绿色化学高中化学校本课程

1、会计学1绿色化学高中化学校本课程绿色化学高中化学校本课程2007年年6月月24日，因日，因天气闷热，滇池蓝藻天气闷热，滇池蓝藻大量繁殖，在昆明滇大量繁殖，在昆明滇池海埂一线的岸边，池海埂一线的岸边，湖水如绿油漆一般。湖水如绿油漆一般。可能造出比原子弹威力更大的毁灭性武器。的总体退化。CCl3ClClDDTNNHOOOOthalidomideOCH3OOOOOAflatoxin B1，黄曲霉毒素，黄曲霉毒素Lysergic acid，麦，麦角酸角酸NNHCH3COOHHOOSafrole，黄樟素，黄樟素用易燃易爆和具有高反应活性的材料。OHOHHOResveratrol吸烟吸烟430，700酗酒

2、酗酒100，000被动吸烟被动吸烟53，000汽车事故汽车事故43，300AIDS37，500杀害杀害24，926火灾火灾3，200可卡因可卡因4，202海洛因和吗啡海洛因和吗啡4，175氡气氡气2，500美国每年可防止的死亡估计美国每年可防止的死亡估计(艾滋病艾滋病)Designing safer and effective target molecules(设计更安全的目标物质）设计更安全的目标物质）1.The designing of new safe and effective molecules.2. The designing of new safer and effective

3、molecules to which effective but not benign.Traditional ways of finding an effective molecule:Practical needssynthesistestsynthesistestNew molecular designing ways :Trial and errorsPractical needsdesigning by SAR(=Safety Analysis Report)synthesisGuided theoreticallytestClCClO Polycarbonate(聚碳酸酯聚碳酸酯)

4、Phosgene is widely used for the production of:isocyanate (异氰酸酯异氰酸酯)polyurethane(聚氨酯聚氨酯)RNH2 + COCl2 RNCO + 2HCl RNHCO2R1The synthesis of isocynate (异氰酸酯异氰酸酯)providing -CO groupClCClOCarbon dioxide is used to substitute phosgene in the production of isocyanate (providing carbonyl group)The function o

5、f phosgene: providing -CO groupRNH2 + CO2RNCO + H2ORNHCO2R1C6H5NH2 + CO2 C6H5N(H)CO2HC6H5N=C=OH2OAniline2CH3OH + COCl2CH3OOCOOCH3 + 2HCl2CH3OH + CO + O2CH3OOCOOCH3 + H2OCatalyst2CH3OH + CO2CH3OOCOOCH3 + H2OThe synthesis of di-methyl carbonateCNHThe synthesis of sodium iminodi-acetate(亚氨基二乙酸二钠)involv

6、es two steps: NH3 + 2CH2O + 2HCN NCCH2NHCH2CN + 2NaOH NaO2CCH2NHCH2 CO2Na + NH3A new starting material HOCH2CH2NHCH2CH2OH (diethanolamine, 二乙醇胺二乙醇胺) is used CH2=CHCH=CH2 + HCNNCCH2CH2CH2CH2CNHOOC(CH2)4COOHH2N(CH2)6NH2C6H12OxidationCH2=CHCH=CH2 + 2CO + 2H2OHC(CH2)4CHOHN=CH(CH2)4CH=NHH2N(CH2)6NH2O2cat

7、alyst2NH3 - 2H2O2H2C6H5CH2Cl +HCNC6H5CH2CN + HCl H2OC6H5CH2Cl + COOH / H2OCould anyone tell me the disadvantages of this methodThe starting material (Benzene) is hazardous (carcinogentic)The release of nitrogen oxides which are multifunctional pollutantsUse of heavy metals (cobalt)Elimination of the

8、 use of , the use of , the corrosive capacity of is not as severe as nitric acid, produced.Kamzuhiko Sato, 1998, , 281:1646-1647The synthesis method is . .Drath and Frost, 1990, 1991Not only , but also develop a new method to use (glucose).Corey and Bersohn , 30 years agoCorey and Bersohn , 30 years

9、 agoused computer to help designing of synthetic routee. g.If the synthesis of a compound needs 5 steps, and 30 methods are possible for each step, thus we will have The progress in computer science and technologyFurther search for the starting material using the former starting material as the targ

10、et molecules until the provided starting material is neededCompare all possible routes, and choose the most favorable one from the viewpoint of economical and environmental effect. The use of as starting material for energy and chemicals production , because of its renewability. One kind of solar en

11、ergyOil: 30-50 yearsNatural Gas: 50-100 yearsCoal: 200-400 yearsBiomass：Starch (淀粉淀粉, amylum) + Lignin (木质素木质素, lignine)Lignin：164 billion ts /year amount used 1.5%Examplesabout 2.83.5 hundreds million of tons can be used as resource of energy.Fundamental scientific challenge:Technical challenges:v

12、Continuous operationv Separation of the productsActual progressesCrosCross sAgricultural waste (polysaccharides多聚糖) Naturally degradable polymerSichuan University, University of Science and Technology, Shandong University, Chemical Institute Academy of China, GuangzhouBiomassAnimal feedsFuelChemical

13、sHaltzapple from Texas A & M Haltzapple from Texas A & M universityuniversity1996, The presidential Green Chemistry Award Direct liquation Indirect conversion gasifierpurificationfangas tankNeededByHomebiomass, airgasifierbiomasstankCO + 2H2=CH3OHreforming reaction bedbiomassFast-growing bam

14、booFast-growing shrubs Convert biomass to useful products green chemically Agricultural wastePaul A Wender 1996the starting material used should be the and ; the operation and manipulation should be , and ;the reaction rate should be and the of the target products, either natural or designed by ours

15、elves, should be Example 1: The traditional Fridel-Crafts （付-克）acylation reaction: Target product/Aluminium chlorode, 1/3COClClClO+Envirocat EPZG1400C, 24hThe use of new catalyst Envirocata. EPZG to replace AlCl3, the amount of catalyst could be reduced to 1/10 of the traditional one, the amount of

16、waste (HCl) is reduced to , while the yield of the target product increased to 70%, and the selectivity of the is increased, the amount of ortho-substituted product is reduced to trace. Micelle could be provided by varying the central atom and the ligand as well as the use of surfacants, thus the in

17、terface could be enlarged and the regional concentration of the reactants could be increased. By varying the structure of the micelle, the stero-structure of the product could also be controlled.Example 2：The alkylation of benzene with ethylene Forming ethyl benzeneThe synthesis of gasoline(汽油） from

18、 carbon dioxide and natural gas(methane, 甲烷) Nickel catalystFT processPlasma: breaking of the reactant moleculesCatalyst: forming of the product moleculesUsing electrochemical ways to eliminate the use of hazardous starting materials and make the reaction to occur at moderate conditionsOOMeBrCH3CH3O

19、CH3CH3electron/VitB12CH3OHOOHCH3CH3CH3CH3OUsing electrochemical waysUnfortunately, the of this route is not as good as expected, and is not yet industrialized.At the anodeH2O-NaClCH3CHCH2CH3CHOHCH2ClAt the cathodeCH3CHOHCH2ClCH3CHCH2OF2CH=CFCF3PbO2/Steel/anode Steel/cathode H2O-HOAc-HNO3The conversi

20、on: , Selectivity: This route has already been industrialized by Hoechst Company CF3CFCF2OC6H5NH2H2O-NH4I/PtNH3I-NH2NH2-NH2At the anodeC6H6 +2 H2O+ 6H+At the cathodeOHOHOOC6H6 + 2 H+ + 2e 织接受绿色化学的效益。术水平。年度年度奖项奖项获奖者获奖者获奖项目获奖项目1996学术奖（学术奖（Academic Award）Prof. Mark Holtzapple, Dept. of Chem. Eng., Texa

21、s A & M Univ.废弃生物质转化成动物饲料、化学品和燃料废弃生物质转化成动物饲料、化学品和燃料（Conversion of Waste Biomass to Animal Feed, Chemicals, and fuel)新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Pharmacia (formerly Monsanto Company)二乙醇胺的催化脱氢二乙醇胺的催化脱氢(The Catalytic Dehydrogenation of Diethanolamine)新工艺奖新工艺奖（Alternative Solve

22、nts and Reaction Conditions Award）The Dow Chemical Company开发纯的二氧化碳作为与环境友好的聚苯乙烯泡开发纯的二氧化碳作为与环境友好的聚苯乙烯泡沫包装材料的发泡剂及其在商业中的应用沫包装材料的发泡剂及其在商业中的应用(The development and commercial Implementation of 100 percent Carbon Dioxide as an Environmentally Friendly Blowing Agent for the Polystyrene foam Packaging Marker)

23、安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Rohm and Haas Company设计对环境更安全的抗海藻贝壳生长的涂料设计对环境更安全的抗海藻贝壳生长的涂料(Designing an Environmentally Safer Marine Antifoulant)中小企业奖（中小企业奖（Small Business Award）The Donlar Corporation热聚天冬氨酸的制备和应用热聚天冬氨酸的制备和应用(Production and use of Thermal Polyaspartic Acid)年度年度奖项奖项获

24、奖者获奖者获奖项目获奖项目1997学术奖（学术奖（Academic Award）Prof. Joseph M. DeSimone, Univ. of North Carolina and North Carolina State Univ.二氧化碳表面活性剂的设计和应用二氧化碳表面活性剂的设计和应用(Design and Application of Surfactants for Carbon Dioxide)新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）BHC CompanyBHC公司的布洛芬生产工艺公司的布洛芬生产工艺(BHC Cmp

25、any Ibuprofen Process)新工艺奖新工艺奖（Alternative Solvents and Reaction Conditions Award）ImationDry ViewTM成像体系成像体系(Dry ViewTM Imaging Systems)安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Albright and Wilson AmericasTHPS灭除有害生物药剂：新的抗微生灭除有害生物药剂：新的抗微生物化学物化学(THPS Biocides: A New Class of Antimicrobial Chemi

26、stry)中小企业奖（中小企业奖（Small Business Award）Legacy Systems IncorporatedColdstripTM: 除去有机物和湿法清洗除去有机物和湿法清洗的新技术的新技术(ColdstripTM: Revolutionary Organic Removal and Wet Cleaning Technology)年度年度奖项奖项获奖者获奖者获奖项目获奖项目1998学术奖（学术奖（Academic Award）(a) Prof. Barry M. Trost, Stanford University(b) Dr. Karen M. Draths, and

27、 Prof. John W. Frost(a)原子经济性概念的提出原子经济性概念的提出(b)应用微生物作为与环境友好的合成反应的催化剂应用微生物作为与环境友好的合成反应的催化剂(a) The development of the Concept of Atom Economy;(b) Use of Microbes as Environmentally-benign Synthetic Catalysts新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Flexsys America L. P.合成合成4氨基二苯胺的新路线氨基二苯胺的新路线(N

28、ew Process for 4-Aminodiphenyl-amine)新工艺奖新工艺奖（Alternative Solvents and Reaction Conditions Award）Argonne National Laboratory以膜分离为基础的生产乳酸酯的新工艺：替代卤代以膜分离为基础的生产乳酸酯的新工艺：替代卤代和有毒溶剂的无毒工艺和有毒溶剂的无毒工艺(Novel Membrane-based process for Prodcing Lactate Esters: Nontoxic Replacements for Halogenated and Toxic Solve

29、nts)安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Rohm and Haas Company以以CONFIRMTM代表的新型系列化学杀虫剂的发明代表的新型系列化学杀虫剂的发明和商业化和商业化(The Invention and commercialization of a New Chemical Family of Insecticides Exemplified by CONFIRMTM Insecticide)中小企业奖中小企业奖（Small Business Award）PYRPCOOL Technologies, Inc.新千年

30、的技术：开发与环境友好的灭火剂和冷却剂新千年的技术：开发与环境友好的灭火剂和冷却剂(Technology for the Third Millennium: the Development of an Environ. Responsible Fire Extinguishment and Cooling Agent)年度年度奖项奖项获奖者获奖者获奖项目获奖项目1999学术奖（学术奖（Academic Award）Terrence J. Collins, Carnegie Mellon Univ.活化氧化剂的试剂活化氧化剂的试剂TAMLTM ：绿色氧化技术中过：绿色氧化技术中过氧化氢的活化氧化

31、氢的活化(TAMLTM Oxidant Activators: General Activation of Hydrogen Peroxide for Green Oxidation Technologies) 新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Lilly Research Laboratory生物催化剂在药物制备方面的实际应用生物催化剂在药物制备方面的实际应用(Practical Application of a Biocatalyst in Pharmaceutical Manufacturing)新工艺奖新工艺奖（Alte

32、rnative Solvents and Reaction Conditions Award）Nalco Chemical CompanyULTIMER的开发和商业化：第一个新型水溶性的开发和商业化：第一个新型水溶性聚合物分散体系聚合物分散体系(The Development and Commercialization of ULTIMER: The First of New Family of Water Soluble Polymer Dispersions)安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Dow AgroSciences

33、LLCSpinosad,一种新的控制昆虫的天然产物一种新的控制昆虫的天然产物(Spinosad, a New Natural Product for Insect Control)中小企业奖（中小企业奖（Small Business Award）Biofine Incorporated (now BioMetics, Inc.)由纤维素生物质经济地转化成化学品由纤维素生物质经济地转化成化学品(Economic Conversion of Cellulosic Biomass to Chemicals)年度年度奖项奖项获奖者获奖者获奖项目获奖项目2000学术奖（学术奖（Academic Awar

34、d）Prof. Chi-Huey Wong, The Scripps Research Institute酶催化剂在有机合成中的应用酶催化剂在有机合成中的应用(Use of Enzymes as Catalysts in Organic Synthesis)新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Roche Colorado Corporation开发合成高活性的抗病毒试剂开发合成高活性的抗病毒试剂Ganciclovir (Cytovene)的新的和高效的方法的新的和高效的方法(Development of a New and Efi

35、cient Synthesis of the Potent Antiviral Agent Ganciclovir (Cytovene)新工艺奖新工艺奖（Alternative Solvents and Reaction Conditions Award）Bayer Corporation利用水作载体的双组分利用水作载体的双组分(2K)聚氨酯涂料聚氨酯涂料(Two-Component (2K) Polyurethane Coatings that Use Water as Carrier)安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Dow

36、AgroSciencesSentricon：开发灭除白蚁群的新体系：开发灭除白蚁群的新体系(Development of the Sentricon Termite Colony Elimination System)中小企业奖（中小企业奖（Small Business Award）RevTech, IncEnvirogluvTM ：用可辐照固化并环境可接受的油：用可辐照固化并环境可接受的油墨装饰玻璃和水泥制品的技术墨装饰玻璃和水泥制品的技术(EnvirogluvTM: A Technology for Decorating Glass and Ceramicware with Radiato

37、n Curable Bnvironmentally Compliant Inks)年度年度奖项奖项获奖者获奖者获奖项目获奖项目2001学术奖（学术奖（Academic Award）Prof. Chao-Jun Li, Tulane Univ.设计一系列能在水和空气中，而不是在有机溶剂设计一系列能在水和空气中，而不是在有机溶剂和惰性气体中进行的过渡金属催化反应和惰性气体中进行的过渡金属催化反应(Design of a Variety of Transition Metal Catalyzed Reactions that Can Run in Air and Water, Rather than

38、 in Organic Solvents and Inert Atmosphere)新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Bayer Corporation and Bayer AG与环境友好的生物可降解的鳌合剂亚氨基双琥珀与环境友好的生物可降解的鳌合剂亚氨基双琥珀酸钠盐的合成酸钠盐的合成(Synthesis of an Environ. Friendly biodegradable Chelating Agent, Sodium Iminodisuccinate)新工艺奖新工艺奖（Alternative Solvents and

39、Reaction Conditions Award）Novozymes North America, Inc.BioPreparationTM技术的开发技术的开发:以酶处理棉织物的以酶处理棉织物的工艺工艺(Development of BioPreparationTM Technology, an Enzymatic Process for Treating Cotton Texitiles)安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）PPG Industries, Inc.在阳离子电镀工艺中以钇代替铅在阳离子电镀工艺中以钇代替铅(Use

40、of Yttrium as a Substitute for Lead in Cationic Electrocoatings)中小企业奖（中小企业奖（Small Business Award）EDEN Bioscience CorporationDevelopment of Messenger农业技术，防御病害农业技术，防御病害和虫害体系的开发和虫害体系的开发(Development of Messenger Agricultural Technology, Defense Systems to Protect against Disease and Pest)年度年度奖项奖项获奖者获奖者获

41、奖项目获奖项目2002学术奖（学术奖（Academic Award）Professor Eric J.BeckmanUniversity of PittsburghDesign of Non-Fluorous, Highly CO2 -Soluble Materials新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Pfizer, Inc.Green Chemistry in the Redesign of the Sertraline Process新工艺奖（新工艺奖（Alternative Solvents and Reaction Co

42、nditions Award）Cargill Dow LLCNature WorksTM polylactic acid （PLA） Process安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Chemical Specialties,Inc. (CSI)alkaline copper quaternary (ACQ) Preserve: The Environmentally Advanced Wood Preservative中小企业奖（中小企业奖（Small Business Award）SC Fluids, Inc.SCORR Sup

43、ercritical CO2 Resist Remover年度年度奖项奖项获奖者获奖者获奖项目获奖项目2004学术奖（学术奖（Academic Award）乔治亚理工学院的乔治亚理工学院的Eckert教授和教授和Liotta教授教授 研究出一种环境友好、性质可调的研究出一种环境友好、性质可调的溶剂，实现了反应、分离一体化溶剂，实现了反应、分离一体化 新合成路线奖新合成路线奖（Alternative Synthetic Pathways Award）Bristol-Myers Squibb公公司司(BMS) 利用植物细胞发酵利用植物细胞发酵(PCF)和萃取技术，和萃取技术，开发了一种生产开发了一

44、种生产Taxol制品的绿色合制品的绿色合成路线成路线 新工艺奖（新工艺奖（Alternative Solvents and Reaction Conditions Award）Buckman Laboratories International公司公司 开发了一种旨在改善纸再生过程的开发了一种旨在改善纸再生过程的酶技术酶技术Optimyze 安全化学品设计奖安全化学品设计奖（Designing Safer Chemicals Award）Engelhard公司公司 开发一系列环境友好的开发一系列环境友好的RightfitTM偶氮颜料偶氮颜料 中小企业奖（中小企业奖（Small Business Award）Jeneil生物表面活性剂公生物表面活性剂