有機化學(xué)七年制復(fù)習(xí)-cla.ppt

1、1,REVIEW,2,我們至少要考70分,3,考不到六十你掛了，我心痛喔,4,It is a shame to cheat in examination,5,考試重點及試題分?jǐn)?shù)分布,一、選擇題（單選題，30小題，每小題1分，共30分,二、命名（5小題，每小題1分，共5分,三、完成下列反應(yīng)式（30小題，每小題1.5分，共45分,五、鑒別題（1小題，10分,六、推測結(jié)構(gòu)題（1小題，5分,七、合成題（1小題，5分,6,第二章：烷烴和環(huán)烷烴,7,8,Stability of radicals,The radical is more steady, and more easy to be formed,

2、9,P.31 2-12 自由基穩(wěn)定性,教科書印刷錯誤,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,14,Stable,Instable,Stable,Instable,15,Stable,Instable,16,17,18,19,第三章：烯烴和炔烴,1) naming

3、for cis-trans isomerism,Cis- : Two same atoms and groups on the double bond, that on the same side of the plane of orbital. Trans: Two same atoms and groups on the double bond, that on the opposite side of the plane of orbital,20,2) naming for Z, E isomerism,The sequence of the preferential groups b

4、ase on the ordinal number of the atoms in molecule,If a b , c d , the molecule is called Z If a b , c d , the molecule is called E,21,The priority sequence of the familiar atoms and groups,I Br Cl F O N C H,CH3)2CH (CH3)2CHCH2 CH3CH2CH2CH2 CH3CH2CH2 CH3CH2 CH3,22,The sequence of negativity,F Cl Br I

5、 OR CH CH H CH3 C2H5 CH(CH3)2 C(CH3)3,23,addition,catalyst: Ni, Pd, Pt,24,Markovnikovs rule: In addition of Lewis acid to alkenes, the Lewis acid will add to the less substituted end of the alkene. The rule works because addition of Lewis acid produce the more substituted, more stable carbocations,S

6、aytzeff 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 contains less hydrogen atoms,25,HX,HX,HX,cyclohexene,1-methylcyclohexene,methylenecyclohexene,26,main pr

7、oduct,First X2 react with H2O to get HO-X, the HO-X add to alkenes is Markovnikov reaction. The less electronegative part will add to the more hydrogen attached end of the alkene. The elimination of hydrogen halides is intramolecular Williamson reaction,27,Peroxide effect,RCH CH2 RCH2 CH2Br,HBr / pe

8、roxide,If addition to alkene react in the presence of any of peroxides, the reaction doesnt abide by Markovnikov rule, and the product is a compound of anti- Markovnikov rule,28,29,Stability of carbocation,tertiary,secondary,primary,methyl,cation stability,30,R1CH CHR2 R1CH CHR2 + MnO2 OH OH,KMnO4 /

9、 OH,cold,oxidation of alkenes,31,CH2=CHCH2CH2C = CR3 R1 R2,KMnO4 / H,O O CO2 + HOOCCH2CH2CR1 + R2CR3,32,Ozonolysis: The reaction of alkene to ozone, in present of any of the reducers, give the products of carbonyl compounds,reductive workup,33,major,minor,Reaction of 1,3-butadiene,The product of 1,4

10、-addition is major, and that of 1,2-addition is minor,major,minor,34,Br2,Distinguish Reactions of Alkenes and Alkynes,RCH CH2 RCOOH + CO2,KMnO4 / H,X2,X2,RC CR RCOOH + R COOH,KMnO4 / H,35,Ag(NH3)2NO3,Cu(NH3)2Cl,brick red deposit,white deposit,36,P. 52 3-11,37,3-13. (1) 己烷， 1-己炔， 3-己炔,ABC,AgNO3/NH3,產(chǎn)

11、生白色沉淀,AC,B,Br2 / H2O,紅棕色消失,C,不褪色,B,不產(chǎn)生白色沉淀,A B C,38,2） 1-戊炔， 2-戊烯， 環(huán)戊烷,A B C,ABC,AgNO3/NH3,產(chǎn)生白色沉淀,BC,A,KMnO4 / H,紫紅色消失,B,不褪色,C,不產(chǎn)生白色沉淀,39,3-17 正碳離子穩(wěn)定性,40,第四章：芳香烴,Hckels rule (rule of 4n+2, 休克爾規(guī)則): All planar, cyclic, fully conjugated molecules with 4n + 2 ( n = 0, 1, 2) electrons will be aromatic (e

12、specially stable). The rule works because such molecules will have molecular orbital systems in which all bonding molecular orbitals are completely full,41,HNO3 / H2SO4,nitrobenzene,42,Friedel-Crafts alkylation reaction,43,44,45,ortho/para locating groups: The groups on the bebzene ring are most eff

13、ective at directing further substitution to the ortho and para position, such as,46,meta locating groups: The groups on the benzene ring are most effective at directing further substitu-tion to the meta position, such as,47,4. Oxidation reaction,oxidant: KMnO4 / H+ , K2Cr2O7 / H+ (potassium dichroma

14、te,48,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,49,50,51,P. 68 4-6由苯或甲苯合成下列化合物,2,separate,52,4-8. 判斷下列化合物是否具有芳香性,53,4-9. (1) 1,3-環(huán)己二烯、苯、甲苯,A B C,ABC,Br2 / H2O,紅棕色消失,BC,A,KMnO4 /

15、 H,紫紅色消失,C,不褪色,B,不褪色,54,2) 苯乙烯、苯乙炔、乙苯,A B C,ABC,AgNO3/NH3,產(chǎn)生白色沉淀,AC,B,Br2 / H2O,紅棕色消失,A,不褪色,C,不產(chǎn)生白色沉淀,55,4-10. 某化合物（A）分子式為C9H12，能被高錳酸鉀氧化得到化合物（B）分子式為C8H6O4。將A進行硝化，只得到兩種一硝基產(chǎn)物。試推測（A）、（B）的結(jié)構(gòu)式，并有反應(yīng)式表示推斷過程,56,Degree of unsaturation(): In a hydrocarbon, the total number of bonds and rings,n4: the number of

16、 atoms with 4 valence (C,n3: the number of atoms with 3 valence ( N,n1: the number of atoms with 1 valence (H ,X,57,structure of compound = 0, saturated =1, a double bond or a ring =2, two double bonds or two rings or a triple bond =4, perhaps a benzen ring,is usually used to deduce the structure of

17、 compounds,58,4-10. 某化合物（A）分子式為C9H12，能被高錳酸鉀氧化得到化合物（B）分子式為C8H6O4。將A進行硝化，只得到兩種一硝基產(chǎn)物。試推測（A）、（B）的結(jié)構(gòu)式，并有反應(yīng)式表示推斷過程,解：化合物A的不飽和度為,化合物B的不飽和度為,59,60,第五章：手性分子,Chiral carbon: The carbon atom attach to four different groups,61,Chiral molecule: A molecule is not superimposable on its mirror image,62,Enantiomers (

18、optical isomers): Nonsuperimposable mirror images, different molecules,63,Racemic mixture(racemate, 外消旋體): A mixture containing equal amounts of two enantiomers forms of a chiral molecule,64,Observed rotation (a) depends on the length of the cell and concentration, as well as the strength of optical

19、 activity, temperature, and wavelength of light,c is concentration in g/mL l is length of path in decimeters (dm,65,Plane of symmetry : The plane which divides the molecule into halves, one part is anothers mirror image,66,Rotate the Fischer projection integral times of 180on the plane or exchange a

20、toms or groups which attach the chiral carbon even times, you will get the same configuration. Rotate the Fischer projection 90or 270 , or exchange atoms or groups which attach the chiral carbon odd times, the configuration will change and you get the enantiomer of the original molecule. You cannot

21、flip over a Fischer Projection,67,68,We also can use Fischer Projection to judge the molecules configuration: 1. establish the priority number of the four groups attached to the chiral carbon. Suppose 1234. 2. If 4 is the group on vertical bonds, and 1 2 3 run clockwise, the configuration is (R); 1

22、2 3 run counterclockwise is (S). 3. If 4 is the group on Horizontal bonds, 1 2 3 run clockwise, the configuration is (S); 1 2 3 run counterclockwise is (R,69,S configuration,R configuration,70,Meso compound: a compound contain chiral carbons but are achiral. The compound must possess two or more ste

23、reocenters,71,P. 84 5-11,存在內(nèi)消旋體的化合物是：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,72,1）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）互為對映體，（2）（3）互為對映體；（1）與（2）（3）為非對映體，（2）與（1）（4）為非對映體,73,第六章：鹵代烴,carbonitrile, nitrile,carboxylic acid,74,75,transition state,sp2 hybr

24、idization,SN2 Reaction,76,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

25、 time. 3. The stereochemistry of the starting material is inverted,77,SN1 Reaction,Nu,78,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

26、 by attack of the nucleophile. 3. Racemization. 4. Sometimes rearrangement is occurred,79,Elimination Reaction,HX,80,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

27、 carbon which contains less hydrogen atoms,81,More examples,82,The rate of E1 and E2 reaction,83,P. 95 6-8,84,6-12. 用化學(xué)方法區(qū)別下列各組化合物,A B C,ABC,AgNO3 heat,不產(chǎn)生白色沉淀,BC,A,KMnO4 / H,紫紅色消失,B,不褪色,C,產(chǎn)生白色沉淀,85,分子式為C5H10的A烴，與溴水不發(fā)生反應(yīng)，在紫外線照射下與等摩爾溴作用得到產(chǎn)物B(C5H9Br)，B與KOH的醇溶液加熱得C(C5H8)，C經(jīng)酸性KMnO4氧化得到戊二酸。寫出A、B、C的結(jié)構(gòu)式及各步

28、反應(yīng)式,解：化合物A的不飽和度為,86,87,第七章：醇、硫醇、酚,sodium alcoholate,88,Hydrochloric acid/dry zinc chloride which is called Lucas reagent,89,1) 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 al

29、cohols do not react with Lucas reagent at room temperature even after one hour,90,2) Dehydration,91,Collins reagent (chromium trioxide in pyridine,92,4. React with cupric hydroxide and periodic acid,The salt is blue color, so you can use this reaction to distinguish 1,2-glycols,93,dimercaptopropanol

30、 or BAL,94,3. Oxidation,disulfide,95,Sequence of acidity,is a symbol which combine A and R together, it means aryl groups or aliphatic groups,96,p-benzoquinone,hydroquinone,1,4-benzoquinone,97,98,white precipitation,2,4,6-tribromophenol,We can use this reaction to distinguish phenol (caution: only p

31、henol, not all phenols.,99,4. react with ferric chloride,All phenols can react with ferric chloride and the products are complex compounds. The products have various color, so we can use this reaction to distinguish phenols and enol,100,P. 111 7-6,101,7-8. 鑒別,3）對苯酚 苯甲醇,AB,FeCl3,產(chǎn)生顏色反應(yīng),B,A,不產(chǎn)生顏色反應(yīng),A

32、B,102,4）1,2-丙二醇 1,3-丙二醇,A B,AB,Cu(OH)2,沉淀消失，生成藍色透明溶液,B,A,沉淀不消失,103,第八章：醚和環(huán)氧化合物,Williamson Ether Synthesis,104,Notes,1. Allyl and benzyl halides are the preference choice. 2. Methyl halides and primary halides are the better choice. Secondary halides are of little use because the alkoxides are strong

33、 bases and the E2 reaction is a prominent side reaction,3. Never use ethenoid halides and benzenoid halide. We have learned in Chapter 6 that the C-X bonds in these two kinds halides are extremely strong,105,Example 1,How to synthesis (CH3)3C-O-CH3 ? It seem there are tow choices. One is (CH3)3C-X r

34、eact with NaO-CH3. Another one is (CH3)3C-ONa react with CH3X. Which one is the right one? Why,106,Example 2,react with,107,Question 1: How to synthesis (CH3)2CH-O-CH2CH3,108,Formation of oxonium salt,109,Rupturing of ether bond,Notes: 1. The less carbon atoms R form iodides. Methyl form CH3I (iodom

35、ethane) 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 HBr,110,React with epoxides,111,Opening of unsymmetrical epoxides in acid is a SN1 reaction. Epoxides react with proton to form a stable car

36、bocation, then react with nucleophiles,112,113,P. 120 8-5,114,8-7. 某化合物A的分子式為C7H8O，A與金屬鈉不發(fā)生反應(yīng)，與濃氫碘酸反應(yīng)生成兩個化合物B和C，B能溶于氫氧化鈉，并與FeCl3作用呈紫色，C與硝酸銀醇溶液作用，生成黃色深沉，試寫出A、B和C的結(jié)構(gòu)及有關(guān)反應(yīng)式,解：化合物A的不飽和度為,115,116,第九章：醛和酮,Friedel-Crafts Acylation Reaction,117,CrO32C5H5N is called Collins reagent,118,cyclohexanone,119,Not

37、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 include aliphatic and aromatic aldehydes,2. Aliphatic methyl ketones,3. Cyclic ketones which the rings contain eight or less carbon atoms

38、,n8,120,121,122,Point out which compounds of the following molecules can react with sodium bisulfite,123,124,Addition of Grignard Reagents,125,Addition of derivatives of ammonia,Schiff base,126,127,2,4-dinitrophenyl hydrazine,2,4-dinitrophenyl hydrazone,yellow precipitation,Formation of 2,4-dinitrop

39、henyl hydrazone can diagnose the presence of a carbonyl group,128,Aldol condensation,129,Mechanism of aldol condensation,carbanion,intermediate,aldol,130,131,crossed aldol condensation,132,2. Haloform reactions,133,haloform,sodium hypohalide,134,135,silver mirror reaction,Oxidation and Reduction,cup

40、rous oxide, brick red color,136,Tollens reagent can react with all aldehydes (aliphatic and aromatic), but Fehlings reagent only can react with aliphatic aldehydes. You can use Fehlings reagent to distinguish aliphatic aldehydes and aromatic aldehydes,137,reduction,lithium aluminium hydride,138,Meta

41、l hydrides (LiAlH4, NaBH4, and many others) can reduce aldehydes and ketones to give alcohols. Compare with hydrogenation reaction, application of metal hydrides is more selective. Metal hydrides only reduce the carbonyl group but not carbon-carbon double bond,139,Clemmensen Reaction,Zn-Hg/HCl: zinc

42、 amalgam,DEG: diethylene glycol, 一縮二乙二醇(HOCH2CH2)2 O TEG: triethylene glycol (HOCH2CH2OCH2)2,methylene,140,If the start material contains acid sensitive groups, Wolff-Kishner-黃鳴龍 Reduction is applied to reduce the carbonyl group. Clemmensen Reaction is used to those carbonyl compounds which contain

43、base sensitive groups,141,P. 132 9-7. 試用下列各試劑與環(huán)戊酮進行反應(yīng)，寫出各產(chǎn)物的結(jié)構(gòu),142,Ag2O/NH3,143,10,144,145,9-14. 鑒別 （2）2-戊酮、3-戊酮、環(huán)己酮,ABC,I2 NaOH,產(chǎn)生黃色沉淀,BC,A,NaHSO3,產(chǎn)生白色沉淀,C,不產(chǎn)生白色沉淀,B,不產(chǎn)生黃色沉淀,A B C,146,第十章：羧酸和取代羧酸,1) FCH2COOH ClCH2COOH BrCH2COOH ICH2COOH CH3OCH2COOH HOCH2COOH CH3COOH 2) FCH2COOH FCH2CH2COOH FCH2CH2C

44、H2COOH 3) CF3COOH F2CHCOOH FCH2COOH,The sequence of acidity,147,COOH,COOH,COOH,COOH,COOH,COOH,NO2,NO2,NO2,OH,OH,COOH,OH,148,1) FCH2COOH ClCH2COOH BrCH2COOH ICH2COOH CH3OCH2COOH HOCH2COOH CH3COOH 2) FCH2COOH FCH2CH2COOH FCH2CH2CH2COOH 3) CF3COOH F2CHCOOH FCH2COOH,The sequence of acidity,149,Sequence

45、of -I effect,150,151,butanedioic anhydride,pentanedioic anhydride,152,phthalic anhydride,153,1) -alcoholic acid,154,2) -alcoholic acids,unsaturated carboxylic acid,155,valerolactone,3) -alcoholic acids and -alcoholic acids,butyrolactone,156,157,ketone body,Ketone body is the incomplete oxidating met

46、abolite of fatty acids. The level of ketone body will remarkable increase when suffer from diabetes,158,P. 146,10-5. 寫出下列反應(yīng)的主要產(chǎn)物,159,160,3,A B C D,ABCD,NaHCO3,不產(chǎn)生CO2,AB,CD,Ag(NH3)2NO3,產(chǎn)生銀鏡,A,不產(chǎn)生銀鏡,B,產(chǎn)生CO2,Ag(NH3)2NO3,產(chǎn)生銀鏡,C,不產(chǎn)生銀鏡,D,10-7 用簡單的化學(xué)方法區(qū)別下列各組化合物,161,10-7. 按酸性由強到弱排出下列各組化合物的順序,1,2,162,9. 解,De

47、gree 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,163,structure of compound = 0, saturated =1, a double bond or a ring =2, two double bonds or

48、 two rings or a triple bond =4, perhaps a benzen ring,is usually used to deduce the structure of compounds,164,A B,C,D,165,10. 解,alcoholic acids,166,A B,A B,167,11. 化合物A(C8H14)經(jīng)催化加氫得化合物B (C8H16)，A經(jīng)臭氧氧化后再經(jīng)Zn/H+處理得化合物C(C8H14O2)，C經(jīng)Tollens試劑加熱反應(yīng)，得D (C8H14O3)，D與I2/NaOH反應(yīng)得3-甲基己二酸。試寫出A，B，C，D的結(jié)構(gòu)式,解,D,C,A,B,

49、168,169,13. 解,170,171,172,14. 化合物A的分子式為C8H8O2能與NaHCO3反應(yīng)。A在光照下與Br2反應(yīng)得分子式為C8H7BrO2 的一對對映體B 和C ； B 和C與NaCN反應(yīng)，得到分子式為C9H7NO2 同一的外消旋體D，D 在酸性水溶液中加熱得到一種無光學(xué)活性的E（2-苯基丙二酸）。試寫出A，B，C，D和E的結(jié)構(gòu)式,解：化合物A的不飽和度為,所以化合物A可能含有苯環(huán)結(jié)構(gòu),173,174,175,第十一章：羧酸衍生物,176,phosphorus pentoxide, dehydrant,177,178,179,This reaction also know

50、 as transesterification reaction,180,acidamide,181,Acid halides, anhydrides and esters are acylating agents. The start material react with these acylating agents can introduce acyl group,182,183,4) Biuret Reaction (縮二脲反應(yīng),Biuret can dissolve in alkali solution. If a little cupric sulfate be added to

51、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 ( 肽鍵 ) such as polypeptide, protein, etc. can take place biuret reaction,184,完成下列反應(yīng)式，寫出主要產(chǎn)物,185,186,187,188,用化學(xué)方法鑒別下列

52、各組化合物,1）乙酸乙酯、-丁酮酸、丁酰胺,A B C,ABC,NaHCO3,不產(chǎn)生CO2,AC,B,HNO2,產(chǎn)生N2,C,不產(chǎn)生N2,A,產(chǎn)生CO2,189,2）乙酐、甲酸甲酯、乙酰溴,A B C,ABC,AgNO3,產(chǎn)生淺黃色沉淀,AB,C,Ag(NH3)2NO3,產(chǎn)生銀鏡,B,不產(chǎn)生銀鏡,A,不產(chǎn)生淺黃色沉淀,190,7.化合物A在酸性水溶液中加熱，生成化合物B（ C5H10O3）B與NaHCO3反應(yīng)放出無色氣體，與CrO3作用生成C （ C5H8O4），B在室溫條件下不穩(wěn)定，易失水生成A。試寫出A，B，C的結(jié)構(gòu)式,解：化合物B的不飽和度為,B在室溫條件下不穩(wěn)定，易失水生成A,B為-羥

53、基酸；A為-內(nèi)酯,191,A B C,192,第十二章：胺和生物堿,Sequence of the basicity of amines,quaternary ammonium salt,quaternary ammonium hydrate,tertiary amine,193,2. Acylation,amide,194,3. Sulfonylation,benzene sulfonyl chloride,p-toluenesulfonyl chloride,I effect,weak acid,crystal,benzene sulfonamide,195,The above react

54、ion 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 dissol

55、ve in sodium hydroxide solution. For tertiary amines, this reaction can not take place,196,4. React with nitrous acid (HNO2,1) Primary amines,197,2) Secondary amines,198,yellow solid,Actually, we use sodium nitrite/hydrochloric acid NaNO2/HCl instead of nitrous acid (HNO2,199,Section 2 Diazo and Azo

56、 Compounds,Diazotization Reaction,benzene diazonium chloride,Reaction of Diazo Salt,1. Substitution,05,200,201,H3PO2: hypophosphorous acid (次磷酸,202,2) How to synthesize 1,3,5-tribromobenzene from benzene,Question: 1) How to synthesize 2-methyl benzoic acid from toluene,203,05,1,204,2,05,205,2. Coupl

57、ed Reaction,206,2. Hydrolysis,207,4) Biuret Reaction (縮二脲反應(yīng),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

58、 two peptide linkages ( 肽鍵 ) such as polypeptide, protein, etc. can take place biuret reaction,208,第十四章：芳香雜環(huán)化合物,furan 呋喃,thiophene 噻吩,pyrrole 吡咯,thiazole噻唑,imidazole咪唑,pyrazole吡唑,oxazole噁唑,1,1,1,209,pyrimidine嘧啶,pyridine, py吡啶,1,210,quinoline 喹啉,isoquinoline異喹啉,indole 吲哚,purine 嘌呤,211,第十五章：糖類,Almost

59、 natural sugars are D sugars,212,Oligosaccharides and polysaccharides can be hydrolyzed to monosaccharides, so all sugars have a reaction as follow,This reaction is named as Molisch reaction, can be used to distinguish saccharides,213,Oxidation,1. React with Tollens, Fehlings or Benedicts reagent,214,Cause: 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