有机化学五复习class省公共课一等奖全国赛课获奖课件.pptx

1REVIEW答疑时间：7月2日15点至17点30分地 点：医基楼化学试验室第1页2我们最少要我们最少要考考60分！分！第2页3It is a shame to cheat in examination 第3页4考试重点及试题分数分布考试重点及试题分数分布一、命名（5小题，每小题1分，共5分）二、选择题（单项选择题，25小题，每小题1分，共25分）三、完成以下反应式（30小题，每小题2分，共60分）四、判别题（1小题，5分）五、推测结构题（1小题，5分）第4页5不列入考试范围章节：不列入考试范围章节：第一章 结论第十三章 有机波谱学基础第十四章 杂环化合物和维生素第十八章 核酸第十九章 代谢路径中辅酶第5页6第二章：烷烃和环烷烃Name ofConformerWedge-HatchedBond StructureSawhorseStructureNewmanProjection第6页7第7页8.Stability of radicals:CH3CH3 C CH3CH3CHCH3CH3CH2CH3The radical is more steady,and more easy to be formed.第8页9P.31 2-12 自由基稳定性：教科书印刷错误第9页10.Chemical properties of alicyclic hydrocarbon1)addition of hydrogenH2,cat.CH3CH2CH3CH3CH2CH2CH3H2,cat.high temp.CH3(CH2)3CH3CH3(CH2)4CH3第10页112)react with halogensBr2BrCH2CH2CH2BrBr2BrCH2CH2CH2CH2BrBr2,hBrBr2,hBraddition:substitution:第11页HX123)addition of hydrogen halidesHX第12页13Stability of cycloalkanes:Anhydrides Esters Acidamides第146页147第147页148(4)Biuret Reaction(缩二脲反应)Biuret can dissolve in alkali solution.If a little cupric sulfate be added to the biuret alkali solution,the color of the solution will turn to violet color.This color reaction is called Biuret Reaction.Compounds contain two or more than two peptide linkages(肽键 )such as polypeptide,protein,etc.can take place biuret reaction.第148页149完成以下反应式，写出主要产物第149页150第150页151第151页152第152页153用化学方法判别以下各组化合物（1）乙酸乙酯、-丁酮酸、丁酰胺 A B CABCNaHCO3不产生CO2ACBHNO2产生N2C不产生N2A产生CO2第153页154（2）乙酐、甲酸甲酯、乙酰溴 A B CABCAgNO3产生浅黄色沉淀ABCAg(NH3)2NO3产生银镜B不产生银镜A不产生浅黄色沉淀第154页155 化合物A在酸性水溶液中加热，生成化合物B（C5H10O3）B与NaHCO3反应放出无色气体，与CrO3作用生成C（C5H8O4），B在室温条件下不稳定，易失水生成A。试写出A，B，C结构式。解：化合物B不饱和度为：=1 25+2 102B在室温条件下不稳定，易失水生成AB为-羟基酸；A为-内酯第155页156 A B C第156页157第十二章：胺和生物碱Sequence of the basicity of aminesquaternary ammonium saltquaternary ammonium hydratetertiary amine第157页1582.Acylationamide 第158页1593.Sulfonylationbenzene sulfonyl chloridep-toluenesulfonyl chloride-I effectweak acidcrystalbenzene sulfonamide第159页160The above reaction is named Hinsberg Reaction.Using this reaction can distinguish primary,secondary and tertiary amines.The products of primary amines react with benzene sulfonyl chloride is weak acid,so can dissolve in sodium hydroxide solution.The products of secondary amines are crystal,and can not dissolve in sodium hydroxide solution.For tertiary amines,this reaction can not take place.第160页1614.React with nitrous acid(HNO2)(1)Primary amines第161页162(2)Secondary amines(3)Tertiary aminesAliphatic tertiary amines do not react with nitrous acid to give an isolable product.nitrosoamines(yellow oil)第162页163yellow solidActually,we use sodium nitrite/hydrochloric acid NaNO2/HCl instead of nitrous acid(HNO2).第163页164Section 2 Diazo and Azo Compounds.Diazotization Reactionbenzene diazonium chloride.Reaction of Diazo Salt1.Substitution05第164页165第165页166H3PO2:hypophosphorous acid(次磷酸次磷酸)第166页1672)How to synthesize 1,3,5-tribromobenzene from benzene?Question:1)How to synthesize 2-methyl benzoic acid from toluene?第167页168051)第168页1692)05第169页1702.Coupled ReactionHOAc,NaOAc第170页1712.Hydrolysis第171页172(4)Biuret Reaction(缩二脲反应)Biuret can dissolve in alkali solution.If a little cupric sulfate be added to the biuret alkali solution,the color of the solution will turn to violet color.This color reaction is called Biuret Reaction.Compounds contain two or more than two peptide linkages(肽键 )such as polypeptide,protein,etc.can take place biuret reaction.第172页173第十五章：糖类Almost natural sugars are D sugars.第173页174Oligosaccharides and polysaccharides can be hydrolyzed to monosaccharides,so all sugars have a reaction as follow:saccharidesconc.H+-H2Oviolet compoundThis reaction is named as Molisch reaction,can be used to distinguish saccharides.第174页175.Oxidation monosaccharides Ag +complex productsTollens reagent1.React with Tollens,Fehlings or Benedicts reagentmonosaccharides Cu2O +complex productsFehlings or Benedicts reagent(brick red color)第175页176Cause:all monosaccharides(include ketoses)can react with Tollens,Fehlings and Benedicts reagent.Reducing sugar:a sugar can react with Tollens,Fehlings and Benedicts reagent.In other words,reducing sugar contain some amount of an oxidizable free aldehyde group.Reducing sugars endow with mutarotation.Nonreducing sugar:a sugar can not react with Tollens,Fehlings and Benedicts reagent.Nonreducing sugars do not endow with mutarotation.第176页177Glycosides are not Reducing SugarsGlycosides lacks a free hemiacetal function;cannot be in equilibrium with a species having an aldehyde function.第177页1782.React with BromineBromine in water is a mild oxidant,it converts only the aldehyde into a carboxylic acid,the primary and secondary hydroxyls are not touched,and the product is called an aldonic acid.aldonic acid第178页179D-galactoseD-galactaric acid or mucic acidQuestion:Is D-galactaric acid a chiral molecule?why?D-galactaric acid is not a chiral molecule,because the molecule contain a plane of symmetry.It is a meso compound.第179页180第180页181sucrose(table sugar)第181页182-1，4-glycosidic linkagemaltose,麦芽糖 -D-glucopyranoseD-glucose第182页1831.Amylose(直链淀粉,糖淀粉)-1，4-glycosidic linkage第183页1842.Amylopectin(支链淀粉,胶淀粉)-1，4-glycosidic linkage-1，6-glycosidic linkage第184页185Iodine is used to distinguish starch.Put the iodine to the solution of starch,the solution show blue color.第185页186Br2/H2O用简便方法区分以下各组化合物（1）葡萄糖和果糖ABAB红棕色消失不褪色AB第186页187托伦试剂（2）葡萄糖和蔗糖ABAB产生银镜反应不产生银镜反应AB第187页188I2（3）蔗糖和淀粉ABAB不显蓝紫色显蓝紫色AB第188页189托伦试剂（4）甲基-D-吡喃葡萄糖苷和2-O-D-吡喃葡萄糖苷ABAB不产生银镜反应产生银镜反应AB第189页190写出D-(+)-半乳糖与以下试剂反应主要产物第190页191第191页192第192页193第十六章：脂类linoleic acid,-linolenic acid and arachidonic acid are essential fatty acids.Essential fatty acids:essential in our diets because our bodies cannot make them,yet use them to make many other fatty acids our bodies must have.第193页194Saponification number:The amount(mg)of KOH that can hydrolyze 1g oils and fats completely.We can use the saponification number to deduce the average molecular weight of oils and fats approximately.saponification numberaverage molecular weightcontent of low molecular weight oils and fatslarge smallsmall largehigh low第194页195(2)Addition of iodineIodine number:the amount of iodine(g)which be absorbed by 100g oils and fats.Iodine number can be used to deduce the unsaturated degree of oils and fats.iodine numberunsaturated degreelarge smallhigh low第195页196Acidic number:the amount(mg)of KOH which can neutralize the dissociated fatty acids of 1g oils and fats.acidic numberdissociated fatty acidthe degree of ranciditylarge smallmore lesslarge small第196页1975-steroidsSubstituents point either down(dashed bond,)or up(solid bond,)第197页1985-steroids第198页199ultravioletVitamin D37-dehydrocholesterolultravioletergosterol麦角甾醇Vitamin D2第199页200第十七章：氨基酸、多肽和蛋白质Almost nature amino acids are L-amino acids.All 20 of the amino acids are necessary for protein synthesis.Our body can synthesize more than one-half of these 20 amino acids from starting materials provided by the food.But there are nine or ten are unable to make in our body,which are called essential amino acids.第200页201valine,Val,Vleucine,Leu,Lthreonine,Thr,Tisoleucine,Ile,I缬氨酸亮氨酸异亮氨酸苏氨酸第201页202methionine,Met,Mlysine,Lys,Kphenylalanine,Phe,Ftryptophan,Try,W(necessary for synthesis of tyrosine)(necessary for synthesis of cysteine)蛋氨酸赖氨酸苯丙氨酸色氨酸第202页203The following amino acids are also essential amino acids:histidine,His,T necessary only for infants第203页204arginine,Arg,R necessary only for cats第204页205pHpIformuladirection of electrophoresis cathode no movement anodecharge state +/第205页2065.React with nitrous acid(HNO2)What difference between nitrous acid react with amino acids and nitrous acid react with aliphatic amines?第206页2078.React with ninhydrinAmino acids react with ninhydrin to form a deep purple molecule,Ruhemanns purple.It is this purple color that is used to detect amino acids except proline,regardless of the identify of the R group,form the same purple molecule on reaction with ninhydrin.Ruhemanns purple第207页208Chemical bonds of proteins:1.Principal bond(主键主键):peptide linkage2.Auxiliary bonds(副键副键):(1)Hydrogen bondbetween main chainsbetween main chain and side chainbetween side chains第208页209(2)Disulfide bondmercaptan第209页210Thiols in adjacent chains can form a disulfide RSSR through spontaneous oxidation.A disulfide bond between cysteine residues in different peptide chains links the otherwise separate chains together,while a disulfide bond between cysteine residues in the same chain forms a loop.第210页211(3)Hydrophobic bond:The nonpolar,“greasy”hydrophobic hydrocarbon portions cluster inside the molecule,maximally protected from the hostile aqueous environment.第211页212(5)Salt bond(ionic bond)(6)Coordinate bond(4)Van der Waals force第212页213Primary structure:the sequence of amino acids in a protein.第213页214Secondary structure:ordered regions of a protein chain.The two most common types of secondary structure are the-helix and the-pleated sheet.第214页2152.PrecipitationTwo main factors for stability of proteins solution:a.electric charge;b.hydration shellIf we can destroy one or two stable factors,the proteins will precipitate from the solution.(1)Salting outThe leading effect of salting out is destroying the hydration shell.(NH4)2SO4 is the common reagent.第215页216(2)Organic solventMethanol,ethanol and acetone can be used to destroy hydration shell and cause precipitation of proteins.(3)Heavy metal saltsAdjusting the pH of the solution until pHpI,then heavy metal salts be added to precipitate proteins.第216页217(4)Alkaloidal reagentsAdjusting the pH of the solution until pHpI,then alkaloidal reagents be added to precipitate proteins.第217页218(5)Antibody-antigen reaction.第218页2193.Denaturation:The destructure of the higher order structure of a protein(not involve with primary structure),sometimes reversible,sometimes not.第219页220PROTEIN DENATURATIONPhysical:HeatingCoolingMechanical treatmentHydrostatic pressure RadiationChemical:AcidsBasesMetals Organic solvents第220页2214.Color reactions:(1)biuret reaction(2)react with ninhydrin(3)react with nitric acid第221页22217-6.写出以下反应中反应产物第222页223cystinehistamine第223页 祝各位亲与“考神”同在：逢考必过逢考必过第224页