新型杯[4]芳烃衍生物的合成及其性能研究
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摘要
杯芳烃(calixarenes)作为继冠醚,环糊精之后的第三代超分子主体,以其易修饰、空腔大小可调、对离子或分子客体均能识别等特性,日益受到人们的重视。功能化杯芳烃在生命科学、分离技术等领域有广阔的应用前景。本文在杯[4]芳烃及其衍生物合成反应和它们的抗氧化、抗紫外性能以及它们对某些过渡金属离子的萃取性能方面进行了以下工作:
1以自制的对叔丁基杯[4]芳烃1及氯乙酸乙酯为原料,得到了收率65.7%的对叔丁基杯[4]芳烃二取代酯衍生物2;以化合物2和85%的水合肼反应,得到了收率85.4%的对叔丁基杯[4]芳烃二取代酰肼衍生物3。化合物2与乙二胺反应,未得到目标产物,而得到对叔丁基杯[4]芳烃联胺类环状化合物4,收率31.0%。
2化合物3与水杨醛反应,得到了收率55.7%的对叔丁基杯[4]芳烃席夫碱类衍生物5;其结构经~1H NMR、~(13)C NMR、IR、MS确证。以PEG-400为相转移催化剂,通过化合物3在氢氧化钠水溶液中与溶于二氯甲烷的肉桂酰氯反应,合成新的化合物对叔丁基杯[4]芳烃肉桂酰类衍生物6,收率44.7%。其结构经~1HNMR、~(13)C NMR、IR确证。
3用紫外分光光度法研究了杯[4]芳烃及其衍生物的紫外吸收光谱,结果表明,化合物5具有抗紫外性能;采用DPPH法测定杯[4]芳烃及其衍生物的抗氧化性能,结果表明,杯[4]芳烃及其衍生物对DPPH具有一定的清除作用,其中以化合物3的清除效果最佳,高达90.6%。
4用原子吸收研究了杯[4]芳烃及其衍生物对过渡金属离子铁(Ⅲ)、铅(Ⅱ)的萃取性能。结果表明:杯[4]芳烃及其衍生物对铁(Ⅲ)、铅(Ⅱ)有良好的萃取效果,化合物3对铁(Ⅲ)的萃取率最高,化合物5对铅(Ⅱ)的萃取率最高,分别可达到53.4%和91.9%。
Calixarenes were the third generation supermolecule after crown ether and cyclodextrin. Due to their easy functionalization and strong complexing properties towards cations, anions and neutral molecules, they have received particular interests by numerous chemists in recent years. Functional calixarenes have been applied successfully to biomimetic research and separation science and technology. Several calix[4]arene and its derivatives were synthesized and their performance of extracted iron , plumbum were studied and their performance of Antioxidizes and antiultraviolet of calixarene and its derivatives were studied too. This thesis includs the following main points:
1 The ester derivative of p-tert-butyl calix[4]arene 2 was synthesized by using self-made p-tert-butylcalix[4]arene & ethyl bromoacetate and its yield got to 65.7%. The compound 3 was synthesized by using coumpound 2 & hydrazine hydrate(85%) and its yield got to 85.4%, Its structure was confirmed by ~1H NMR, ~(13)C NMR, IR, MS. By using compoud 2 & 1,2-diaminoaethan ,we did not get the aim coumpound,but got a new coumpound 4 and its yield got to 31.0%.Its structure was confirmed by ~1H NMR, ~(13)C NMR, IR.
2 By using compoud 4 & salicylaldehyde the compound 5 was synthesized in the ethyl alcohol and its yield got to 55.7%. The compound 6 was synthesized by using coumpound 3 & Cinnamoyl chloride and by using PEG-400 as Catalyst,and its yield got to 44.7% .Their structure was confirmed by ~1H NMR, ~(13)C NMR, IR, MS.
3 The performance of antiultraviolet of calix[4]arene and its deriva-tives was studied by using UV spectrophotometer. The result shows that compoud 5 had performance of antiultraviolet. Performance of antioxidizes of calix[4]arene and its derivatives wa studied with the methed of DPPH.and the result shows that calix[4]arene and its derivatives had the function of eliminating DPPH, the copound 3 was the best ,its rate of elimination was up to90.6%.
4 It studied that performance of extraction iron, plumbum of calix[4]arene and its derivatives by the means of TAS-986 spectrophotometer. The result shows that calix[4]arene and its derivatives had extracted well iron & plumbum and their rates of extraction were got to 53.4% and 91.9%.
1以自制的对叔丁基杯[4]芳烃1及氯乙酸乙酯为原料,得到了收率65.7%的对叔丁基杯[4]芳烃二取代酯衍生物2;以化合物2和85%的水合肼反应,得到了收率85.4%的对叔丁基杯[4]芳烃二取代酰肼衍生物3。化合物2与乙二胺反应,未得到目标产物,而得到对叔丁基杯[4]芳烃联胺类环状化合物4,收率31.0%。
2化合物3与水杨醛反应,得到了收率55.7%的对叔丁基杯[4]芳烃席夫碱类衍生物5;其结构经~1H NMR、~(13)C NMR、IR、MS确证。以PEG-400为相转移催化剂,通过化合物3在氢氧化钠水溶液中与溶于二氯甲烷的肉桂酰氯反应,合成新的化合物对叔丁基杯[4]芳烃肉桂酰类衍生物6,收率44.7%。其结构经~1HNMR、~(13)C NMR、IR确证。
3用紫外分光光度法研究了杯[4]芳烃及其衍生物的紫外吸收光谱,结果表明,化合物5具有抗紫外性能;采用DPPH法测定杯[4]芳烃及其衍生物的抗氧化性能,结果表明,杯[4]芳烃及其衍生物对DPPH具有一定的清除作用,其中以化合物3的清除效果最佳,高达90.6%。
4用原子吸收研究了杯[4]芳烃及其衍生物对过渡金属离子铁(Ⅲ)、铅(Ⅱ)的萃取性能。结果表明:杯[4]芳烃及其衍生物对铁(Ⅲ)、铅(Ⅱ)有良好的萃取效果,化合物3对铁(Ⅲ)的萃取率最高,化合物5对铅(Ⅱ)的萃取率最高,分别可达到53.4%和91.9%。
Calixarenes were the third generation supermolecule after crown ether and cyclodextrin. Due to their easy functionalization and strong complexing properties towards cations, anions and neutral molecules, they have received particular interests by numerous chemists in recent years. Functional calixarenes have been applied successfully to biomimetic research and separation science and technology. Several calix[4]arene and its derivatives were synthesized and their performance of extracted iron , plumbum were studied and their performance of Antioxidizes and antiultraviolet of calixarene and its derivatives were studied too. This thesis includs the following main points:
1 The ester derivative of p-tert-butyl calix[4]arene 2 was synthesized by using self-made p-tert-butylcalix[4]arene & ethyl bromoacetate and its yield got to 65.7%. The compound 3 was synthesized by using coumpound 2 & hydrazine hydrate(85%) and its yield got to 85.4%, Its structure was confirmed by ~1H NMR, ~(13)C NMR, IR, MS. By using compoud 2 & 1,2-diaminoaethan ,we did not get the aim coumpound,but got a new coumpound 4 and its yield got to 31.0%.Its structure was confirmed by ~1H NMR, ~(13)C NMR, IR.
2 By using compoud 4 & salicylaldehyde the compound 5 was synthesized in the ethyl alcohol and its yield got to 55.7%. The compound 6 was synthesized by using coumpound 3 & Cinnamoyl chloride and by using PEG-400 as Catalyst,and its yield got to 44.7% .Their structure was confirmed by ~1H NMR, ~(13)C NMR, IR, MS.
3 The performance of antiultraviolet of calix[4]arene and its deriva-tives was studied by using UV spectrophotometer. The result shows that compoud 5 had performance of antiultraviolet. Performance of antioxidizes of calix[4]arene and its derivatives wa studied with the methed of DPPH.and the result shows that calix[4]arene and its derivatives had the function of eliminating DPPH, the copound 3 was the best ,its rate of elimination was up to90.6%.
4 It studied that performance of extraction iron, plumbum of calix[4]arene and its derivatives by the means of TAS-986 spectrophotometer. The result shows that calix[4]arene and its derivatives had extracted well iron & plumbum and their rates of extraction were got to 53.4% and 91.9%.
引文
[1]胡昌明.杯芳烃[J].化学通报,1993,(2):17-21.
[2]Hayes B T,Hunter R F.Calix[4]arene and its Synthesis[J].J.Appl.Chem.,1958,8:743-745.
[3]郭兵.新型主体分子-杯芳烃研究进展[J].合成化学,2000,8(5):395-399.
[4]Gutsche C D,Muthukrishnan R.Calixarene.Analysis of the product mixtures produced by the base-catalyzed condensation of formaldehyde with para-substituted phnols[J].J.Org.Chem.,1978,43:4905-4906.
[5]黄志镗,杨联明.杯芳烃研究进展[J].化学进展,1994,6(3):173-177.
[6]余晓冬,吴采樱.杯芳烃构象的分子力学研究[J].高等学校化学学报,1998,19(9):1492-1494.
[7]李鸿图,范平.对叔丁基杯[8]芳烃酯类衍生物的合成[J],辽宁大学学报自然科学版.1999,26(3):253-255.
[8]戈云,蔡亚华,颜朝国.一种杯芳烃酯类衍生物的简洁合成方法[J],化学试剂,2005,27(2),111-112.
[9]Elizabeth M.Collins,M.Anthony McKervey,Evelyn Madigan,Mary B.Moran,Michael Owens,George Ferguson and Stephen J.Harris。 Chemically modified calix[4]arenes.Regioselective synthesis of 1,3-(distal)derivatives and related compounds.X-Ray crystal structure of a diphenol-dinitrile[J],Journal of the Chemical Society,Perkin Transactions 1,1991,3137-3142.
[10]朱建国.氯丙基取代的杯芳烃衍生物的合成[J],河南科技大学学报,2006,27(1):92-95.
[11]吕鉴全.钳状杯[4]芳烃为探针的固态PVC膜汞离子选择性电极[J],高等学校化学学报,2005,26(2):238-9240.
[12]安琳.对叔丁基杯芳烃[n]芳烃酰胺衍生物的合成及其对某些金属离子的的萃取性能[J],应用化学,2005,22(9):980-983.
[13]杨发福.杯[4]芳烃硫脲衍生物的合成及其对阴离子的络合性能[J].有机化学.2002,22(12):1040-1043.
[14]汤又文.几种新型杯[4]芳烃衍生物的合成[J].化学试剂,2004,26(5):277-278.
[15]Cedric B,et al.Mobility of gold and silver ions around a macrocyclic poly-phosphane,Supramolecular architecture of a digold-calix[4]arene complex [J].J.Chem.Soc.,Dalton Trans.,1998:2115-2121.
[16]郑企雨(ZhenQY),黄志镗(HuangZT).化学进展 ProgressinChemistry),1997,9:151-159.
[17]Harvey P D.Wide-rim and outer-face functionalizations of calix[4]arene[J].Coordination Chemistry Reviews,2002:289-309.
[18]周伟,刁国旺.杯[4]芳烃磺酸钠的合成及其表征[J].扬州大学学报(自然科学版),2003,16(2):16-20.
[19]吕鉴泉.杯芳烃的功能化修饰及其在分子识别中的应用[J].化学进展,2001,13(3):209-215.
[20]MaShinkai S.Metal-induced contsumoto H,formational change in pyrene-[32]Matsumoto H,Shinkai S.Metal-induced conformational change in pyrene-appended calix[4]crown-4 which is useful for metal sensing and guest tweezing[J].Tetrahedron Lett,1996,37:77-80.
[21]Bagatin I A,et al.Calix[4]arene Ligands with Phosphorus-Containing Groups Tethered at the Upper Rim[J].Inorg.Chem.,1999,38(7):1585-1591.
[22]Georghiou P E,et al.Syntheses of Calix[4]naphthalenes Derived from 1-Naphthol[J].Org.Chem.,1995,60(22):7284-7289.
[23]Georghiou P E,et al.Spirodienone and Bis(spirodienone)Derivatives of Calix[4]naphthalenes[J].Org.Chem.,1998,63(6):1819-1826.
[24]Georghiou P E,et al.Complexes formed from[60]fullerene and calix[4]naphthalenes[J].Tetrahedron Lett.,1999,40:611-614.
[25]延玺.杯芳烃-卟啉化合物的合成及性质[J].有机化学,2005,25(4):375-385.
[26]吕鉴泉,陈朗星,郭洪声,何锡文等.杯芳烃的功能化修饰及其要分子识别的应用.化学进展,2001,13:209-213.
[27]褚惠虹.硫杂杯芳烃及其衍生物的合成与表征[J].有机化学,2003,23(11):1255-1259.
[28]黄志镗.杯芳烃的研究进展[A].全国第七届大环化合物学术讨论会论文集[C].中国化学会.济南.1994:8.
[29]Iwamoto K,Shinkai S.Synthesis and ion selectivity of all conformation isomers of tetrakis[(ethoxycarbonyl)methoxy]calyx[4]arene[J].J.Org.Chem.,1992,57,7066.
[30]Gutsche C D,et al.The synthesis characterization and properties of the calixarenes from p-tert-butylphenol[J].J.Am.Chem.Soc.,1981,103(13):3782-3792.
[31]史春越.杯芳烃对有机小分子识别作用的研究进展[J].辽宁大学学报(自然科学版),2003,30(1):82-86.
[32]Mckervey M A,et al.Molecular receptors.Synthesis and x-ray crystal structure of a calix[4]arene tetracarbonate-acetonitrile(1:1)clathrate[J].J.Org.Chem.,1986,51(I9):3581-3584.
[33]Shikai S,et al.NMR determination of association constants for calixarene complexes.Evidence for the formation of a 1:2 complex with calix[8]arene[J].J.Am.Chem.Soc.,1988,110(21):7214-7215.
[34]孟羽中.新型杯芳烃衍生物的合成及其配位性质研究[D].天津:南开大学,2000.
[45]Murakami H,Shinkai S."Metal-switched" molecular receptor site designed on a calix[4]arene platform[J].Tetrahedron Lett.,1993,34:4237-4240.
[36]Loeber C,et al.Multifunctional phosphane and phosphane oxide ligands derived from p-tert-butylcalix[4]arene.Synthesis of a large diphosphane with C_2 symmetry and behaving as a cis or trans binding ligand[J].J Org.metal.Chem.,1994,475(1-2):297-305.
[37]Ungaro R,Pochini A.Calixarene-based cation receptors and carriers[J].Top.Inclusion Sci.,1991:127-147.
[38]Zhang L T,et al.Calixarene as host in aqueous media:inclusion complexation of ferrocene derivatives by a water-soluble calix[6]arene[J].J.Chem.Soc.,Chem.Commun.,1993:1017-1019.
[39]孙红保.杯芳烃对铁的配位及其超分子化学研究进展[J].化学通报,2000(4):8-12.
[40]郑炎松.杯芳烃的配位性质[J].化学进展,1999,11(3):275-285.
[41]Rudkuch D M,et al.Calix[4]arene Salenes:A Bifunctional Recepter for NaH_2PO_4[J].J.Org.Chem.,1994(13):3683-3686.
[42]Beer P D,et al.Anion recognition properties of new-rim bis[rhenium(I)bipyridyl,ruthenium(Ⅱ)bis(bipyridyl),cobaltocenium]calix[4]arene receptors dictated by lower-rim substituents[J].J Chem.Soc.Chem.Commun,1996:2161-2162.
[43]Deligue X,et al.Multicavitands Ⅱ:Synthesis of a non centrosymmetric hollow molecular unit(koiland)based on fusion of two p-tert-butylcalix[4]arenes by both silicon and titanium atoms[J].Tetrahedron Lett.,1993,34(47):7561-7564.
[44]Dienst E V,et al.Novel water-soluble cyclodextrin-calix[4]arene host molecules with strongly enhanced binding properties[J].J.Chem.Soc.Chem.Commun,1995,(11):1151-1152.
[55]杨发福,陈远荫.大环杯芳烃冠醚的研究现状与展望[J].合成化学,2003,11(3):203-208.
[46]Dmitry M,et al.Capped Biscalix[4]arene-Zn-Porphyrin:Metal loreceptor with a Rigid Cavity[J].J.Org.Chem.,1995,60(20):6585-6587.
[47]Iqbal M,et al.Calixarenes 21:The conformations and structures of the products of aroylation of the calix[4]arenas[J].Tetrahedron,1987,43:4917-4930.
[48]Gutsche C D,Bauer L J.Calixarenes.13.The conformational properties of calix[4]arenes,calix[6]arenes,calix[8]arenes,and oxacalixarenes[J].J.Am.Chem.Soc.,1985,107(21):6052-6059.
[49]李赏.杯芳烃衍生物的合成、结构及其配位性质研究[D].天津:南开大学,2000.
[50]Mekervey M A,et al.Synthesis,X-ray crystal structures,and cation transfer properties of alkyl calixaryl acetates,a new series of molecular receptors[J].J.Chem.Chem.Soc,Chem.Commun,1985,(7):388-390.
[51]Castellano R K,et al.Tetramethoxy Calix[4]arenes Revisited:Conformational Control through Self-Assembly[J].J.Am.Chem.Soc.,1996,118(41):10002-10003.
[52]Orr G W,et al.Controlling Molecular Self-Organization:Formation of Nano meter-Scale Spheres and Tubules[J].Science,1999,285(5430):1049-1052.
[53]Cormar Gerhard et al.Stabilisatorn fur hochpolymere,niedermolekulare organische Verbindugen und Ole.DD,290905A.1991.
[54]Seiffarth Klaus et al.Stabilisatoren fur niedermolekulare und Hochpolymere,organische Materialien.DD,273844A1.1989.
[55]洪学传.杯芳烃-新型有机材料抗氧剂[J],合成材料老化与应用,1999,2:19-24.
[56]张峻.杯[4]芳烃衍生物对稀土敏化发光的研究[J].河南科学,2003,21(6):707-708.
[57]潘现军,张晓梅.新型杯[4]芳烃的衍生物的合成及结构表征[J].安徽理工大学 学报(自然科学版),2006,(1):52-55.
[58]Hu,Xu-Bo.A Convenient Approach of Preparation of Calix[4]arenas Bearing Ester Pendants[J].HECHENG HUAXUE 2000,18(2):151-154.
[59]杨发福.含酰胺和硫脲单元的杯[4]芳烃衍生物的合成[J].合成化学.2005,13(1):53.54.
[60]ChatterjeeSN,AgarwalSanjiv,BoseBiplab.Anapproach towards understanding the genesis of sunlighrt-induced skin cancer.BiochemBiophys,1990,27(4):25463.
[61]洪学传.杯芳烃-新型有机材料光稳定剂[J].中国塑料.2000,14(1):71-75.
[62]付荣.用二苯代苦味酰基自由基分光光度法测定川芎、红景天和黄芪的抗氧化活性[J].大连轻工业学院学报.2004,23(2):114-117.
[63]陆国弟,等.杯芳烃的配位化学(Ⅺ)[J].同济大学学报,1999,27(3):375-378.
[64]蒋海英,潘现军,张晓梅.新型杯[4]芳烃衍生物对pb~(2+),Cd~(2+)的萃取性质[J].应用化工,2006,35(12):922-923.
[2]Hayes B T,Hunter R F.Calix[4]arene and its Synthesis[J].J.Appl.Chem.,1958,8:743-745.
[3]郭兵.新型主体分子-杯芳烃研究进展[J].合成化学,2000,8(5):395-399.
[4]Gutsche C D,Muthukrishnan R.Calixarene.Analysis of the product mixtures produced by the base-catalyzed condensation of formaldehyde with para-substituted phnols[J].J.Org.Chem.,1978,43:4905-4906.
[5]黄志镗,杨联明.杯芳烃研究进展[J].化学进展,1994,6(3):173-177.
[6]余晓冬,吴采樱.杯芳烃构象的分子力学研究[J].高等学校化学学报,1998,19(9):1492-1494.
[7]李鸿图,范平.对叔丁基杯[8]芳烃酯类衍生物的合成[J],辽宁大学学报自然科学版.1999,26(3):253-255.
[8]戈云,蔡亚华,颜朝国.一种杯芳烃酯类衍生物的简洁合成方法[J],化学试剂,2005,27(2),111-112.
[9]Elizabeth M.Collins,M.Anthony McKervey,Evelyn Madigan,Mary B.Moran,Michael Owens,George Ferguson and Stephen J.Harris。 Chemically modified calix[4]arenes.Regioselective synthesis of 1,3-(distal)derivatives and related compounds.X-Ray crystal structure of a diphenol-dinitrile[J],Journal of the Chemical Society,Perkin Transactions 1,1991,3137-3142.
[10]朱建国.氯丙基取代的杯芳烃衍生物的合成[J],河南科技大学学报,2006,27(1):92-95.
[11]吕鉴全.钳状杯[4]芳烃为探针的固态PVC膜汞离子选择性电极[J],高等学校化学学报,2005,26(2):238-9240.
[12]安琳.对叔丁基杯芳烃[n]芳烃酰胺衍生物的合成及其对某些金属离子的的萃取性能[J],应用化学,2005,22(9):980-983.
[13]杨发福.杯[4]芳烃硫脲衍生物的合成及其对阴离子的络合性能[J].有机化学.2002,22(12):1040-1043.
[14]汤又文.几种新型杯[4]芳烃衍生物的合成[J].化学试剂,2004,26(5):277-278.
[15]Cedric B,et al.Mobility of gold and silver ions around a macrocyclic poly-phosphane,Supramolecular architecture of a digold-calix[4]arene complex [J].J.Chem.Soc.,Dalton Trans.,1998:2115-2121.
[16]郑企雨(ZhenQY),黄志镗(HuangZT).化学进展 ProgressinChemistry),1997,9:151-159.
[17]Harvey P D.Wide-rim and outer-face functionalizations of calix[4]arene[J].Coordination Chemistry Reviews,2002:289-309.
[18]周伟,刁国旺.杯[4]芳烃磺酸钠的合成及其表征[J].扬州大学学报(自然科学版),2003,16(2):16-20.
[19]吕鉴泉.杯芳烃的功能化修饰及其在分子识别中的应用[J].化学进展,2001,13(3):209-215.
[20]MaShinkai S.Metal-induced contsumoto H,formational change in pyrene-[32]Matsumoto H,Shinkai S.Metal-induced conformational change in pyrene-appended calix[4]crown-4 which is useful for metal sensing and guest tweezing[J].Tetrahedron Lett,1996,37:77-80.
[21]Bagatin I A,et al.Calix[4]arene Ligands with Phosphorus-Containing Groups Tethered at the Upper Rim[J].Inorg.Chem.,1999,38(7):1585-1591.
[22]Georghiou P E,et al.Syntheses of Calix[4]naphthalenes Derived from 1-Naphthol[J].Org.Chem.,1995,60(22):7284-7289.
[23]Georghiou P E,et al.Spirodienone and Bis(spirodienone)Derivatives of Calix[4]naphthalenes[J].Org.Chem.,1998,63(6):1819-1826.
[24]Georghiou P E,et al.Complexes formed from[60]fullerene and calix[4]naphthalenes[J].Tetrahedron Lett.,1999,40:611-614.
[25]延玺.杯芳烃-卟啉化合物的合成及性质[J].有机化学,2005,25(4):375-385.
[26]吕鉴泉,陈朗星,郭洪声,何锡文等.杯芳烃的功能化修饰及其要分子识别的应用.化学进展,2001,13:209-213.
[27]褚惠虹.硫杂杯芳烃及其衍生物的合成与表征[J].有机化学,2003,23(11):1255-1259.
[28]黄志镗.杯芳烃的研究进展[A].全国第七届大环化合物学术讨论会论文集[C].中国化学会.济南.1994:8.
[29]Iwamoto K,Shinkai S.Synthesis and ion selectivity of all conformation isomers of tetrakis[(ethoxycarbonyl)methoxy]calyx[4]arene[J].J.Org.Chem.,1992,57,7066.
[30]Gutsche C D,et al.The synthesis characterization and properties of the calixarenes from p-tert-butylphenol[J].J.Am.Chem.Soc.,1981,103(13):3782-3792.
[31]史春越.杯芳烃对有机小分子识别作用的研究进展[J].辽宁大学学报(自然科学版),2003,30(1):82-86.
[32]Mckervey M A,et al.Molecular receptors.Synthesis and x-ray crystal structure of a calix[4]arene tetracarbonate-acetonitrile(1:1)clathrate[J].J.Org.Chem.,1986,51(I9):3581-3584.
[33]Shikai S,et al.NMR determination of association constants for calixarene complexes.Evidence for the formation of a 1:2 complex with calix[8]arene[J].J.Am.Chem.Soc.,1988,110(21):7214-7215.
[34]孟羽中.新型杯芳烃衍生物的合成及其配位性质研究[D].天津:南开大学,2000.
[45]Murakami H,Shinkai S."Metal-switched" molecular receptor site designed on a calix[4]arene platform[J].Tetrahedron Lett.,1993,34:4237-4240.
[36]Loeber C,et al.Multifunctional phosphane and phosphane oxide ligands derived from p-tert-butylcalix[4]arene.Synthesis of a large diphosphane with C_2 symmetry and behaving as a cis or trans binding ligand[J].J Org.metal.Chem.,1994,475(1-2):297-305.
[37]Ungaro R,Pochini A.Calixarene-based cation receptors and carriers[J].Top.Inclusion Sci.,1991:127-147.
[38]Zhang L T,et al.Calixarene as host in aqueous media:inclusion complexation of ferrocene derivatives by a water-soluble calix[6]arene[J].J.Chem.Soc.,Chem.Commun.,1993:1017-1019.
[39]孙红保.杯芳烃对铁的配位及其超分子化学研究进展[J].化学通报,2000(4):8-12.
[40]郑炎松.杯芳烃的配位性质[J].化学进展,1999,11(3):275-285.
[41]Rudkuch D M,et al.Calix[4]arene Salenes:A Bifunctional Recepter for NaH_2PO_4[J].J.Org.Chem.,1994(13):3683-3686.
[42]Beer P D,et al.Anion recognition properties of new-rim bis[rhenium(I)bipyridyl,ruthenium(Ⅱ)bis(bipyridyl),cobaltocenium]calix[4]arene receptors dictated by lower-rim substituents[J].J Chem.Soc.Chem.Commun,1996:2161-2162.
[43]Deligue X,et al.Multicavitands Ⅱ:Synthesis of a non centrosymmetric hollow molecular unit(koiland)based on fusion of two p-tert-butylcalix[4]arenes by both silicon and titanium atoms[J].Tetrahedron Lett.,1993,34(47):7561-7564.
[44]Dienst E V,et al.Novel water-soluble cyclodextrin-calix[4]arene host molecules with strongly enhanced binding properties[J].J.Chem.Soc.Chem.Commun,1995,(11):1151-1152.
[55]杨发福,陈远荫.大环杯芳烃冠醚的研究现状与展望[J].合成化学,2003,11(3):203-208.
[46]Dmitry M,et al.Capped Biscalix[4]arene-Zn-Porphyrin:Metal loreceptor with a Rigid Cavity[J].J.Org.Chem.,1995,60(20):6585-6587.
[47]Iqbal M,et al.Calixarenes 21:The conformations and structures of the products of aroylation of the calix[4]arenas[J].Tetrahedron,1987,43:4917-4930.
[48]Gutsche C D,Bauer L J.Calixarenes.13.The conformational properties of calix[4]arenes,calix[6]arenes,calix[8]arenes,and oxacalixarenes[J].J.Am.Chem.Soc.,1985,107(21):6052-6059.
[49]李赏.杯芳烃衍生物的合成、结构及其配位性质研究[D].天津:南开大学,2000.
[50]Mekervey M A,et al.Synthesis,X-ray crystal structures,and cation transfer properties of alkyl calixaryl acetates,a new series of molecular receptors[J].J.Chem.Chem.Soc,Chem.Commun,1985,(7):388-390.
[51]Castellano R K,et al.Tetramethoxy Calix[4]arenes Revisited:Conformational Control through Self-Assembly[J].J.Am.Chem.Soc.,1996,118(41):10002-10003.
[52]Orr G W,et al.Controlling Molecular Self-Organization:Formation of Nano meter-Scale Spheres and Tubules[J].Science,1999,285(5430):1049-1052.
[53]Cormar Gerhard et al.Stabilisatorn fur hochpolymere,niedermolekulare organische Verbindugen und Ole.DD,290905A.1991.
[54]Seiffarth Klaus et al.Stabilisatoren fur niedermolekulare und Hochpolymere,organische Materialien.DD,273844A1.1989.
[55]洪学传.杯芳烃-新型有机材料抗氧剂[J],合成材料老化与应用,1999,2:19-24.
[56]张峻.杯[4]芳烃衍生物对稀土敏化发光的研究[J].河南科学,2003,21(6):707-708.
[57]潘现军,张晓梅.新型杯[4]芳烃的衍生物的合成及结构表征[J].安徽理工大学 学报(自然科学版),2006,(1):52-55.
[58]Hu,Xu-Bo.A Convenient Approach of Preparation of Calix[4]arenas Bearing Ester Pendants[J].HECHENG HUAXUE 2000,18(2):151-154.
[59]杨发福.含酰胺和硫脲单元的杯[4]芳烃衍生物的合成[J].合成化学.2005,13(1):53.54.
[60]ChatterjeeSN,AgarwalSanjiv,BoseBiplab.Anapproach towards understanding the genesis of sunlighrt-induced skin cancer.BiochemBiophys,1990,27(4):25463.
[61]洪学传.杯芳烃-新型有机材料光稳定剂[J].中国塑料.2000,14(1):71-75.
[62]付荣.用二苯代苦味酰基自由基分光光度法测定川芎、红景天和黄芪的抗氧化活性[J].大连轻工业学院学报.2004,23(2):114-117.
[63]陆国弟,等.杯芳烃的配位化学(Ⅺ)[J].同济大学学报,1999,27(3):375-378.
[64]蒋海英,潘现军,张晓梅.新型杯[4]芳烃衍生物对pb~(2+),Cd~(2+)的萃取性质[J].应用化工,2006,35(12):922-923.