, we found that colorless and transparent needle-like crystal was produced in the product. The obtained crystal was tested and the molecular formula of the complex was found to be MgCl _ 2 _ 2H _ MPA. Based on the crystal structure, we speculate that the Schlenk equilibrium may also exist in the organosilicon Grignard reagents similar to the carbon Grignard reagents. The result of the crystal further verifies the production of organosilicon Grignard reagent. Hydroxyalkyldisiloxane is one of the most important raw materials for the synthesis of high performance silicone modified polyurethane and silicone modified polyurea. The main preparation methods are hydrosilyl addition method and organometallic synthesis method, but hydrosilyl addition method needs hydroxyl protection, the reaction steps are complicated, and the organometallic synthesis method is not suitable for industrial production because of its high operational requirements. A new synthetic method has been developed for the preparation of 1'3'- bis (A- hydroxypropyl)-1'1'1'3'3 '-tetramethyl disiloxane. The carboxylic ester was synthesized by the addition reaction of allyl acetate and dimethylhydrochlorosilane. The carboxylic ester was hydrolyzed under acidic conditions and purified simply to obtain 1k3- bis (緯 -hydroxypropyl) tetramethyl disiloxane directly. The method is simple, easy to operate, less side reaction, high yield and high purity.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ264.1

【參考文獻】

相關(guān)期刊論文 前8條

1 陳向前;邵月剛;唐紅定;;γ-甲基丙烯酰氧基丙基三甲氧基硅烷的合成研究[J];杭州化工;2013年04期

2 張建威;陳軍;周遠建;;1,3-雙(3-羥丙基)-1,1,3,3-四甲基二硅氧烷(BHTS)的合成及表征[J];有機硅材料;2012年04期

3 柴子斌;吳清洲;陳關(guān)喜;馮建躍;;羥基保護-硅氫加成合成1,3-雙(γ-羥丙基)-1,1,3,3-四甲基二硅氧烷[J];精細化工;2010年09期

4 向文軍;胡海平;雷興家;李飛;;甲苯溶液中惰性鹵代芳烴格氏試劑的制備[J];河北化工;2007年09期

5 朱曉麗,張慶思,馮圣玉;有機硅改性水性聚氨酯的研究進展[J];中國皮革;2005年03期

6 姜紅芹,張墩明,蔣錫群,劉蕓,楊昌正;1,3-雙(3-羥丙基)-1,1,3,3-四甲基二硅氧烷的制備[J];精細化工;2004年03期

7 馮玉玲;格氏試劑——重要的金屬有機化合物[J];石家莊大學學報;1999年04期

8 方少明,侯守君,程海軍,張留成;合成1，3－二（3－羥丙基）四甲基二硅氧烷的新方法[J];合成化學;1996年03期

相關(guān)碩士學位論文 前1條

1 叢麗曉;有機硅改性水性聚氨酯的研究[D];山東大學;2008年

，

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