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题名: Brønsted酸性功能化离子液体的合成及其在酯化和喹唑啉酮合成中的应用研究
作者: 李心忠
答辩日期: 2008-06-10
导师: 吾满江•艾力
专业: 有机化学
授予单位: 中国科学院研究生院
授予地点: 北京
学位: 博士
关键词: Brønsted酸性功能化离子液体 ; 微波 ; 无溶剂合成 ; Fischer酯化 ; 4(3H)-喹唑啉酮
摘要: 本文的主要工作是合成新型基于磺酸基、羧基官能团的Brønsted酸性功能化离子液体,并以其作为反应的介质与催化剂,同时引入无溶剂合成、微波技术等绿色化学手段研究了Fischer酯化和4(3H)-喹唑啉酮类化合物的合成。具体包括以下几方面的内容:在本文第二章和第三章,以吡啶或N-甲基咪唑、苄基氯为底物,经季铵化、离子交换二步反应,合成出了未见报道基于N-苄基吡啶阳离子和1-苄基-3-甲基咪唑阳离子,阴离子别为BF4-,HSO4-,H2PO4-,p-TSA-,CF3COO-,ClCH2COO-的十二种新型酸性功能化离子液体。并对离子液体的粘度、密度、极性进行了表征。其中N-苄基吡啶硫酸氢根盐([BYBE][HSO4])、1-苄基-3-甲基咪唑硫酸氢根([MIMBE][HSO4])和N-苄基吡啶磷酸二氢根盐([BYBE][H2PO4])、1-苄基-3-甲基咪唑磷酸二氢根盐([MIMBE][H2PO4])表现Brønsted酸性,其它八种离子液体表现Lewis酸性。在本文第四章,从2,3-吡啶二羧酸、苄基氯、1-溴丁烷出发,经季铵化、离子交换二步反应,合成了八种未见报道的有机阳离子为2,3-(N-苄基)-吡啶二羧酸和2,3-(N-正丁基吡啶)二羧酸阳离子,相配有机阴离子为BF4-,CF3COO-,无机阴离子为HSO4-,H2PO4-的新型Brønsted酸性功能化离子液体。八种离子液体在室温下均为液相,并表现出强Brønsted酸性。在本文第五章,以1-苄基-3-甲基咪唑氯化物([MIMBE][Cl])和,N-苄基吡啶氯化物([BYBE][Cl])为母体化合物,经二条合成路线首次得到了基于有机阳离子上芳基磺酸侧链的新型Brønsted酸性功能化离子液体1-(4-磺酸基)苄基-3-甲基咪唑硫酸氢根盐([MIMBES][HSO4])和N-(4-磺酸基)苄基吡啶硫酸氢根盐([BEBYS][HSO4])。[MIMBES][HSO4]和[BEBYS][HSO4]作为反应介质与催化剂在无溶剂条件下,实现了长链脂肪酸与甲醇、乙醇室温下的绿色Fischer酯化。C4~C18的脂肪酸甲酯、乙酯的产率为84.6~99%。离子液体可循环使用3次,催化活性稍有下降。在本文第六章,首次以四种酸性功能化离子液体[MIMBE][HSO4]、[BYBE][HSO4]、[MIMBE] [H2PO4] 、[BYBE][H2PO4]为反应介质与催化剂,研究了苄醇与C2~C16的直链脂肪酸、苯甲酸;苯甲酸与C3~C16的脂肪醇在无溶剂和微波辐射反应条件下的Fischer酯化反应。当苯甲酸或苄醇与离子液体的摩尔比为1:0.5时,无需外加催化剂反应即可在化学计量条件下进行,12~20min完成反应,苯甲酸酯与苄酯的产率分别为77%~98%和78%~98.5%,离子液体循环使用3次,催化活性仅下降1.8%~3.4%。在本文第七章,首次以Brønsted酸性功能化离子液体[MIMBES][HSO4]与[BYBES][HSO4]作为反应介质与催化剂,分别研究了2-取代-4(3H)-喹唑啉酮、2,3-二取代-4(3H)-喹唑啉酮和3-取代-4(3H)-喹唑啉酮化合物的三组分、一锅法微波合成。1)2-取代-4(3H)-喹唑啉酮的合成:反应以2-氨基苯甲酸为底物,酰氯作为C2引入单元,乙酸铵作为N3引入单元。离子液体用量10mol%,反应时间6min,产率87~93%。此合成方法具有通用性,2-位上可引入芳基和烷基。二种离子液体反应结果接近。离子液体可循环使用三次,反应活性稍有下降。2)2,3-二取代-4(3H)-喹唑啉酮的合成:在2-取代-4(3H)-喹唑啉酮的合成取得成功的基础上,我们以取代芳胺、脂肪胺为N3引入单元,成功地进行了2,3-二取代-4(3H)-喹唑啉酮的合成,离子液体用量10mol%,反应时间6min,产率74~92%,二种离子液体均得到了良好效果。3)3-取代-4(3H)-喹唑啉酮化合物的合成:合成以2-氨基苯甲酸为底物,原甲酸三乙酯、甲酸作为C2引入单元,芳胺、脂肪胺为N3引入单元。反应结果为离子液体用量5mol%,反应时间4~6min,产率69~94%,原甲酸三乙酯、甲酸二条合成路线产率接近,甲酸路线具有原料上的优势。
英文摘要:
The main work presented in this dissertation is about the design and synthesis of novel BAILs and the study of using them acted as medium/catalysts in Fischer esterifications and the synthesis of 4(3H)-quinazolinones carried out under solvent- free and microwave irradiation conditions.The contents are listed as following: In chapter 2 and 3 of this dissertation, we describe the synthesis of twelve novel acidic ionic liquids using N-methylimidazole, pyridine and benzyl chloride as starting materials involving quaterisation and anion exchange two-step reactions.These BAILs based on N-benzylpyridinium and 1-benzyl-3-methylimidazolium cation, the anions are BF4-, HSO4-, H2PO4-, p-TSA-, CF3COO-, ClCH2COO- respectively. Their viscosity, density, polarity were also characterized, in which N-benzylpyridinium hydrogensulfa te([BYBE][HSO4]),1-benzyl-3-methylimidazolium hydrogensulfate ([MIMBE][HS O4]) and N-benzylpyridinium hydrogenphosphate ([BYBE][ [H2PO4]), 1-benzyl-3- methylimidazolium hydrogen phosphate([MIMBE][H2PO4] represented Brønsted acid ity , the rest represented Lewis acidity. In chapter 4 of this dissertation, eight novel BAILs based on 2,3-pyridinedicarbo xylic acid cation were synthesized and characterized, the synthesis of these ionic liquids using 2,3-pyridinedicarboxylic acid, benzyl chloride, n-butyl bromide as starting materials via quaterisation and anion exchange reactions, the anions are BF4-, CF3COO-, HSO4-, H2PO4- respectively. These BAILs possess strong Brønsted acidity and are liquids at room temperature. In chapter 5 of this dissertation, two novel Brønsted acidic ionic liquids: 1-(4-sul fonic acid benzyl)-3-methylimidazolium hydrogensulfate ([MIMBES][HSO4]) and N -(4-sulfonic acid benzyl)pyridinium hydrogensulfate ([BYBES][HSO4]) were synthe sized and characterized, the synthesis of using 1-benzyl-3-methylimidazolium and N- benzyl pyridinium chlorides as starting material via two synthetic routes.They served as medium and catalyst realized the Fischer esterifications of long chain aliphatic acids (C4~C18) with methanol and ethanol carried out at room temperature under solvent–free conditions, it was found that in the presence of 10mol% ionic liquids reactions carried out smoothly with good to excellent isolated yields(84.6~99%). These ionic liquids could be recovered easily and recycled three times without any significant loss in catalytic activity. [MIMBES][HSO4] gave better results for shorter cabon chain aliphatic acids than [BYBES][HSO4],but for longer carbon chain substrates [BYBES][HSO4] gave better results than [MIMBES][HSO4]. In chapter 6 of this dissertation, the Fischer esterifications of benzoic acid with C3~C16 aliphatic alcohols and C2~C16 aliphatic acids, benzoic acid with benzyl alcohol using [MIMBE][HSO4], [BYBE][HSO4], [MIMBE][H2PO4], and [BYBE][ H2 PO4] as medium and catalyst under solvent-free and microwave irradiation conditions was study. it was found the reactions carried out smoothly without the need of added catalyst with good to excellent isolated yields (77~98.5%) in the presence of 50mol%BAILs. These BAILs could be recovered easily and recycled three times only 1.8~3.4% loss in their catalytic activity. In chapter 7 of this dissertation, the synthesis of 2-substituted-4(3H)-quinazolinon es, 2,3-disubstituted-4(3H)-quinazolinones and 2-substituted-4(3H)-quinazolinones in [MIMBES][HSO4]and [BYBES][HSO4] under three component, one-pot, microwave irradiation conditions was study, in which,1)The synthesis of 2-substituted-4(3H) -quinazolinones using 2-aminobenzoic acid as substrate, acyl chloride as C2 unit, ammonium acetate as N3 unit,it was found that the reactions completed within 6min with the yields of 87~93% in the presence of 10mol% BAILs.This synthetic method has generality for target compounds, aryl and alkyl can be introduced 2-position.BAILs could be recovered easily and recycled three times without any significant loss in catalytic activity. 2) Base on the synthesis of 2-substituted-4(3H)-quinazolinones, we using aromatic and aliphatic amine as N3 unit, successful synthesis of 2,3-disubstituted-4(3H) -quinazolinones, it was found that the yields of 74~92% was obtained within 6~8min in the presence of 10mol% BAILs.[MIMBES][HSO4] gave better results than [BYBES][HSO4]. 3) The synthesis of 3-substituted-4(3H) -quinazolinones using 2-aminobenzoic acid as substrate, ortho ester or formic acid as C2 unit, aromatic and aliphatic amine as N3 unit, it was found that the reactions completed within 4~6min with the yields of 69~94% in the presence of 5mol% BAILs. BAILs could be recovered easily and recycled three times without any significant loss in catalytic activity.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3522
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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
李心忠. Brønsted酸性功能化离子液体的合成及其在酯化和喹唑啉酮合成中的应用研究[D]. 北京. 中国科学院研究生院. 2008.
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