苯醚类衍生物的合成及表征
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摘要
苯醚类化合物是一类重要的有机化合物，在很多方面都有巨大的应用价值。在农业上可以用于农田中农作物的除草剂。同时苯醚类化合物也是一类重要的抑菌剂，由于对生产生活中常见的多种细菌病毒具有高效的杀灭和抑制作用，因而广泛地应用于各类卫生消毒用品中。此外，还有一类苯醚类化合物用作表面活性剂。苯醚类化合物还是一类重要的有机合成中间体，可以在苯环上接上特定的官能团以用于下一步的反应，常见的有用作合成TLCP、HD-244等。
偶氮化合物是指含有氮氮双键的一类化合物。偶氮化合物存在两种结构，顺式结构和反式结构。在大多数情况下，偶氮化合物是以反式结构存在的。偶氮化合物是一类特殊的化合物，在合理的外界刺激下，化合物的结构会发生变化。用特定波长入1的单色光照射化合物，反式结构转变为顺式结构；用另一波长入2的单色光连续照射化合物，顺式结构又会可逆的回复到反式结构。我们将以上可逆的过程称之为光致变色现象。正是由于这种特殊的现象，偶氮化合物可用作光信息存储材料，分子开关等。同时，由于偶氮化合物大多都有鲜艳的颜色，而被用作一类染料。因此，偶氮化合物很具有研究价值，而国内外的许多学者也为偶氮化合物的研究做出了巨大的贡献。
酰胺化合物是指含有酰胺键的一类化合物。酰胺键也称肽键，是蛋白质结构的基本组成部分。酰胺基团具有较好的生物活性，在生物学上可以模拟生物生命的具体过程；在农业方面可作为除草剂、杀虫剂和杀菌剂；在医学方面可以作为抗肿瘤药物；同时由于酰胺化合物大多含有氮、氧等杂原子，可作为多齿螯合配体，与金属离子形成稳定的络合物等。
本文一共合成了两系列苯醚类衍生物，即偶氮类苯醚衍生物和酰胺类苯醚衍生物。
通过葡萄糖还原法合成了偶氮类苯醚衍生物化合物，并对偶氮类苯醚衍生物进行了表征，同时对其光致变色性质进行了研究，取得了较好的效果。
合成了酰胺类苯醚衍生物，并对酰胺类苯醚衍生物进行了表征，与Cu~(2+)反应生成了一种新的络合物，对此络合物进行了表征，提出了酰胺类苯醚衍生物做荧光传感器的构想。
Phenyl ether compound was one important kind of organic compounds, and hadgreat value in many ares. In agriculture it can be used of herbicide for the crops in thefarmland. At the same time, phenyl ethers are also an important class of fundicideswhat can kill and inhibit efficiently bacterias and viruses what can be foundeverywhere, so that it is widely used in various of sanitation and disinfection supplies.In addition, there is another phenyl ethers what are employed as surfactants. Phenylethers are an important intermideates for organic systhesis which can be connected toa specific functional group in the benzene ring for the next reaction, what is commonin TLCP、HD-244and so on.
Azo compounds are the ones containing–N=N-bond. Azo compounds have twostructures: trans structures and cis structures. At the most times, Azo compounds existin trans form. Azo compound is a special kind of compound, the structure ofcompounds will chang with a suitable extermal stimulus. Irradiated with amonochromatic light of specific wavelength入_1,the trans structure will chang to cisstructure; if we continue irradiating with a monochromatic light of specificwavelength入_2,the cis structure will restore trans structure. We call that reversibleprocess photochemical isomerization. It is because of that particular phenomenon, azocompounds are used as optical information storage materials, molecular switches, andso on. Most azo compounds have bright colors, so they can be used as dyes. Therefore,the azo compounds have great value in explore. Many scholars at home and abroadmake tremendous contributions to the study of azo compound.
Amide compounds are the ones containing amide bond. Amide bond is alsocalled peptide bond what is an essential part of the protein structure. Amide group hasa great biological activity. In Biology, amide compounds can be used to simulate thebiological life process. In agriculture, amide compounds can be employed as herbicides, insecticides and fungicides. In medicine, some amide compounds aresynthesized as anticancer drugs. In addition, because most of amide compoundscontain nitrogen, oxygen and another heteroatoms, what are used as polydentateligands, amide compounds can react with metal ion to form a new metal complex.
Two kinds of phenyl ether derivatives were synthesized in this paper: one isphenyl ether derivatives with azo group, the other is amides of phenyl etherderivatives.
The azo compounds were synthesized througth the glucose reduction reaction,and every compound was characterized clearly. We also examined their properties ofreversible cis-trans photoisomerizations, and gained good results.
The amide compounds were synthesized and were characterized definitely. Anew copper(Ⅱ) complexe was prepared and characterized. Because of itsphotophysical propeties, the idea of fluorescent sensors was proposed.
偶氮化合物是指含有氮氮双键的一类化合物。偶氮化合物存在两种结构，顺式结构和反式结构。在大多数情况下，偶氮化合物是以反式结构存在的。偶氮化合物是一类特殊的化合物，在合理的外界刺激下，化合物的结构会发生变化。用特定波长入1的单色光照射化合物，反式结构转变为顺式结构；用另一波长入2的单色光连续照射化合物，顺式结构又会可逆的回复到反式结构。我们将以上可逆的过程称之为光致变色现象。正是由于这种特殊的现象，偶氮化合物可用作光信息存储材料，分子开关等。同时，由于偶氮化合物大多都有鲜艳的颜色，而被用作一类染料。因此，偶氮化合物很具有研究价值，而国内外的许多学者也为偶氮化合物的研究做出了巨大的贡献。
酰胺化合物是指含有酰胺键的一类化合物。酰胺键也称肽键，是蛋白质结构的基本组成部分。酰胺基团具有较好的生物活性，在生物学上可以模拟生物生命的具体过程；在农业方面可作为除草剂、杀虫剂和杀菌剂；在医学方面可以作为抗肿瘤药物；同时由于酰胺化合物大多含有氮、氧等杂原子，可作为多齿螯合配体，与金属离子形成稳定的络合物等。
本文一共合成了两系列苯醚类衍生物，即偶氮类苯醚衍生物和酰胺类苯醚衍生物。
通过葡萄糖还原法合成了偶氮类苯醚衍生物化合物，并对偶氮类苯醚衍生物进行了表征，同时对其光致变色性质进行了研究，取得了较好的效果。
合成了酰胺类苯醚衍生物，并对酰胺类苯醚衍生物进行了表征，与Cu~(2+)反应生成了一种新的络合物，对此络合物进行了表征，提出了酰胺类苯醚衍生物做荧光传感器的构想。
Phenyl ether compound was one important kind of organic compounds, and hadgreat value in many ares. In agriculture it can be used of herbicide for the crops in thefarmland. At the same time, phenyl ethers are also an important class of fundicideswhat can kill and inhibit efficiently bacterias and viruses what can be foundeverywhere, so that it is widely used in various of sanitation and disinfection supplies.In addition, there is another phenyl ethers what are employed as surfactants. Phenylethers are an important intermideates for organic systhesis which can be connected toa specific functional group in the benzene ring for the next reaction, what is commonin TLCP、HD-244and so on.
Azo compounds are the ones containing–N=N-bond. Azo compounds have twostructures: trans structures and cis structures. At the most times, Azo compounds existin trans form. Azo compound is a special kind of compound, the structure ofcompounds will chang with a suitable extermal stimulus. Irradiated with amonochromatic light of specific wavelength入_1,the trans structure will chang to cisstructure; if we continue irradiating with a monochromatic light of specificwavelength入_2,the cis structure will restore trans structure. We call that reversibleprocess photochemical isomerization. It is because of that particular phenomenon, azocompounds are used as optical information storage materials, molecular switches, andso on. Most azo compounds have bright colors, so they can be used as dyes. Therefore,the azo compounds have great value in explore. Many scholars at home and abroadmake tremendous contributions to the study of azo compound.
Amide compounds are the ones containing amide bond. Amide bond is alsocalled peptide bond what is an essential part of the protein structure. Amide group hasa great biological activity. In Biology, amide compounds can be used to simulate thebiological life process. In agriculture, amide compounds can be employed as herbicides, insecticides and fungicides. In medicine, some amide compounds aresynthesized as anticancer drugs. In addition, because most of amide compoundscontain nitrogen, oxygen and another heteroatoms, what are used as polydentateligands, amide compounds can react with metal ion to form a new metal complex.
Two kinds of phenyl ether derivatives were synthesized in this paper: one isphenyl ether derivatives with azo group, the other is amides of phenyl etherderivatives.
The azo compounds were synthesized througth the glucose reduction reaction,and every compound was characterized clearly. We also examined their properties ofreversible cis-trans photoisomerizations, and gained good results.
The amide compounds were synthesized and were characterized definitely. Anew copper(Ⅱ) complexe was prepared and characterized. Because of itsphotophysical propeties, the idea of fluorescent sensors was proposed.
引文
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[4] XIONG F, FRANCIS J S. New brominated diphenyl Ether from an vnidentifieclspecies of dysiclea species[J]. J.Nat.Prods,1996,59(11),1102-1103,
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[8]虞鑫海等.新型聚酰亚胺的合成及其性能[J].绝缘材料通讯,2000(6):10-12
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[20]DONG H L,JA H I. An Azophenol-based Chromogenic Pyrophosphate Sensor inWater[J]. J. AM. CHEM. SOC,2003,125,77527753.
[21]DOMENICO A, EUGENIO A. Synthesis and Characterization of SegmentedLiquid Crystalline Polymers with the Azo Group in the Main Chain[J].Macromolecules,2004,37,6418-6423.
[22]MEDONCA C R., SANTOS D S, BALOGH D T. Optical storage in mixedLangmuir-Blodgett(LB) films of azopolymers and cadmium stearate[J].Polymer,2001,42:6539-6544
[23]陈清元,何蕴韶等.对二甲基丙烯酰胺偶氮苯的合成[J].南方医科大学学报,2006,26(10):1465-1466.
[24]AMOLD M S, AYOURIS P,PAN Z W. Field-effect transistors based on singlesemiconducting oxides nanobelts[J]. J Phys Chem B,2003,107:659-663.
[25]SHINKAI S, NAKAJI T, OGAWA T, SHIGEMATSU K, MANABE O.Photoresponsive Crown Ethers.2.Photocontrol of Ion Extraction and IonTransport by a Bis(crown ether) with a Butterfly-like Motion[J]. J. Am. Chem.Soc,1981,103,111
[26]颜星中,蔡志岗,杨佩青等.偶氮苯功能化聚酯的合成与二阶非线性光学特性[J].高分子材料科学与工程，1997,13（4）：104-108.
[27]LIU Z F, HASHIMOTO K, FUJISHIMA P. Photoelectrochemical informationstorage using an azobenzene derivative[J]. Nature,347,658–660.
[28]刘长令.杀虫剂及杀蜻剂的研究进展[J].农药群学与营理,1998,2:28一31.
[29]BEEK J R; LYNEH M P. l，5一disubstituted一IH一Pyrazole一4一carboxamide derivatives useful as hethieides and aquatie algieides[J],1985,GB2149402.
[30]徐尚成.杂环杀虫剂研究开发的新进展[J].红苏讼工,1999,27(3):4-7.
[31]IESLIE R.H, LAN G. B, DAVID W H, EDGAR W P. Derivatives ofN-phenylpyrazoles[P].US5608077,1997.
[32]李宗成.近年来开发的农药新品种[J].农或2001,40(3):43一45
[33]刘长令.农用杀菌剂开发的新进展[J].农药料学与营:理,2000,21(3):20一26
[34]HUPPATZ J L. Systemic fungieides: the synthesis of certain Pyrazole analogs ofcarboxin[J].Aust.J.Chem,1983，36(l):135一147
[35]SUZUKI H, MITA T.JP02268156[Chem.Abstr.1990,114,247266r]
[36]HANANURE M, NISHIKOBO M. JP0249708.
[37]NATSUME B, KYOMUA N, KIKUTAL K. Pyrazoleearboxajrnide,inseetieidaland mitieidal composition，and fungididal composition for use inagriculture and hortieulture[J],1991,EP0462573AJ.
[38]BEEK J R, LYNCH M P.1，5一disubstituted一1H一Pyrazole一4一carboxamide derivatives useful as herbieides and aquatic algieides[J].1985,GB2149403.
[39]王大翔.杂环化合物在农药发展中的重要作用[J].农或1995,34(1):4一9
[40]薛振祥.国外化学农药发展动向及前景[J].化工技术经济,1998,2:l一9
[41]缪应江.酰胺类除草剂的安全性[J].农药快讯,2002,(20）:2-4.
[42]苏少泉.稻田高活性杀稗剂苯噻草胺的开发与使用[J].1999,38(3):1-6.
[43]薛思佳,阎琳,方海斌. N-(4,6-二取代嘧啶一2-基)-2,4-二氯苯氧乙酰胺的合成及其生物活性测定[J].上海师范大学学报,2007,36(26):79-82.
[44]丁玉珍等.链状聚醚用作萃取剂的研究—不同取代基的三甘酰双胺萃取轻稀土[J].化学试剂,1986,8(4）,201-204.
[45]秦宝锋,王耀宁,焦天权,胡丽天.以对氨基苯甲酸乙酯为端基的酰胺型开链冠醚的合成与表征[J].化学试剂,2005,27(12),749~75.
[46] KUMARESH G, GOUTAM M. Triphenylamine-based novel PET sensors in selectiverecognition of dicarboxylic acids[J].Tetrahedron Letters,2006,47:2365–2369
[2] LINDSAY J, ANDREW A. The marine natural product3,5-dibromo-2-(2,4-dibromophenoxg) phenol, Inhibits contraetile actirity in the guinea pig ileum[J].Clin.Exp.Pharmacol.Physiol,1993,20,697-704
[3] JAVER S, JOHN D E. A new brominated diphenyl Ether from a philippinedysiclea species [J].J.Nat.Prods,1990,53(3),757-760·
[4] XIONG F, FRANCIS J S. New brominated diphenyl Ether from an vnidentifieclspecies of dysiclea species[J]. J.Nat.Prods,1996,59(11),1102-1103,
[5] DIAN H, RU A E, PETER P. Four new bioaective polybrominatedDiphenylEthers of the sponge dysidea herbacea from west Sumatra, Indonesia[J].J.Nat.Prods,1997,60(12),1313-1316.
[6] COLEMAN G H, PERKI NS R P. Alkylated diphenyloxide US,2170809[P].1939-08-29
[7]白亚东等.辛烷基二苯醚二磺酸钠的合成及性能研究[J].应用化工,2009,38(4):49-63.
[8]虞鑫海等.新型聚酰亚胺的合成及其性能[J].绝缘材料通讯,2000(6):10-12
[9]宋涛等.3,4’-二氨基二苯醚合成工艺的研究进展[J].化工中间体,2008(9):65-68.
[10]POWERS E J, SERAD G A. High Performance Polymers: Their Origin andDevelopment[J].ProQuest-CSA,1986,355-373
[11]王玉环等.4，4′-二苯醚二甲酸合成工艺研究[J].河北化工,2007,30(11):41-42.
[12]RICHARD B L, JACKSON A. Purification of2,4,4’-trichloro-2′-hydroxyd-iphenyle-ther solvent extraction[P].US:4486610,1984-12-04
[13]JUSKOWIAK M, OLSZANOWSKI A, Jurasz K. Preparation of chlorinatedderivatives of o-phenoxyphenol[P].Pol.PL:149406,1990-03-3
[14]BOCK H, RUDOLPH G.. Color and Consitituion of Azo Compound[J]. WileyOnline Library,1965,4（6）：457-471.
[15]HARTLEY G. S. The cis-form of azobenzene[J]. Nature,1937,140,281
[16]RAU H.B. Organic photoconductive materials: Recent trends and development[J].Phys. Chem.,1969,73:810-819.
[17]CHAMP. R. B., SHATTUCK M D., Electrophotographic processes using disazopigments[P]. US:3898084,1975-08-05.
[18]TODOROV T., TOMOVA N L. Nikolova. High-sensitivity material with reversiblephoto-induced anisotropy[J]. Opt. Commun,1983,47,123
[19]TAKAYOSHI N, HIROAKI T. Formation of Langmuir-Blodgett films of afullerene[J]. Chem. Lett,1992,173.
[20]DONG H L,JA H I. An Azophenol-based Chromogenic Pyrophosphate Sensor inWater[J]. J. AM. CHEM. SOC,2003,125,77527753.
[21]DOMENICO A, EUGENIO A. Synthesis and Characterization of SegmentedLiquid Crystalline Polymers with the Azo Group in the Main Chain[J].Macromolecules,2004,37,6418-6423.
[22]MEDONCA C R., SANTOS D S, BALOGH D T. Optical storage in mixedLangmuir-Blodgett(LB) films of azopolymers and cadmium stearate[J].Polymer,2001,42:6539-6544
[23]陈清元,何蕴韶等.对二甲基丙烯酰胺偶氮苯的合成[J].南方医科大学学报,2006,26(10):1465-1466.
[24]AMOLD M S, AYOURIS P,PAN Z W. Field-effect transistors based on singlesemiconducting oxides nanobelts[J]. J Phys Chem B,2003,107:659-663.
[25]SHINKAI S, NAKAJI T, OGAWA T, SHIGEMATSU K, MANABE O.Photoresponsive Crown Ethers.2.Photocontrol of Ion Extraction and IonTransport by a Bis(crown ether) with a Butterfly-like Motion[J]. J. Am. Chem.Soc,1981,103,111
[26]颜星中,蔡志岗,杨佩青等.偶氮苯功能化聚酯的合成与二阶非线性光学特性[J].高分子材料科学与工程，1997,13（4）：104-108.
[27]LIU Z F, HASHIMOTO K, FUJISHIMA P. Photoelectrochemical informationstorage using an azobenzene derivative[J]. Nature,347,658–660.
[28]刘长令.杀虫剂及杀蜻剂的研究进展[J].农药群学与营理,1998,2:28一31.
[29]BEEK J R; LYNEH M P. l，5一disubstituted一IH一Pyrazole一4一carboxamide derivatives useful as hethieides and aquatie algieides[J],1985,GB2149402.
[30]徐尚成.杂环杀虫剂研究开发的新进展[J].红苏讼工,1999,27(3):4-7.
[31]IESLIE R.H, LAN G. B, DAVID W H, EDGAR W P. Derivatives ofN-phenylpyrazoles[P].US5608077,1997.
[32]李宗成.近年来开发的农药新品种[J].农或2001,40(3):43一45
[33]刘长令.农用杀菌剂开发的新进展[J].农药料学与营:理,2000,21(3):20一26
[34]HUPPATZ J L. Systemic fungieides: the synthesis of certain Pyrazole analogs ofcarboxin[J].Aust.J.Chem,1983，36(l):135一147
[35]SUZUKI H, MITA T.JP02268156[Chem.Abstr.1990,114,247266r]
[36]HANANURE M, NISHIKOBO M. JP0249708.
[37]NATSUME B, KYOMUA N, KIKUTAL K. Pyrazoleearboxajrnide,inseetieidaland mitieidal composition，and fungididal composition for use inagriculture and hortieulture[J],1991,EP0462573AJ.
[38]BEEK J R, LYNCH M P.1，5一disubstituted一1H一Pyrazole一4一carboxamide derivatives useful as herbieides and aquatic algieides[J].1985,GB2149403.
[39]王大翔.杂环化合物在农药发展中的重要作用[J].农或1995,34(1):4一9
[40]薛振祥.国外化学农药发展动向及前景[J].化工技术经济,1998,2:l一9
[41]缪应江.酰胺类除草剂的安全性[J].农药快讯,2002,(20）:2-4.
[42]苏少泉.稻田高活性杀稗剂苯噻草胺的开发与使用[J].1999,38(3):1-6.
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