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单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,*,功能化离子液体及其衍生物在有机反应中的应用研究,指导教师：,答 辩 人：,Content,Part,前 言,Part,新型离子液体支载,Schiff,碱的合成,Part,离子液体支载,Schiff,碱在,Suzuki-,Miyaura,偶联反应中的应用研究,Part V,苯并吡喃类衍生物的合成,Part V,致 谢,Part V,结论与展望,Part VI,发表论文,离子液体,热稳定性高,离子电导率高,可以重新回,收使用,热容量大,种类繁多,无可燃性,低蒸汽压,Part,引言,离子液体作为,溶剂和催化剂,Heck,偶联反应,DielsAlder,反应,Michael,加成反应,Beckmann,重排反应,Knoevenagel,缩合反应,FriedelCrafts,反应,Suzuki,偶联反应,Part,引言,离子液体,的功能化,阳离子烷基,侧链的功能化,阴离子,的功能化,含双官能,团的功能化,Part,引言,Part,引言,Rther,et al,.,Chem.Mater.,2010,22,10381045.,Part,引言,在本课题组研究,Pd,催化的,C-C,偶联反应,的基础上,开发新型的功能化离子液体,及其衍生物,对,Suzuki-Miyaura,偶联反应，,Knoevenagel,缩合反应和,Michael,加成反应等有机反,应的组合反应的研究,选题思路,Part,引言,FILs,Knoevenagel,condensation,Michael,addition,Suzuki,coupling,第 二 章,新型离子液体支载,Schiff,碱的合成,离子液体,离子液体支载,Schiff,碱,芳香醛,Part,新型离子液体支载,Schiff,碱的合成,Synthesis of ionic liquid 2-aeminPF,6,Part,Synthesis of ionic liquid-supported Schiff base,Synthesis of ionic liquid-supported Schiff base,Bin Li,Yi-Qun Li,et al.,ARKIVOC,2009,xi,165,Table 2.1 Synthesis of ionic liquid-supported Schiff base,Entry,Ar,Products,Yields,a,/%,Mp/,C,1,4-Cl-C,6,H,4,3a,21,103-105,2,2,4-2Cl-C,6,H,3,3b,41,129-131,3,4-OCH,3,-C,6,H,4,3c,37,122-124,4,4-NO,2,-C,6,H,4,3d,44,180-182,5,3-NO,2,-C,6,H,4,3e,54,133-135,6,2-HO-C,6,H,4,3f,36,132-134,7,4-Me-C,6,H,4,3g,34,131-133,8,4-Br-C,6,H,4,3h,30,decomp.220,9,3-OCH,3,-4-OHC,6,H,3,3i,43,178-180,Part,新型离子液体支载,Schiff,碱的合成,Bin Li,Yi-Qun Li,et al.Acta Cryst.,2009,E65,o1427,第 三 章,离子液体支载,Schiff,碱在,Suzuki-Miyaura,偶联反应中的应用研究,Bin Li,Yi-Qun Li*,et al.,ARKIVOC,(Accepted),Part,Study of Suzuki coupling reaction,Entry,Ligand,Time(h),Yield(%),b,1,2,3,4,5,6,4-NO,2,3-NO,2,2-OH,4-CH,3,O,2,4-(Cl),2,4-OH,3-CH,3,O,1,1,0.5,0.5,1.5,0.5,87,88,98,87,92,87,Table 1,Influence of ligands,L,on the palladium-catalyzed Suzuki coupling of,4-indoanisole with phenylboronic acid,Part,Suzuki-Miyaura,偶联反应中的应用研究,Table 2,Effect of bases,solvents,and temperatures on the Suzuki-Miyaura,coupling reaction of 4-indoanisole and phenylboronic acid,Entry,Base,Solvent,Temp(),Time(h),Yield(%),b,1,2,3,4,5,6,7,8,9,10,11,12,13,K,2,CO,3,Na,2,CO,3,KOH,NaOH,NaHCO,3,CaO,CsCO,3,Na,3,PO,4,.12H,2,O,K,2,CO,3,K,2,CO,3,K,2,CO,3,K,2,CO,3,K,2,CO,3,EtOH,EtOH,EtOH,EtOH,EtOH,EtOH,EtOH,EtOH,H,2,O,CH,3,CN,DMF,cyclohexane,EtOH,78,78,78,78,78,78,78,78,78,78,78,78,50,0.5,1,1,0.5,5,5,0.5,0.5,1,5.5,1,5,1,98,46,75,87,33,27,93,65,38,60,87,NR,c,88,Table 3 PdCl,2,/Ligand L3 catalyzed coupling reaction of aryl halides with aryl boronic acids,Entry,X,R,1,R,2,Time(h),Yield(%),b,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,I,I,I,I,I,I,I,I,I,I,I,Br,Br,Br,Br,Br,Br,Br,Br,Cl,H,H,H,H,H,4-OCH,3,4-OCH,3,4-OCH,3,4-OCH,3,4-OCH,3,4-COOH,H,H,4-NO,2,3-NO,2,4-OH,4-COOCH,3,4-OCH,3,2-NO,2,4-NO,2,H,Cl,F,CH,3,OCH,3,H,Cl,F,CH,3,OCH,3,H,Cl,OCH,3,H,H,H,H,H,H,H,0.5,0.5,0.5,0.5,0.5,0.5,0.5,0.5,0.5,0.5,1,0.5,0.5,1,6,1.5,3,1.5,5,24,92,94,92,93,98,98,84,87,96,84,95,88,89,95,86,84,86,94,NR,c,44,d,Part,Suzuki-Miyaura,偶联反应中的应用研究,催化剂重复使用性能,Part,Suzuki-Miyaura,偶联反应中的应用研究,第四章,苯并吡喃类衍生物的合成,无溶剂条件下功能化离子液体催化的芳香醛、丙二腈和,达米酮“一锅法”三组分反应,通过串联的,Suzuki-Miyaura,偶联、,Knoevenagel,缩合、,以及,Michael,加成反应合成新型的苯并吡喃衍生物,Part V,苯并吡喃类衍生物的合成,第一节,无溶剂条件下功能化离子液体催化的芳香醛、丙二腈和,达米酮“一锅法”三组分反应,Table 4.1 Synthesis of 2-Amino-3-cyano-4-aryl-7,7-dimethyl-5-oxo-4,H,-5,6,7,8-tetrahydrobenzobpyrans by the catalyst ionic liquid,Entry,Ar,Products,Times/min,Yields,a,/%,Mp/,C,Lit.Mp/,C,1,4-NO,2,-C,6,H,4,4a,60,92,175-177,177-178,2,3-NO,2,-C,6,H,4,4b,60,87,208-210,204-205,3,2,4-2Cl-C,6,H,3,4c,50,94,181-183,180-182,4,4-Cl-C,6,H,4,4d,60,86,216-217,214-216,5,4-Br-C,6,H,4,4e,50,92,190-192,196-198,6,C,6,H,5,4f,30,88,208-210,208-211,7,4-Me,2,N-C,6,H,4,4g,40,84,203-205,208-210,8,3-OCH,3,-4-OHC,6,H,3,4h,50,83,228-230,-,9,4-HO-C,6,H,4,4i,35,85,206-208,206-208,10,4-Me-C,6,H,4,4j,40,81,212-214,210-212,11,2-HO-C,6,H,4,4k,60,85,120-122,-,12,4-OCH,3,-C,6,H,4,4l,60,77,192-194,192-194,Part V,苯并吡喃类衍生物的合成,第二节,通过串联的,Suzuki-Miyaura,偶联、,Knoevenagel,缩合、以及,Michael,加成反应合成新型的苯并吡喃衍生物,Knoevenagel,condensation,Michael,addition,Suzuki,coupling,FILs,Part V,苯并吡喃类衍生物的合成,Part V,苯并吡喃类衍生物的合成,Synthesis of ionic liquid PhCH,2,Me,2,N,+,CH,2,CH,2,NMe,2,Cl,-,Part V,苯并吡喃类衍生物的合成,Part V,苯并吡喃类衍生物的合成,Crystal structure of compound,6a,Part V,结论与展望,1.,首次将功能化离子液体和芳香醛反应，合成新型的离子液体支载,Schiff,碱,2.,首次将离子液体支载,Schiff,碱作为配体，与,Pd,形成催化体系，催化芳基卤,化物和芳基硼酸的,Suzuki-Miyaura,偶联反应,3.,用碱性功能化离子液体,2-aeminPF,6,催化合成了,2-,氨基,-3-,氰基,-4-,芳基,-7,7-,二甲基,-5-,氧,-4-,氢,-5,6,7,8-4H-,苯并,b,吡喃,4.,首次用串联的,Suzuki-Miyaura,偶联、,Knoevenagel,缩合、以及,Michael,加成,反应的组合反应合成新型的苯并吡喃类衍生物，为偶联反应、缩合反应、,加成反应等不同类型反应之间的组合应用提供了一个新的思路,5.,本论文共合成新化合物,14,个,结 论,Part V,结论与展望,1.,可以将离子液体支载,Schiff,碱,/Pd,催化体系应用在,Heck,等,偶联反应中,2.,可以进行离子液体支载,Schiff,碱的性能及生物活性等方面,的研究,3.,可以开发新的偶联反应、缩合反应、加成反应等不同类型,反应之间的交叉运用及其“一锅法”反应研究,展 望,
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