氨基硫脲与醛酮加成—缩合反应理论研究
|
摘要
硫脲衍生物因具有特殊的功能结构,使其在生物医学、工农业生产、日常生活及其它学科的各个领域都有非常重要的用途,对化学学科的各个分支及一些边缘学科也有很重要的作用。但是对于硫脲衍生物与其他物质反应的理论研究还很少,热力学参数的数据还不完善。量子化学方法可应用于分子热力学、光谱和反应动力学性质的研究。因此利用量子化学研究硫脲衍生物与醛、酮加成一缩合反应系统中反应物和产物的电子结构、光谱性质和热力学性质,将对此类反应活性、可行性和外部条件的控制从理论上得到较好的预示,具有重要的理论意义和实际应用价值。
本论文主要研究内容为:
(1)对香草醛和氨基硫脲亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的香草醛分子中主要原子的Mulliken净电荷,推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
(2)对氨基硫脲和水杨醛亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的水杨醛分子中主要原子的Mulliken净电荷,推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
(3)对氨基硫脲和4-氯查尔酮亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的4-氯查尔酮分子中主要原子的Mulliken净电荷,可以推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
Thiourea derivatives have been playing important roles in biology, medicine,daily life,industrial and agricultural production because of their special functional structure.They have potential applications in various branches of chemistry and some marginal subjects.However,less theoretical researches have been carried on the reaction between thiourea derivatives and other substances,while thermodynamic parameters of the reactions are still faultiness.Quantum chemical methods can be applied to investigate molecular thermodynamics,spectroscopy and reaction kinetics.Recently,intense researches of quantum chemistry have been focused on the electronic structure,spectroscopic properties and thermodynamic properties of the reactants and products through addition -condensation reaction of thiourea derivatives with aldehydes and ketones,which may play important roles in theoretical researches and practical applications.
The major research contents are as follows:
(1) For reactants and products in nucleophilic addition-condensation reaction of vanillin with thiosemicarbazide,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G. From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of vanillin,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries.The changes of enthalpy and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
(2)For reactants and products in nucleophilic addition-condensation reaction of thiosemicarbazide with salicylaldehyde,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G.From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of salicylaldehyde,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries.The changes of enthalpy changes and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
(3) For reactants and products in nucleophilic addition-condensation reaction of thiosemicarbazide with 4-chlorochalcone,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G.From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of 4-chlorochalcone,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries. The changes of enthalpy changes and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
本论文主要研究内容为:
(1)对香草醛和氨基硫脲亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的香草醛分子中主要原子的Mulliken净电荷,推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
(2)对氨基硫脲和水杨醛亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的水杨醛分子中主要原子的Mulliken净电荷,推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
(3)对氨基硫脲和4-氯查尔酮亲核加成-缩合反应体系的反应物和生成物,用量子化学密度泛函方法在B3LYP/6-31G水平上进行几何构型全优化,将从获得的4-氯查尔酮分子中主要原子的Mulliken净电荷,可以推测该化合物具有较高的亲核加成反应活性。对优化后的构型进行振动分析,得到不同温度下反应物和生成物的热力学性质,据此计算相应温度下该反应的焓变、吉布斯自由能变和平衡常数。在此基础上采用含时密度泛函方法(TD-DFT)计算分子激发态的电子跃迁能,得到对应激发态的吸收波长。
Thiourea derivatives have been playing important roles in biology, medicine,daily life,industrial and agricultural production because of their special functional structure.They have potential applications in various branches of chemistry and some marginal subjects.However,less theoretical researches have been carried on the reaction between thiourea derivatives and other substances,while thermodynamic parameters of the reactions are still faultiness.Quantum chemical methods can be applied to investigate molecular thermodynamics,spectroscopy and reaction kinetics.Recently,intense researches of quantum chemistry have been focused on the electronic structure,spectroscopic properties and thermodynamic properties of the reactants and products through addition -condensation reaction of thiourea derivatives with aldehydes and ketones,which may play important roles in theoretical researches and practical applications.
The major research contents are as follows:
(1) For reactants and products in nucleophilic addition-condensation reaction of vanillin with thiosemicarbazide,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G. From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of vanillin,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries.The changes of enthalpy and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
(2)For reactants and products in nucleophilic addition-condensation reaction of thiosemicarbazide with salicylaldehyde,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G.From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of salicylaldehyde,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries.The changes of enthalpy changes and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
(3) For reactants and products in nucleophilic addition-condensation reaction of thiosemicarbazide with 4-chlorochalcone,their geometry configurations were optimized by means of quantum chemistry DFT/B3LYP/6-31G.From the Mulliken atomic net charge of main elements,as well as E_(HOMO) and E_(LUMO) data of 4-chlorochalcone,it can be assumed that the compound has a higher activity of nucleophilic addition reaction.The thermodynamic properties of reactants and products were obtained via vibrational analyses for all optimal geometries. The changes of enthalpy changes and Gibbs free energy,and standard equilibrium constants were calculated.Then,by calculating the energies of electron transitions at excited states of molecule,the UV-Vis data of excited states were obtained.
引文
[1]邢其毅等.基础有机化学[M].高等教育出版社,1983.
[2]宋宝安,张华,金林红等.新型硫脲化合物的合成与生物活性研究[J].化学通报,2003,(3):200-203.
[3]胡永全,朱振林等.石灰氮及其衍生物[M].北京,化学工业出版社,2007,406.
[4]李欣,孙国新.二氧化硫脲的制备研究[J].济南大学学学报,2006,(20):35-37.
[5]胡国强.二氧化硫脲合成工艺的优化研究[J].化学世界,1999,(12):639-642.
[6]宋宝安,胡德禹,曾松.双酰基脲新化合物的合成及杀虫活性[J].化学通报,2002,(1):44-46.
[7]刘源发,孙国峰,孙晓红等.1-芳酰基-3-(2-苯并噻唑)硫脲化合物毒力测定[J].西北大学学报(自然科学版),2003,33(1):49-51.
[8]孙晓红,高润利,刘源发等.硫脲类化合物杀菌剂的合成[J].化学工程,2003,31(2):75-77.
[9]薛思佳,管谦.2H-1,2,4-噻二座并[2,3-a]嘧啶衍生物的合成及除草活性研究(Ⅴ)[J].有机化学,2002,22(9):646-650.
[10]曹坳程,赵国锋,张朝贤.一种新的乙酰乳酸合成酶抑制剂结合模型[J].农药译丛,1998,20(2):11-12.
[11]亦冰.水杨酸嘧啶类除草剂-Pyriminobac-methyl[J].农药译丛,1998,20(6):63-64.
[12]苏少泉.新的ALS抑制剂-嘧啶水杨酸类除草剂[J].农药译丛,1977,19(3):14-16.
[13]孙晓红,刘元发,王慧芳.硫脲衍生物的合成和生物活性研究[J].化学工程,2006,36(7):54-57.
[14]王红,王玉炉,李建平.氨基硫脲及其衍生物的研究现状[J].河南大学学报(自然科学版),1993,21(2):65-69.
[15]任仲皎等.氯化锌催化下由硫代氨基硫脲合成吖嗪[J].化学试剂,1995,17(6):379.
[16]李瑞年.氨基硫脲合成新工艺研究[J].安徽化工,2000,103(2):14-15.
[17]张霞,刘万毅,张境.缩氨基硫脲类化合物的应用及展望[J].宁夏工程技术,2005,4(1):78-85.
[18]SING R.B.,GARG B.S.,SINGH RP.,Analytical application of thiosemicarbazones and semicarbazones:a review[J].Talanta,1978,25(11-12):619.
[19]SALINAS F.,JIMENEZ SANCHEZ J.C.,GALEANO DIAZ T.Spectrophotometric determination of iron in wines,foods,and minerals with 5,5-dimethyl-1,2,3-cyclohex-anetirone 1,2-dioxime 3-thiosemicarbazone[J].Analytical Chemistry,1986,58(4):824.
[20]CALLEJON MOCHON M,MUNOZ LEYVA J.A.Spectrophotometric determination of peirodate with the bisthiosemicarbazones of phthalimide and 1,3-indandione[J].Microchemical Journal,1986,34(1):83.
[21]Robbins Jeffrey D.Neal,J.R.A simple synthesis of certain unsymmetrically substituted N,N'-dialkylthioureas.Synthetic Commun,1986,16(8):891-895.
[22]Vasilev,G.Izvorska,N.Lilov D,et al.Synthesis of some alkyl esters of m-phenylthioureidobenzoic acid and their influence on the growth and development of callus tissues,1986,39(2):93-98.
[23]王仲南,薛思佳.N-乙氧甲酰基-N'-(取代吡啶基)硫脲衍生物的合成及除草活性测定[J].华中师范大学学报,2000,34(3):295-298.
[24]张炎,李中华.N-芳酰基-N'-酰基烷基硫脲衍生物的合成[J].华中师范大学学报,2000,34(3):299-301.
[25]熊晔蓉,卢水明.1,3,4-惡二唑酰基硫脲衍生物的合成[J].华中师范大学学报,2000,34(3):310-312.
[26]李淑贤,汪焱刚.N'-5-四唑基-芳甲酰基硫脲的合成及其生物活性研究[J].有机化学,2003,23(11):1311-1313.
[27]程卫华,司宗兴.1-芳酰基-4-(5-芳基-2-呋喃甲酰基)氨基硫脲衍生物的合成及其生物活性[J].应用化学,2000,17(4):35-37.
[28]黄唯平,马衡,李庆春等.四个酰基硫脲衍生物及其配合物的合成与表征[J].化学研究与应用,1995,7(3):250-254.
[29]张铸勇.精细有机合成单元反应[M].上海,华东化工学院出版社,1990.
[30]孙纲春,曲建强,王流芳等.吲哚基丁烯酮缩氨基硫脲配合物的合成及生物活性[J].化学研究与应用,2006,18(1):85-88.
[31]李冬青,谭明雄,刘星等.吡啶甲醛缩氨基硫脲类希夫碱的合成[J].化工时刊,2004,18(11):36-37.
[32]曹克广,王忠刚.含葡萄糖基因缩氨基硫脲SchiffBase的合成[J].承德石油高等专科学报,2002,4(2):1-3.
[33]周双生,周根陶.新型磺化二醛及其缩氨基硫脲的合成[J].化学试剂,2002,22(3):168-169.
[34]Katiyar Meera,Rani Sarita,Gupta,S.P.Synthesis and fungitoxicity of someallyl-substituted phenylthioureas.Acta Ciencia Indica,Chemistry.1980,6(4):209-211.
[35]Budesinsky,B.W.Svec,J.Photometric determination of silver and mercury with glyoxal dithiosemicarbazone.Analytica Chimica Acta.1971,55(1):115-24.
[36]Kleemann,Axel,Klenk,Herbert,Schulz,Wolfgang.Thiosemicarbazide.德国专利:GWXXBX DE3204149,1983-08-18.
[37]Kukla M.J.,Breslin H.J.,Diamond CJ.,et al.Synthesis and anti-HIV-lactivity of 4,5,6,7-tetrahydro-5-methylimidazo[4,5,1-jk][1,4]benzodiazepin-2(1H)-one(TIBO)derivatives.Journal of medicinal chemistry,1991,34(11):3187-3197.
[38]张自义,陈立民.1-异烟酰基-4-芳酰基氨基硫脲化合物的研究[J].高等学校化学学报,1981,2(1):50-53.
[39]Amin,F.M.El-Zanfally,S.H.,Khalifa,M.Synthesis of certain substitutedurea and urea and thiourea derivatives structurally related to analgetics and antipyretics.Egyptian Journal of Pharmaceutical Sciences,1973,14(2):217-222.
[40]Phetsuksiri,Benjawan,Baulard,A.R.,Cooper,A.M.et al.Antimycobacterial activities of isoxyl and new derivatives through the inhibition of mycolic acid synthesis.Antimicrobial Agents and Chemotherapy,1999,43(5):1042-1051.
[41]张自义,杨珂新,曾福礼.酰氨基硫脲及其相关杂环衍生物的研究(Ⅴ)——1-(吡啶-4'-甲酰基)-4-芳基氨基硫脲及其相应的氮、硫、氧五员杂环化合物的合成[J].高等学校化学学报,1988,9(3):284-292.
[42]张自义,陈立民,冯小明等.酰氨基硫脲及其相关杂环化合物的研究(Ⅳ)——1-氰乙酰基-4-取代芳酰基硫脲及1,2,4-三唑类化合物的研究[J].高等学校化学学报,1987,8(3):229-232.
[43]Waletzky,Emanuel,Bliznick,Alexander.Thiosemicarbazide rodenticide.US Patent 2582940.1952-01-15.
[44]Dietrich,H.,Waldraff,C.,Willms,et al.Preparation of phenylsulfonyl azinylureas as herbicides and plant growth regulators.PCT Int.Appl.2000047566 -A1.2000-08-17.
[45]Lorenz,K.,Willms,L.,Bauer,K.,et al.Preparation of pyrimidinylureidosulfonylbenzoates and related compounds as herbicides and plantgrowth regulators.DE 19702200-A1.1998-07-30.
[46]Gesing E.R.F.,Kirsten R.,Kluth J.,et al.Substituted aryl sulfonyl(thio)urea usedasherbicides.WO9732861-A1.1997-09-12.
[47]周连君,张淑芳.吸附溶出伏安法测定水中痕量铅[J].青岛化工学院学报,1995,16(2):175-178.
[48]周连君,尤进茂,李怀娜等.吸附溶出伏安法测定痕量钒[J].冶金分析,1996,16(3):17-21.
[49]Diamandis E.P.MicrochimActa,1980,2(1-2):27-38.
[50]Hehre W.J.,Radom L.,Schleyer P.V.R.Ab Initio Molecular Orbital Theory.John Wiley &Sons,Inc.1986.
[51]McQuarrie D.A.Quantum chemisity University Science Books:Mill Vally.CA.1983.
[52]Chong D.P.Recent Advances in Density Functional Methods.Part Ⅱ.Singapore:World Scientific,1995,11:782.
[53]Parr R.G.,Yang W.Density-functional theory of atoms and molecules.Oxford University Press:Oxford,1989.
[54]Loewdin P.O.Correlation Problem in Many-Electron Quantum Mechanics.Advan Chem Phys.,1959,2:207.
[55]Foresman J.B.,Gordon M.H.,Pople J.A.,Frisch M.J.Toward a Systematic Molecular Orbital Theory for Excited States.J.Chem.Phys.,1992,96:135-136.
[56]Krishnan R.,Schlegel H.B.,Pople J.A.Derivate Studies in Configuration Interaction Theory.J.Chem.Phys.,I980,72:4654-4655.
[57]Brooks B.R.,Laidig W.D.,Saxe P.,Goddard J.D.,Yamaguchi Y.,Schaefer H.F.Analytic Gradient from Correlated Wave Functions via the Tow-Particle Density Matrix and the Unitary Group Approach.J Chem Phys.,1980,72:4652-4653.
[58]Slater F.A.,Trucks G.Q.,Bartlett R.J.Analytic Energy Derivatives in Many-Body Methods I.First Derivatives.J.Chem.Phys.,1989,90:1752-1766.
[59]Pople J.A.,Raghavachari K.Quadratic Configuration Interaction,A General Technique for Determining Electron Correlation Energies.J.Chem.Phys.,1987,87:5968-5975.
[60]曹阳.结构与材料[M].高等教育出版社,2003,189-230.
[61]徐光宪,黎乐民,王得民.量子化学[M].科学出版社,2001,200-477.
[62]薛定宇,陈阳泉.高等应用数学问题的MATLAB求解[M].清华大学出版社,2004:328-329.
[63]Song B.A.,Zhang H.,Jin L.H.,Hu D.,Huang R.M.,Liu G.,3-Phenyl-1-(2-pyridyl)thiourea,Huaxue Tongbao Patent,2003,66(3):200-202.
[64]Venkatachalam T.K.,Qazi S.,Samuel P.,Uckun F.M.Substituted heterocyclic thiourea compounds as a new class of anti-allergic agents inhibiting IgE/FcεRI receptor mediated mast cell leukotriene release.Bioorganic & Medicinal Chemistry,2003,11(6):1095-1105.
[65]于海涛,黄旭日等.B_2F_2分子异构体的量子化学计算研究[J].高等学校化学学报,2002,23:888-892.
[66]李宝宗.甲醛与甲酰胺相互作用的从头算研究[J].化学物理学报,2004,17(4):434-436.
[67]侯新娟,杨建丽,李永旺.煤大分子结构的量子化学研究[J].燃料化学学报,1999,27:143-148.
[68]张伏龙.环三硅烯及其相关分子的量子化学计算研究[J].甘肃联合大学学报(自然科学版),2005,19(1):37-40.
[69]凌关庭,王亦芸,唐述朝.食品添加剂手册[M].北京,化学工业出版社,1989.
[70]Delgado T.,Gomez C.C.Relationship between phenolic com-pounds of low molecular weight as indicator of the aging con-dition and quality of brandies[J].Am.J.Enol.vatic.1990,41(4):342-345.
[71]Markus,P H.Process for the preparation of phenylaldehydes.EP0542348A2,993.
[72]李永红,王丰收,孙志浩.酶法转化异丁香酚制备香草醛的研究[J].工业微生物,2004,34(3):1-6.
[73]何新亚,刘金霞,曹晓红,叶英植.硫代巴比妥酸光度法测定香草醛[J].分析实验室,1999,18(5):56-58.
[74]杜明,刘养清,刘明杰,徐秉玖.香草醛-磷酸体系荧光分光光度法测定黄芪甲甙[J].北京医科大学学报,2000,32:248-250.
[75]NieLi,ZhangXuan,WuFangying,et al.Anion Recognition by N-Benzamido-N'-phenylthioureas in Aqueous-Organic Binary Solvents.Acta Chimica Sinica,2004,62(4):369-372.
[76]ZhangJing,LiuWanyi,ZhangXia.Study of the Characterization of β-Cyclodextrin-Acetylferrocene-Thiosemicarbazone Inclusion Complex and Micro-Environmental Effects.Spectroscopy Spectral Analysis,2005,25(10):1568-1572.
[77]Dong Hoon Lee,Ho Yong Lee,Jong-In Hong.Anion Sensor Based on the Indoaniline-Thiourea System.Tetrahedron Lett,2002,43(40):7273-7276.
[78]Wu Fangying,Wen Zhenchang,Jiang Yunbao.Thiourea-Based Receptors for Anion Recognition and Sensing.Prog Chem,2004,16(5):776-784.
[79]张少全,刘新,江崇球,石恩国.香草醛缩氨基硫脲的合成及其与汞的荧光反应[J].山东理工大学学报(自然科学版),2005,19(4):74-76.
[80]Hehre W.J.,Radom L.,Pople J.A.AbInitio Molecular Orbital Theory.New York:John Wiley & Sons,1986.227.
[81]杨颇,高孝恢.性能-结构-化学键.北京,高等教育出版社,1987,156-158.
[82]张霞,刘万毅,田大年.4-氯查尔酮缩氨基硫脲微环境效应的紫外-可见光谱研究.分析科学学报,2006,22(4):389-392.
[83]张凤云,毛富春,李红.香草醛溶液的化学稳定性研究[J].西北林学院学报,2001,16(4):60-61.
[84]葛晓霞,冯林,刘金凯,江崇球.香草醛缩氨基硫脲-铅高灵敏荧光反应的研究及其应用[J].分析实验室,2004,23(7):41-43.
[85]姚宏亮,李方实.水杨醛的应用及方法述评[J].江苏化工,2007,(3):17-19.
[86]Karin Jahnke,Beate Podschune.Acid-base catalytic mechanism of dihydrop yrimidinase from pH studies,biochemistry,1993,32:5160-5165.
[87]Cooper,Robin D.G.,Hydroxy substituted phenylglycylamido-3-heterocyclic thiomethylacephalosporins,US Pat.,US3946003,1976.
[88]Popescu F.,Zinc electroplating baths,US Pat.,US3778359,1973
[89]Nitto Boseki Co.Ltd.,Zinc plating with sodium zincate solns-contg aromatic aldehyde and polyamino-sulphone,giving high gloss,GR Pat.,DE2608644,1976.
[90]汪元博.酯化氧化法合成水杨醛.天津大学硕士学位论文,2006,11-13.
[91]张自义等.氨基硫脲及其相关化合物化学.化学研究与应用,1991,3:3-20.
[92]何芳,江崇球.水杨醛氨基硫脲的合成及其铍的荧光熄灭反应[J].分析测试室,2002,6(21):57-59.
[93]李永强,王金中,王崇妍,张远馥.水杨醛缩氨基硫脲-铜荧光淬灭反应的研究与应用 [J].分析测试学报,2007,2(26):232-234.
[94]姚宏亮,李方实.紫外光谱法测定水杨醛-苯酚混合物中的水杨醛的含量[J].化学分析计量,2008,2(17):45-47.
[95]李红,张少全.水杨醛缩氨基硫脲-铅荧光反应的研究与应用[J].山东师范大学学报,2004,1(19):107-109.
[96]Yun Linwu,YaoHusueh.HsuehPao.1965.12(s):523-532.
[97]Pluijcrs C.W.,Kuars Sijpesterijn A.,Annl Appl Biol.1966.57(3):465-473.
[98]Berniee Grafstein.Seienee,1963.142:973-975.
[99]胡永全,朱振林等.石灰氮及其衍生物[M].化学工业出版社,北京,2007,428-429.
[100]任仲皎等.氯化锌催化下由硫代氨基脲合成吖嗪[J].化学试剂,1995,17(16):379-380.
[101]张霞,刘万毅,田大年.4-氯查尔酮缩氨基硫脲微环境效应的紫外-可见光谱研究[J].分析科学学报,2006,22(4):389-392.
[102]张霞,刘万毅,田大年.新试剂4-氯查尔酮缩氨基硫脲与铜(Ⅱ)显色反应的研究[J].分析实验室,2006,6(25):59-61.
[103]Yunusa U.Theoretical Investigation of the Structure and Vibrational Spectra of Diethynyl Ketone.J Mol Struct,2005,728(1-3):111-115.
[104]Ricardo V.R.,Eduardo E.F.,Johan F,et al.TheoreticalStudyof a Series of N-(N-Propyl)-N'-(Para-R-Benzoyl)-Thioureas with trans[Pt(py)_2Cl_2]Through Chemistry Reactivity Descriptors Based on Density Functional Theory.J Mol Struct,2008,862(1-3):92-97.
[105]Pedro M.,Vanni M.,Tomas T.Nucleophilic Additions of Lithiated Allylphenylsulfone to Nitrones:Experimental and Theoretical Investigations.Tetrahedron,2005,61(13):3335-3347.
[106]张兆斌,李华,张永刚等.丁烷热裂解自由基反应模型的建立和验证.石油化工,2007,36(1):44-48.
[2]宋宝安,张华,金林红等.新型硫脲化合物的合成与生物活性研究[J].化学通报,2003,(3):200-203.
[3]胡永全,朱振林等.石灰氮及其衍生物[M].北京,化学工业出版社,2007,406.
[4]李欣,孙国新.二氧化硫脲的制备研究[J].济南大学学学报,2006,(20):35-37.
[5]胡国强.二氧化硫脲合成工艺的优化研究[J].化学世界,1999,(12):639-642.
[6]宋宝安,胡德禹,曾松.双酰基脲新化合物的合成及杀虫活性[J].化学通报,2002,(1):44-46.
[7]刘源发,孙国峰,孙晓红等.1-芳酰基-3-(2-苯并噻唑)硫脲化合物毒力测定[J].西北大学学报(自然科学版),2003,33(1):49-51.
[8]孙晓红,高润利,刘源发等.硫脲类化合物杀菌剂的合成[J].化学工程,2003,31(2):75-77.
[9]薛思佳,管谦.2H-1,2,4-噻二座并[2,3-a]嘧啶衍生物的合成及除草活性研究(Ⅴ)[J].有机化学,2002,22(9):646-650.
[10]曹坳程,赵国锋,张朝贤.一种新的乙酰乳酸合成酶抑制剂结合模型[J].农药译丛,1998,20(2):11-12.
[11]亦冰.水杨酸嘧啶类除草剂-Pyriminobac-methyl[J].农药译丛,1998,20(6):63-64.
[12]苏少泉.新的ALS抑制剂-嘧啶水杨酸类除草剂[J].农药译丛,1977,19(3):14-16.
[13]孙晓红,刘元发,王慧芳.硫脲衍生物的合成和生物活性研究[J].化学工程,2006,36(7):54-57.
[14]王红,王玉炉,李建平.氨基硫脲及其衍生物的研究现状[J].河南大学学报(自然科学版),1993,21(2):65-69.
[15]任仲皎等.氯化锌催化下由硫代氨基硫脲合成吖嗪[J].化学试剂,1995,17(6):379.
[16]李瑞年.氨基硫脲合成新工艺研究[J].安徽化工,2000,103(2):14-15.
[17]张霞,刘万毅,张境.缩氨基硫脲类化合物的应用及展望[J].宁夏工程技术,2005,4(1):78-85.
[18]SING R.B.,GARG B.S.,SINGH RP.,Analytical application of thiosemicarbazones and semicarbazones:a review[J].Talanta,1978,25(11-12):619.
[19]SALINAS F.,JIMENEZ SANCHEZ J.C.,GALEANO DIAZ T.Spectrophotometric determination of iron in wines,foods,and minerals with 5,5-dimethyl-1,2,3-cyclohex-anetirone 1,2-dioxime 3-thiosemicarbazone[J].Analytical Chemistry,1986,58(4):824.
[20]CALLEJON MOCHON M,MUNOZ LEYVA J.A.Spectrophotometric determination of peirodate with the bisthiosemicarbazones of phthalimide and 1,3-indandione[J].Microchemical Journal,1986,34(1):83.
[21]Robbins Jeffrey D.Neal,J.R.A simple synthesis of certain unsymmetrically substituted N,N'-dialkylthioureas.Synthetic Commun,1986,16(8):891-895.
[22]Vasilev,G.Izvorska,N.Lilov D,et al.Synthesis of some alkyl esters of m-phenylthioureidobenzoic acid and their influence on the growth and development of callus tissues,1986,39(2):93-98.
[23]王仲南,薛思佳.N-乙氧甲酰基-N'-(取代吡啶基)硫脲衍生物的合成及除草活性测定[J].华中师范大学学报,2000,34(3):295-298.
[24]张炎,李中华.N-芳酰基-N'-酰基烷基硫脲衍生物的合成[J].华中师范大学学报,2000,34(3):299-301.
[25]熊晔蓉,卢水明.1,3,4-惡二唑酰基硫脲衍生物的合成[J].华中师范大学学报,2000,34(3):310-312.
[26]李淑贤,汪焱刚.N'-5-四唑基-芳甲酰基硫脲的合成及其生物活性研究[J].有机化学,2003,23(11):1311-1313.
[27]程卫华,司宗兴.1-芳酰基-4-(5-芳基-2-呋喃甲酰基)氨基硫脲衍生物的合成及其生物活性[J].应用化学,2000,17(4):35-37.
[28]黄唯平,马衡,李庆春等.四个酰基硫脲衍生物及其配合物的合成与表征[J].化学研究与应用,1995,7(3):250-254.
[29]张铸勇.精细有机合成单元反应[M].上海,华东化工学院出版社,1990.
[30]孙纲春,曲建强,王流芳等.吲哚基丁烯酮缩氨基硫脲配合物的合成及生物活性[J].化学研究与应用,2006,18(1):85-88.
[31]李冬青,谭明雄,刘星等.吡啶甲醛缩氨基硫脲类希夫碱的合成[J].化工时刊,2004,18(11):36-37.
[32]曹克广,王忠刚.含葡萄糖基因缩氨基硫脲SchiffBase的合成[J].承德石油高等专科学报,2002,4(2):1-3.
[33]周双生,周根陶.新型磺化二醛及其缩氨基硫脲的合成[J].化学试剂,2002,22(3):168-169.
[34]Katiyar Meera,Rani Sarita,Gupta,S.P.Synthesis and fungitoxicity of someallyl-substituted phenylthioureas.Acta Ciencia Indica,Chemistry.1980,6(4):209-211.
[35]Budesinsky,B.W.Svec,J.Photometric determination of silver and mercury with glyoxal dithiosemicarbazone.Analytica Chimica Acta.1971,55(1):115-24.
[36]Kleemann,Axel,Klenk,Herbert,Schulz,Wolfgang.Thiosemicarbazide.德国专利:GWXXBX DE3204149,1983-08-18.
[37]Kukla M.J.,Breslin H.J.,Diamond CJ.,et al.Synthesis and anti-HIV-lactivity of 4,5,6,7-tetrahydro-5-methylimidazo[4,5,1-jk][1,4]benzodiazepin-2(1H)-one(TIBO)derivatives.Journal of medicinal chemistry,1991,34(11):3187-3197.
[38]张自义,陈立民.1-异烟酰基-4-芳酰基氨基硫脲化合物的研究[J].高等学校化学学报,1981,2(1):50-53.
[39]Amin,F.M.El-Zanfally,S.H.,Khalifa,M.Synthesis of certain substitutedurea and urea and thiourea derivatives structurally related to analgetics and antipyretics.Egyptian Journal of Pharmaceutical Sciences,1973,14(2):217-222.
[40]Phetsuksiri,Benjawan,Baulard,A.R.,Cooper,A.M.et al.Antimycobacterial activities of isoxyl and new derivatives through the inhibition of mycolic acid synthesis.Antimicrobial Agents and Chemotherapy,1999,43(5):1042-1051.
[41]张自义,杨珂新,曾福礼.酰氨基硫脲及其相关杂环衍生物的研究(Ⅴ)——1-(吡啶-4'-甲酰基)-4-芳基氨基硫脲及其相应的氮、硫、氧五员杂环化合物的合成[J].高等学校化学学报,1988,9(3):284-292.
[42]张自义,陈立民,冯小明等.酰氨基硫脲及其相关杂环化合物的研究(Ⅳ)——1-氰乙酰基-4-取代芳酰基硫脲及1,2,4-三唑类化合物的研究[J].高等学校化学学报,1987,8(3):229-232.
[43]Waletzky,Emanuel,Bliznick,Alexander.Thiosemicarbazide rodenticide.US Patent 2582940.1952-01-15.
[44]Dietrich,H.,Waldraff,C.,Willms,et al.Preparation of phenylsulfonyl azinylureas as herbicides and plant growth regulators.PCT Int.Appl.2000047566 -A1.2000-08-17.
[45]Lorenz,K.,Willms,L.,Bauer,K.,et al.Preparation of pyrimidinylureidosulfonylbenzoates and related compounds as herbicides and plantgrowth regulators.DE 19702200-A1.1998-07-30.
[46]Gesing E.R.F.,Kirsten R.,Kluth J.,et al.Substituted aryl sulfonyl(thio)urea usedasherbicides.WO9732861-A1.1997-09-12.
[47]周连君,张淑芳.吸附溶出伏安法测定水中痕量铅[J].青岛化工学院学报,1995,16(2):175-178.
[48]周连君,尤进茂,李怀娜等.吸附溶出伏安法测定痕量钒[J].冶金分析,1996,16(3):17-21.
[49]Diamandis E.P.MicrochimActa,1980,2(1-2):27-38.
[50]Hehre W.J.,Radom L.,Schleyer P.V.R.Ab Initio Molecular Orbital Theory.John Wiley &Sons,Inc.1986.
[51]McQuarrie D.A.Quantum chemisity University Science Books:Mill Vally.CA.1983.
[52]Chong D.P.Recent Advances in Density Functional Methods.Part Ⅱ.Singapore:World Scientific,1995,11:782.
[53]Parr R.G.,Yang W.Density-functional theory of atoms and molecules.Oxford University Press:Oxford,1989.
[54]Loewdin P.O.Correlation Problem in Many-Electron Quantum Mechanics.Advan Chem Phys.,1959,2:207.
[55]Foresman J.B.,Gordon M.H.,Pople J.A.,Frisch M.J.Toward a Systematic Molecular Orbital Theory for Excited States.J.Chem.Phys.,1992,96:135-136.
[56]Krishnan R.,Schlegel H.B.,Pople J.A.Derivate Studies in Configuration Interaction Theory.J.Chem.Phys.,I980,72:4654-4655.
[57]Brooks B.R.,Laidig W.D.,Saxe P.,Goddard J.D.,Yamaguchi Y.,Schaefer H.F.Analytic Gradient from Correlated Wave Functions via the Tow-Particle Density Matrix and the Unitary Group Approach.J Chem Phys.,1980,72:4652-4653.
[58]Slater F.A.,Trucks G.Q.,Bartlett R.J.Analytic Energy Derivatives in Many-Body Methods I.First Derivatives.J.Chem.Phys.,1989,90:1752-1766.
[59]Pople J.A.,Raghavachari K.Quadratic Configuration Interaction,A General Technique for Determining Electron Correlation Energies.J.Chem.Phys.,1987,87:5968-5975.
[60]曹阳.结构与材料[M].高等教育出版社,2003,189-230.
[61]徐光宪,黎乐民,王得民.量子化学[M].科学出版社,2001,200-477.
[62]薛定宇,陈阳泉.高等应用数学问题的MATLAB求解[M].清华大学出版社,2004:328-329.
[63]Song B.A.,Zhang H.,Jin L.H.,Hu D.,Huang R.M.,Liu G.,3-Phenyl-1-(2-pyridyl)thiourea,Huaxue Tongbao Patent,2003,66(3):200-202.
[64]Venkatachalam T.K.,Qazi S.,Samuel P.,Uckun F.M.Substituted heterocyclic thiourea compounds as a new class of anti-allergic agents inhibiting IgE/FcεRI receptor mediated mast cell leukotriene release.Bioorganic & Medicinal Chemistry,2003,11(6):1095-1105.
[65]于海涛,黄旭日等.B_2F_2分子异构体的量子化学计算研究[J].高等学校化学学报,2002,23:888-892.
[66]李宝宗.甲醛与甲酰胺相互作用的从头算研究[J].化学物理学报,2004,17(4):434-436.
[67]侯新娟,杨建丽,李永旺.煤大分子结构的量子化学研究[J].燃料化学学报,1999,27:143-148.
[68]张伏龙.环三硅烯及其相关分子的量子化学计算研究[J].甘肃联合大学学报(自然科学版),2005,19(1):37-40.
[69]凌关庭,王亦芸,唐述朝.食品添加剂手册[M].北京,化学工业出版社,1989.
[70]Delgado T.,Gomez C.C.Relationship between phenolic com-pounds of low molecular weight as indicator of the aging con-dition and quality of brandies[J].Am.J.Enol.vatic.1990,41(4):342-345.
[71]Markus,P H.Process for the preparation of phenylaldehydes.EP0542348A2,993.
[72]李永红,王丰收,孙志浩.酶法转化异丁香酚制备香草醛的研究[J].工业微生物,2004,34(3):1-6.
[73]何新亚,刘金霞,曹晓红,叶英植.硫代巴比妥酸光度法测定香草醛[J].分析实验室,1999,18(5):56-58.
[74]杜明,刘养清,刘明杰,徐秉玖.香草醛-磷酸体系荧光分光光度法测定黄芪甲甙[J].北京医科大学学报,2000,32:248-250.
[75]NieLi,ZhangXuan,WuFangying,et al.Anion Recognition by N-Benzamido-N'-phenylthioureas in Aqueous-Organic Binary Solvents.Acta Chimica Sinica,2004,62(4):369-372.
[76]ZhangJing,LiuWanyi,ZhangXia.Study of the Characterization of β-Cyclodextrin-Acetylferrocene-Thiosemicarbazone Inclusion Complex and Micro-Environmental Effects.Spectroscopy Spectral Analysis,2005,25(10):1568-1572.
[77]Dong Hoon Lee,Ho Yong Lee,Jong-In Hong.Anion Sensor Based on the Indoaniline-Thiourea System.Tetrahedron Lett,2002,43(40):7273-7276.
[78]Wu Fangying,Wen Zhenchang,Jiang Yunbao.Thiourea-Based Receptors for Anion Recognition and Sensing.Prog Chem,2004,16(5):776-784.
[79]张少全,刘新,江崇球,石恩国.香草醛缩氨基硫脲的合成及其与汞的荧光反应[J].山东理工大学学报(自然科学版),2005,19(4):74-76.
[80]Hehre W.J.,Radom L.,Pople J.A.AbInitio Molecular Orbital Theory.New York:John Wiley & Sons,1986.227.
[81]杨颇,高孝恢.性能-结构-化学键.北京,高等教育出版社,1987,156-158.
[82]张霞,刘万毅,田大年.4-氯查尔酮缩氨基硫脲微环境效应的紫外-可见光谱研究.分析科学学报,2006,22(4):389-392.
[83]张凤云,毛富春,李红.香草醛溶液的化学稳定性研究[J].西北林学院学报,2001,16(4):60-61.
[84]葛晓霞,冯林,刘金凯,江崇球.香草醛缩氨基硫脲-铅高灵敏荧光反应的研究及其应用[J].分析实验室,2004,23(7):41-43.
[85]姚宏亮,李方实.水杨醛的应用及方法述评[J].江苏化工,2007,(3):17-19.
[86]Karin Jahnke,Beate Podschune.Acid-base catalytic mechanism of dihydrop yrimidinase from pH studies,biochemistry,1993,32:5160-5165.
[87]Cooper,Robin D.G.,Hydroxy substituted phenylglycylamido-3-heterocyclic thiomethylacephalosporins,US Pat.,US3946003,1976.
[88]Popescu F.,Zinc electroplating baths,US Pat.,US3778359,1973
[89]Nitto Boseki Co.Ltd.,Zinc plating with sodium zincate solns-contg aromatic aldehyde and polyamino-sulphone,giving high gloss,GR Pat.,DE2608644,1976.
[90]汪元博.酯化氧化法合成水杨醛.天津大学硕士学位论文,2006,11-13.
[91]张自义等.氨基硫脲及其相关化合物化学.化学研究与应用,1991,3:3-20.
[92]何芳,江崇球.水杨醛氨基硫脲的合成及其铍的荧光熄灭反应[J].分析测试室,2002,6(21):57-59.
[93]李永强,王金中,王崇妍,张远馥.水杨醛缩氨基硫脲-铜荧光淬灭反应的研究与应用 [J].分析测试学报,2007,2(26):232-234.
[94]姚宏亮,李方实.紫外光谱法测定水杨醛-苯酚混合物中的水杨醛的含量[J].化学分析计量,2008,2(17):45-47.
[95]李红,张少全.水杨醛缩氨基硫脲-铅荧光反应的研究与应用[J].山东师范大学学报,2004,1(19):107-109.
[96]Yun Linwu,YaoHusueh.HsuehPao.1965.12(s):523-532.
[97]Pluijcrs C.W.,Kuars Sijpesterijn A.,Annl Appl Biol.1966.57(3):465-473.
[98]Berniee Grafstein.Seienee,1963.142:973-975.
[99]胡永全,朱振林等.石灰氮及其衍生物[M].化学工业出版社,北京,2007,428-429.
[100]任仲皎等.氯化锌催化下由硫代氨基脲合成吖嗪[J].化学试剂,1995,17(16):379-380.
[101]张霞,刘万毅,田大年.4-氯查尔酮缩氨基硫脲微环境效应的紫外-可见光谱研究[J].分析科学学报,2006,22(4):389-392.
[102]张霞,刘万毅,田大年.新试剂4-氯查尔酮缩氨基硫脲与铜(Ⅱ)显色反应的研究[J].分析实验室,2006,6(25):59-61.
[103]Yunusa U.Theoretical Investigation of the Structure and Vibrational Spectra of Diethynyl Ketone.J Mol Struct,2005,728(1-3):111-115.
[104]Ricardo V.R.,Eduardo E.F.,Johan F,et al.TheoreticalStudyof a Series of N-(N-Propyl)-N'-(Para-R-Benzoyl)-Thioureas with trans[Pt(py)_2Cl_2]Through Chemistry Reactivity Descriptors Based on Density Functional Theory.J Mol Struct,2008,862(1-3):92-97.
[105]Pedro M.,Vanni M.,Tomas T.Nucleophilic Additions of Lithiated Allylphenylsulfone to Nitrones:Experimental and Theoretical Investigations.Tetrahedron,2005,61(13):3335-3347.
[106]张兆斌,李华,张永刚等.丁烷热裂解自由基反应模型的建立和验证.石油化工,2007,36(1):44-48.