有机化学五年制复习(class ).ppt

1、1,REVIEW,答疑时间：7月2日15点至17点30分 地 点：医基楼化学实验室,2,我们至少要考60分！,3,It is a shame to cheat in examination,4,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（单选题，25小题，每小题1分，共25分）,三、完成下列反应式（30小题，每小题2分，共60分）,四、鉴别题（1小题，5分）,五、推测结构题（1小题，5分）,5,不列入考试范围的章节：,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 代谢途径中的辅酶,6,第二章：烷烃和环烷烃,7,8

2、,. Stability of radicals:,The radical is more steady, and more easy to be formed.,9,P.31 2-12 自由基稳定性：,教科书印刷错误,10,. Chemical properties of alicyclic hydrocarbon,1) addition of hydrogen,11,2) react with halogens,addition:,substitution:,12,3) addition of hydrogen halides,HX,13,Stability of cycloalkanes

3、:,14,Stable,Instable,Stable,Instable,15,Stable,Instable,16,17,?,18,19,Stability of carbocation,+,+,+,+,tertiary,secondary,primary,methyl,cation stability,20,3-17 正碳离子稳定性：,21,第四章：芳香烃,Hckels rule (rule of 4n+2, 休克尔规则): All planar, cyclic, fully conjugated molecules with 4n + 2 ( n = 0, 1, 2) electrons

4、 will be aromatic (especially stable). The rule works because such molecules will have molecular orbital systems in which all bonding molecular orbitals are completely full.,22,HNO3 / H2SO4,nitrobenzene,23,Friedel-Crafts alkylation reaction,24,25,26,ortho/para locating groups: The groups on the bebz

5、ene ring are most effective at directing further substitution to the ortho and para position, such as:,27,meta locating groups: The groups on the benzene ring are most effective at directing further substitu-tion to the meta position, such as:,28,4. Oxidation reaction,oxidant: KMnO4 / H+ , K2Cr2O7 /

6、 H+ (potassium dichromate),29,Oxidants convert most alkyl side chains on benzene rings into the acid group, COOH. However, for the oxidation to succeed there must be at least one benzyl hydrogen.,30,31,32,P. 68 4-6由苯或甲苯合成下列化合物,（2）,separate,33,4-8. 判断下列化合物是否具有芳香性,34,每一成环原子上计1个电子，环内“-”加1个电子，“+”减去1个电子。

7、,每一环外“-” 计为2个电子，“+”计为0个电子。,35,4-9. (1) 1,3-环己二烯、苯、甲苯,A B C,ABC,Br2 / H2O,红棕色消失,BC,A,KMnO4 / H+,紫红色消失,C,不褪色,B,不褪色,36,(2) 苯乙烯、苯乙炔、乙苯,A B C,ABC,AgNO3/NH3,产生白色沉淀,AC,B,Br2 / H2O,红棕色消失,A,不褪色,C,不产生白色沉淀,37,4-10. 某化合物（A）分子式为C9H12，能被高锰酸钾氧化得到化合物（B）分子式为C8H6O4。将A进行硝化，只得到两种一硝基产物。试推测（A）、（B）的结构式，并有反应式表示推断过程。,38,Deg

8、ree of unsaturation(): In a hydrocarbon, the total number of bonds and rings.,n4: the number of atoms with 4 valence (C),n3: the number of atoms with 3 valence ( N),n1: the number of atoms with 1 valence (H ,X),39,structure of compound = 0, saturated and no ring =1, a double bond or a ring =2, two d

9、ouble bonds or two rings or a triple bond =4, perhaps a benzen ring, is usually used to deduce the structure of compounds.,40,4-10. 某化合物（A）分子式为C9H12，能被高锰酸钾氧化得到化合物（B）分子式为C8H6O4。将A进行硝化，只得到两种一硝基产物。试推测（A）、（B）的结构式，并有反应式表示推断过程。,解：化合物A的不饱和度为：,化合物B的不饱和度为：,41,42,第五章：手性分子,Chiral carbon: The carbon atom attach

10、 to four different groups.,*,*,*,43,Chiral molecule: A molecule is not superimposable on its mirror image.,44,Enantiomers (optical isomers): Nonsuperimposable mirror images, different molecules.,45,Racemic mixture(racemate, 外消旋体): A mixture containing equal amounts of two enantiomers forms of a chir

11、al molecule.,46,S configuration,R configuration,47,Plane of symmetry : The plane which divides the molecule into halves, one part is anothers mirror image.,48,Meso compound: a compound contain chiral carbons but are achiral. The compound must possess two or more stereocenters.,49,P. 84 5-11,存在内消旋体的化

12、合物是：2,3-二溴丁烷和2,4-二溴戊烷。,2,3-二溴丁烷,2,3-二溴戊烷,2,4-二溴戊烷,50,（1）2R，3R-3-溴-2-丁醇 （2）2R，3S-3-溴-2-丁醇,(3) 2S，3R-3-溴-2-丁醇 (4) 2S，3S-3-溴-2-丁醇,5-13. 答：,（1）（4）互为对映体，（2）（3）互为对映体；（1）与（2）（3）为非对映体，（2）与（1）（4）为非对映体。,51,第六章：卤代烃,(carbonitrile, nitrile),(carboxylic acid),52,53,transition state,sp2 hybridization,SN2 Reaction,

13、54,The rate of the SN2 reaction:,Summary of SN2 reaction: 1. The rate of reaction is proportional to the concentrations of both the substrate and the displacing agent. 2. The reaction is completed in one step. The forming of new bond and breaking of old bond is achieved in same time. 3. The stereoch

14、emistry of the starting material is inverted.,55,SN1 Reaction,Nu-,56,The rate of the SN1 reaction:,Summary of SN1 reaction: 1. The rate of reaction is proportional to the concen-trations of the substrate. 2. The reaction is completed in two steps. An initial ionization is followed by attack of the n

15、ucleophile. 3. Racemization. 4. Sometimes rearrangement is occurred.,57,Elimination Reaction,+ HX,58,Saytzeff elimination: Formation of the more substituted alkene in an elimination reaction. In other words, when halogen hydride be removed from alkyl halides, the proton come from the carbon which co

16、ntains less hydrogen atoms.,59,More examples:,60,The rate of E1 and E2 reaction:,61,P. 95 6-8.,62,6-12. 用化学方法区别下列各组化合物,A B C,ABC,AgNO3 heat,不产生白色沉淀,BC,A,KMnO4 / H+,紫红色消失,B,不褪色,C,产生白色沉淀,63,分子式为C5H10的A烃，与溴水不发生反应，在紫外线照射下与等摩尔溴作用得到产物B(C5H9Br)，B与KOH的醇溶液加热得C(C5H8)，C经酸性KMnO4氧化得到戊二酸。写出A、B、C的结构式及各步反应式。,解：化合物A

17、的不饱和度为：,64,65,第七章：醇、硫醇、酚,sodium alcoholate,66,Hydrochloric acid/dry zinc chloride which is called Lucas reagent.,67,1) Tertiary alcohols react with Lucas reagent at once and release heat.,2) Secondary alcohols react with Lucas reagent within 5 minutes and no obvious heat release.,3) Primary alcohols

18、 do not react with Lucas reagent at room temperature even after one hour.,68,(2) Dehydration,69,Collins reagent (chromium trioxide in pyridine),70,4. React with cupric hydroxide and periodic acid,The salt is blue color, so you can use this reaction to distinguish 1,2-glycols.,71,dimercaptopropanol o

19、r BAL,72,3. Oxidation,disulfide,73,p-benzoquinone,hydroquinone,(1,4-benzoquinone),74,75,white precipitation,2,4,6-tribromophenol,We can use this reaction to distinguish phenol (caution: only phenol, not all phenols.),76,4. react with ferric chloride,All phenols can react with ferric chloride and the

20、 products are complex compounds. The products have various color, so we can use this reaction to distinguish phenols and enol.,77,P. 111 7-6.,78,7-8. 鉴别,（3）对苯酚 苯甲醇,AB,FeCl3,产生颜色反应,B,A,不产生颜色反应,A B,79,（4）1,2-丙二醇 1,3-丙二醇,A B,AB,Cu(OH)2,沉淀消失，生成蓝色透明溶液,B,A,沉淀不消失,80,第八章：醚和环氧化合物,Williamson Ether Synthesis,第

21、六章 卤代烃 P. 87,81,Formation of oxonium salt,82,Rupturing of ether bond,Notes: 1. The less carbon atoms R form iodides. Methyl form CH3I (iodomethane) quantificationally. 2. For aromatic ethers, the aliphatic part form iodides and the aryl form phenols. 3. Diaryl ethers are not easy to cleave by HI or

22、HBr.,83,React with epoxides,84,Opening of unsymmetrical epoxides in acid is a SN1 reaction. Epoxides react with proton to form a stable carbocation, then react with nucleophiles.,85,86,P. 120 8-5.,87,8-7. 某化合物A的分子式为C7H8O，A与金属钠不发生反应，与浓氢碘酸反应生成两个化合物B和C，B能溶于氢氧化钠，并与FeCl3作用呈紫色，C与硝酸银醇溶液作用，生成黄色深沉，试写出A、B和C的结

23、构及有关反应式。,解：化合物A的不饱和度为：,88,89,第九章：醛和酮,Friedel-Crafts Acylation Reaction,90,CrO32C5H5N is called Collins reagent.,91,cyclohexanone,92,Not all ketones can react with hydrocyanic acid or sodium bisulfite. Which aldehydes and ketones can react with hydrocyanic acid or sodium bisulfite? 1. All aldehydes i

24、nclude aliphatic and aromatic aldehydes.,2. Aliphatic methyl ketones.,3. Cyclic ketones which the rings contain eight or less carbon atoms,n7,93,94,95,Point out which compounds of the following molecules can react with sodium bisulfite:,96,97,Addition of Grignard Reagents,98,Addition of derivatives

25、of ammonia,Schiff base,99,100,2,4-dinitrophenyl hydrazine,2,4-dinitrophenyl hydrazone,yellow precipitation,Formation of 2,4-dinitrophenyl hydrazone can diagnose the presence of a carbonyl group.,101,Aldol condensation,102,Mechanism of aldol condensation :,carbanion,intermediate,aldol,103,104,crossed

26、 aldol condensation,105,2. Haloform reactions,106,haloform,(sodium hypohalide),107,P.129 倒数3行,108,silver mirror reaction,. Oxidation and Reduction,cuprous oxide, brick red color,109,Tollens reagent can react with all aldehydes (aliphatic and aromatic), but Fehlings reagent only can react with alipha

27、tic aldehydes. You can use Fehlings reagent to distinguish aliphatic aldehydes and aromatic aldehydes.,110,reduction:,lithium aluminium hydride,111,Metal hydrides (LiAlH4, NaBH4, and many others) can reduce aldehydes and ketones to give alcohols. Compare with hydrogenation reaction, application of m

28、etal hydrides is more selective. Metal hydrides only reduce the carbonyl group but not carbon-carbon double bond.,112,Clemmensen Reaction,Zn-Hg/HCl: zinc amalgam,methylene,113,P. 132 9-7. 试用下列各试剂与环戊酮进行反应，写出各产物的结构,114,Ag2O/NH3,115,10.,116,117,9-14. 鉴别 （2）2-戊酮、3-戊酮、环己酮,ABC,I2 NaOH,产生黄色沉淀,BC,A,NaHSO3,产

29、生白色沉淀,C,不产生白色沉淀,B,不产生黄色沉淀,A B C,118,第十章：羧酸和取代羧酸,1) FCH2COOH ClCH2COOH BrCH2COOH ICH2COOH CH3OCH2COOH HOCH2COOH CH3COOH 2) FCH2COOH FCH2CH2COOH FCH2CH2CH2COOH 3) CF3COOH F2CHCOOH FCH2COOH,The sequence of acidity:,119,COOH,COOH,COOH,COOH,COOH,COOH,NO2,NO2,NO2,OH,OH,COOH,OH,120,1) FCH2COOH ClCH2COOH Br

30、CH2COOH ICH2COOH CH3OCH2COOH HOCH2COOH CH3COOH 2) FCH2COOH FCH2CH2COOH FCH2CH2CH2COOH 3) CF3COOH F2CHCOOH FCH2COOH,The sequence of acidity:,121,Sequence of -I effect:,122,phosphorus pentoxide, dehydrant,123,butanedioic anhydride,pentanedioic anhydride,124,phthalic anhydride,125,1) -alcoholic acid,12

31、6,2) -alcoholic acids,-unsaturated carboxylic acid,127,-valerolactone,3) -alcoholic acids and -alcoholic acids,-butyrolactone,128,129,ketone body,Ketone body is the incomplete oxidating metabolite of fatty acids. The level of ketone body will remarkable increase when suffer from diabetes.,130,P. 146

32、,10-5. 写出下列反应的主要产物,131,132,(3),A B C D,ABCD,NaHCO3,不产生CO2,AB,CD,Ag(NH3)2NO3,产生银镜,A,不产生银镜,B,产生CO2,Ag(NH3)2NO3,产生银镜,C,不产生银镜,D,10-6 用简单的化学方法区别下列各组化合物,133,10-7. 按酸性由强到弱排出下列各组化合物的顺序,(1),(2),134,化合物A(C8H14)经催化加氢得化合物B (C8H16)，A经臭氧氧化后再经Zn/H+处理得化合物C(C8H14O2)，C经Tollens试剂加热反应，得D (C8H14O3)，D与I2/NaOH反应得3-甲基己二酸。试

33、写出A，B，C，D的结构式。,解：,D,C,A,B,135,136,137,138,139,化合物A的分子式为C8H8O2能与NaHCO3反应。A在光照下与Br2反应得分子式为C8H7BrO2 的一对对映体B 和C ； B 和C与NaCN反应，得到分子式为C9H7NO2 同一的外消旋体D，D 在酸性水溶液中加热得到一种无光学活性的E（2-苯基丙二酸）。试写出A，B，C，D和E的结构式。,解：化合物A的不饱和度为：,所以化合物A可能含有苯环结构,140,141,142,第十一章：羧酸衍生物,143,144,This reaction also know as transesterificatio

34、n reaction.,145,acidamide,146,Acid halides, anhydrides and esters are acylating agents. The start material react with these acylating agents can introduce acyl group.,147,148,(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

35、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.,149,完成下列反应式，写出主要产物,150,151,152,153,用化学方法鉴别下列各组化合物,（1）乙酸乙酯、-丁

36、酮酸、丁酰胺,A B C,ABC,NaHCO3,不产生CO2,AC,B,HNO2,产生N2,C,不产生N2,A,产生CO2,154,（2）乙酐、甲酸甲酯、乙酰溴,A B C,ABC,AgNO3,产生浅黄色沉淀,AB,C,Ag(NH3)2NO3,产生银镜,B,不产生银镜,A,不产生浅黄色沉淀,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的结构式。,解：化合物B的不饱和度为：,B在室温条件下不稳定，易失水生成A,B为-羟基酸；A为-内酯,156,A

37、 B C,157,第十二章：胺和生物碱,Sequence of the basicity of amines,quaternary ammonium salt,quaternary ammonium hydrate,tertiary amine,158,2. Acylation,amide,159,3. Sulfonylation,benzene sulfonyl chloride,p-toluenesulfonyl chloride,-I effect,weak acid,crystal,benzene sulfonamide,160,The above reaction is named

38、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

39、hydroxide solution. For tertiary amines, this reaction can not take place.,161,4. React with nitrous acid (HNO2),(1) Primary amines,162,(2) Secondary amines,163,yellow solid,Actually, we use sodium nitrite/hydrochloric acid NaNO2/HCl instead of nitrous acid (HNO2).,164,Section 2 Diazo and Azo Compou

40、nds,. Diazotization Reaction,benzene diazonium chloride,. Reaction of Diazo Salt,1. Substitution,05,165,166,H3PO2: hypophosphorous acid (次磷酸),167,2) How to synthesize 1,3,5-tribromobenzene from benzene?,Question: 1) How to synthesize 2-methyl benzoic acid from toluene?,168,05,1),169,2),05,170,2. Cou

41、pled Reaction,HOAc, NaOAc,171,2. Hydrolysis,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

42、 two or more than two peptide linkages ( 肽键 ) such as polypeptide, protein, etc. can take place biuret reaction.,173,第十五章：糖类,Almost natural sugars are D sugars.,174,Oligosaccharides and polysaccharides can be hydrolyzed to monosaccharides, so all sugars have a reaction as follow:,This reaction is na

43、med as Molisch reaction, can be used to distinguish saccharides.,175,. Oxidation,1. React with Tollens, Fehlings or Benedicts reagent,176,Cause: all monosaccharides (include ketoses) can react with Tollens, Fehlings and Benedicts reagent.,Reducing sugar: a sugar can react with Tollens, Fehlings and

44、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.,177,Glycoside

45、s are not Reducing Sugars,Glycosides lacks a free hemiacetal function; cannot be in equilibrium with a species having an aldehyde function.,178,2. React with Bromine,Bromine in water is a mild oxidant, it converts only the aldehyde into a carboxylic acid, the primary and secondary hydroxyls are not

46、touched, and the product is called an aldonic acid.,aldonic acid,179,Question: 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.,180,181,sucrose (table sugar),182,maltose, 麦芽糖,-D-glucopyra

47、nose,D-glucose,183,1. Amylose (直链淀粉, 糖淀粉),184,2. Amylopectin (支链淀粉,胶淀粉),185,Iodine is used to distinguish starch. Put the iodine to the solution of starch, the solution show blue color.,186,Br2/H2O,用简便方法区别下列各组化合物,（1）葡萄糖和果糖,A,B,AB,红棕色消失,不褪色,A,B,187,托伦试剂,（2）葡萄糖和蔗糖,A,B,AB,产生银镜反应,不产生银镜反应,A,B,188,I2,（3）蔗

48、糖和淀粉,A,B,AB,不显蓝紫色,显蓝紫色,A,B,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,A,B,AB,不产生银镜反应,产生银镜反应,A,B,190,写出D-(+)-半乳糖与下列试剂反应的主要产物,191,192,193,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,

49、 yet use them to make many other fatty acids our bodies must have.,194,Saponification 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 number,avera

50、ge molecular weight,content of low molecular weight oils and fats,large small,small large,high low,195,(2) Addition of iodine,Iodine 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 number,un

51、saturated degree,large small,high low,196,Acidic number: the amount (mg) of KOH which can neutralize the dissociated fatty acids of 1g oils and fats.,acidic number,dissociated fatty acid,the degree of rancidity,large small,more less,large small,197,Substituents point either down (dashed bond, a) or

52、up (solid bond, b),198,199,ultraviolet,Vitamin D3,7-dehydrocholesterol,ultraviolet,ergosterol麦角甾醇,Vitamin D2,200,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 ac

53、ids 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.,201,valine, Val, V,leucine, Leu, L,threonine, Thr, T,isoleucine, Ile, I,缬氨酸,亮氨酸,异亮氨酸,苏氨酸,202,methionine, Met, M,lysine, Lys, K,phenylalanine, Phe, F,try

54、ptophan, 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,203,The following amino acids are also essential amino acids:,histidine, His, T,necessary only for infants,204,arginine, Arg, R,necessary only for cats,205,pHpI,formula,206,5. React with nit

55、rous acid (HNO2),What difference between nitrous acid react with amino acids and nitrous acid react with aliphatic amines?,207,8. React with ninhydrin,Amino 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,208,Chemical bonds of proteins:,1. Principal bond (主键): peptide linkage,2. Auxiliary bonds (副键):,(1) Hydrogen bond