有機化學：FinalReview

1、Final Review1. Give IUPAC names to the following compounds 2. Draw structures corresponding to the following IUPAC names: Alkanes (cycloalkanes)Alkenes (dienes，cyclonealkenes)AlkynesEnynesAromatic hydrocarbonsHalogen-substituted hydrocarbons Alcohols and phenols1. Find the parent；2. number the paren

2、t；3. Cite different substituents in alphabetical order；4. Write the full name in correct format.(1)(2) Nomenclature of E, Z isomers of alkenes .(3) Nomenclature of R, S isomers of chiral carbons.(4) The most stable conformation of alkenes and cycloalkanes (cyclohexane).CH3CH2CCCH3H3CCH3CH3CCCH3CH2CH

3、3H5-Ethyl-3,5,6,6-tetramethyl-3-hepteneHCCH3PhCH(5S, 3E)-(3R)-Final Review3-phenyl-1-butyneThe most stable conformation of trans-1- Chloro-3-methylcyclohexaneFinal ReviewCH3ClFinal Review3. Predict the major product(s) of the following reactions: Types of Reactions: (1) Free radical substitution rea

4、ctionRelative reactivity: allylic, benzylic free radical 3C 2C 1C Reaction conditions : X2 / hv,or heat; NBS (2) Free radical addition reactionCH3CH2CH=CH2CH3CH2CHHCH2BrROORHBrAnti-Markovnikov additionOnly HBrFinal Review(3) Electrophilic Aromatic Substitution:XHX2FeHNO3H2SO4H2SO4NO2SO3HRXAlCl3AlCl3

5、RCOClRC-ROZn-HgHClCH2RSubstituent Effects定位規(guī)則定位規(guī)則(1) Reversible, (2) HighT para occupy the position1) Alklation reagents: RX， C=C, 2) C+ rearrangement(RCO)2OThe alkylation and acylation reaction doesnt succeed on an aromatic ring that is substituted by a strongly electron-withdrawing group.SO3HSO3H1

6、6596%H2SO4 CH3X 1RX 2RX 3RX烯丙基烯丙基,芐基芐基 3 2RX 1RX CH3XR-X的反應活性的反應活性構(gòu)型翻轉(zhuǎn)構(gòu)型翻轉(zhuǎn)外消旋化外消旋化立體化學立體化學= kRXNu- ( (二級反二級反應應) )= kRX ( (一級反應一級反應) )動力學動力學反應機理反應機理SN2SN1R XslowRXR+X-R+Nu-fastR Nu(two steps)R X+Nu-NuCX-Nu R+X-(one step)離去基團離去基團I- Br- Cl- F-I- Br- Cl- F-Final ReviewFor Nucleophilic Substitutions of a

7、lkyl halides, please note: SN1, C+, rearrangement Selectivity of SN1, SN2 reactionBrBrNaI丙酮BrIStereochemistry of the SN1, SN2 reactions:CH3Cn-C3H7C2H5BrH2OCH3Cn-C3H7C2H5OH+CHOCH3n-C3H7C2H5SN1， Racemization HCH3BrHNaI丙丙酮酮HCH3HISN2， Walden InversionFinal ReviewROH:Allyl alcohol，benzyl alcohol， 3o ROH

8、and 2o ROH -SN1; 1o ROH -SN2R OH+ HXROH2+XR X+ H2OZnCl2Final ReviewCCH3H3CCH3CH2OHHCl(1) SOCl2ZnCl2CCH3H3CCH3CH2ClCClH3CCH3CH2CH3ROHHXRXPX3RXSOCl2RXSN1, C+ , rearrangementno rearrangementno rearrangement(7) The Diels-Alder Cycloaddition ReactionFinal ReviewThe configuration of the dienophile is reta

9、ined (構(gòu)型保持構(gòu)型保持)+OCH3OHHOCH3OHHCOOCH3COOCH3+COOCH3COOCH3+CHCH2 HCCHCuCl-NH4Cl80-85oCCH2CHCCHH2LindlarCH2CHCHCH2dienophille(8) Elimination reactionFinal ReviewRX( (KOH-EtOH) )ROH(H+)-H，to form most stable alkeneseliminate HXH2ONote please :E1, C+, rearrangement CH2CHCH3BrC2H5OHNaOHCH=CHCH3The stereoch

10、emistry of E2: anti periplanar CH3HHBrKOHHHCH3(9) Oxidation reactionFinal ReviewOxidation of alkenes:CC+ RCOOOHCC+ORCOOHRCHCH2+KMnO4OH-RCHCH2OHOH+MnO2coldMnO4冷冷HHHOOHOH-Syn-additionKMnO4CHR1COOHR1CRRCORR+H+CCH3CH3CHCH3C OH3CH3CO CHCH3+O3Zn+ H2OPropose the structure of alkenes Oxidation of alkynes:Fi

11、nal ReviewRCOHRCCRRCOHO+OH2OKMnO4 O3H2ORCOHRCOHO+OPropose the structure of alkynes Oxidation of Alkylbenzene Side Chains CH2CH3COOHC(CH3)3no reactionKMnO4KMnO4Final ReviewOxidation of alcoholsRCH2OHRCOHOKMnO4or K2Cr2O7RCH2OHRCHOPCCR CHOHRH+K2CrO7R CORHIO4CH2CHCH2OHOHOH+CH2O+HOCHO+CH2OOHCrO3OOFinal R

12、eviewAlkynes + H2Ni, Pt, Pd catalystLandlar or P-2 catalyst(Z) or cis -AlkenesAlkanesNa or Li (NH3)(E) or trans -Alkenes(10) Reduction reaction:CC=CHCH2CH2OHCHCH3H2 (1 mol)Pd-CaCO3CH2=CHC=CHCH2CH2OHCH3The reactivity of hydrogenation :Alkynes Alkenes(11) The acidity of terminal alkynes, alcohols and

13、phenolsFinal ReviewHCCHNa NH2Liq. NH3CCNaHNa NH2Liq. NH3CCNaNaR OHR ONaRXR ORNaOH+ NaOHONaRXORCH3I(CH3)2SO4OCH3orRX碳鏈增長的炔烴碳鏈增長的炔烴Final Review確定確定反應的部位反應的部位: : 在多官能團化合物中，判斷反應在在多官能團化合物中，判斷反應在哪個官能團上哪個官能團上 發(fā)生發(fā)生, ,一般要考慮：選擇性氧化、選擇性還原、一般要考慮：選擇性氧化、選擇性還原、 選擇性取代、選擇性加成、分子內(nèi)還是分子間反選擇性取代、選擇性加成、分子內(nèi)還是分子間反 應等。應等?？紤]考慮立

14、體選擇性問題：消除反應：順消還是反消立體選擇性問題：消除反應：順消還是反消? ? 加成反應：順加還是反加加成反應：順加還是反加? ? 親核取代：親核取代：SN1: :重排，外消旋、重排，外消旋、 SN2：構(gòu)型翻轉(zhuǎn)。：構(gòu)型翻轉(zhuǎn)?？紤]考慮反應的終點問題：氧化：階段氧化還是徹底氧化反應的終點問題：氧化：階段氧化還是徹底氧化 還原：階段還原還是徹底還原、還原：階段還原還是徹底還原、 ClOAlCl3Zn/HgHCl/Cl2hvKOHCH3OH2. Zn/HOAc1.O3Final ReviewOClCHOCHO2. H2O2/OH-BH3/THFBrKNH21.HOFinal Review4. Sho

15、rt answer questions: Alkanes： comparing the boiling point of the alkanes The stability of conformational Isomer (構(gòu)象構(gòu)象) of alkanes and the most stable conformation of substituted cyclohexanes. The stability of C+ and C（共軛和誘導效應）（共軛和誘導效應）Alkenes and Alkynes：The stability of alkenes.The relative reactiv

16、ity of hydrogenation reaction(氫化氫化)(烯烴和炔烴烯烴和炔烴, , 不同烯烴之間不同烯烴之間)The relative reactivity of electrophilic additions (烯烴和炔烴烯烴和炔烴, , 不同烯烴之間不同烯烴之間)Final ReviewConjugated dienesThe stability of 1, 2- and 1.4-addition productFactors favoring the Diels-Alder reaction: diene, dienophileAromatic hydrocarbon (

17、including 稠環(huán)芳烴稠環(huán)芳烴)The relative reactivity of electrophilic substitution reactionSubstituent Effects(定位規(guī)則定位規(guī)則)position and reactivity of electrophilic substitution reactionHuckels ruleFinal ReviewStereochemistrySome basic conception: 手性，光學活性，對映異構(gòu)體，內(nèi)消旋，手性，光學活性，對映異構(gòu)體，內(nèi)消旋， 外消旋等外消旋等(英文怎么講英文怎么講)1 1）對稱因素）

18、對稱因素2 2）手性碳原子，只有一個手性碳一定有手性，但兩個手性碳？）手性碳原子，只有一個手性碳一定有手性，但兩個手性碳？3 3）不含手性中心，丙二烯型，取代聯(lián)苯）不含手性中心，丙二烯型，取代聯(lián)苯How to determine whether a compound is chiral or achiral?Indentify the relationship between the pairs of molecules: same compounds, enantiomers (非對映異構(gòu)體非對映異構(gòu)體) or diastereomers(非對映非對映異構(gòu)體異構(gòu)體) Halogen-Subs

19、tituted HydrocarbonsFinal ReviewComparing the nucleophilicity(親核性親核性) of different nucleophile(親核試劑親核試劑)The relative reactivity of nucleophilic substitutionsAgNO3-EtOH -(SN1)NaI + Acetone-(SN2)The relative reactivity of elimination reaction: NaOH + EtOH, ,醇鈉或醇鉀醇鈉或醇鉀)The nucleophilic substitutions of

20、 Phenyl Halides (苯基鹵代烴苯基鹵代烴) X?NO2NO2Final ReviewAlcohols:Comparing the relative acidity of different alcohols.Hydrogen-bond with the physical properties of alcools.The relative activity of alcohols with Lucas reagent.Comparing the relative acidity of substituted phenols.Final ReviewSpectroscopy比較不同

21、的官能團比較不同的官能團紅外吸收紅外吸收頻率的大小頻率的大小a. OH, b. 烯烴的順反異構(gòu)烯烴的順反異構(gòu), c. 末端炔烴末端炔烴d. 苯環(huán)和決定苯環(huán)上取代的數(shù)目和相對位置苯環(huán)和決定苯環(huán)上取代的數(shù)目和相對位置f. 根據(jù)胡可定律推測吸收峰頻率的相對大小根據(jù)胡可定律推測吸收峰頻率的相對大小IR：1H NMR：a. 影響化學位移的因素影響化學位移的因素b. 典型官能團化學位移大小的比較典型官能團化學位移大小的比較 c. 耦合裂分耦合裂分a) At what position, and on what ring, would you expect the following substances

22、to undergo electrophilic substitution? : (5%)Final ReviewNO2C(CH3)3CH(CH3)2OHOSO3HHNClOFinal Review Which would you expect to be aromatic compounds according to Huckel 4n+2 rule? A( )B( )CODOE( )( )( )1.Br2 / CCl4- - - alkenes, alkynes and 3-member ring2.KMnO4- - alkenens, alkynes and benzenes with

23、side chain3.Diels-Alder反應（順丁烯二酸酐）反應（順丁烯二酸酐）- - conjugated dienes 4.Ag(NH3)2NO3 or Cu(NH3)2Cl - terminal alkynes5.AgNO3-EtOH-alkyl halides 6.Lucas (ZnCl2 / HCl)-alcohols7.The acidity of phenols- separate phenols 8.Br2 / H2O- phenols 9.FeCl3 - phenols and enols (烯醇烯醇) Final Review Distinguish compound

24、s using simple chemical tests: what you would do and what you would see. How would you distingush between the following compounds using simple chemical tests? Tell what you would do and what you would see. (9%) Cyclopentane, 1-Pentyne and 2-Pentyne Final ReviewAg(NH3)2NO3+Br2/CCl4+褪色5. Propose reaso

25、nable mechanisms to the following reactions:Final Review(1) Substitution reaction (取代反應取代反應)a. Free radical：脂肪烴和芳烴側(cè)鏈的取代反應脂肪烴和芳烴側(cè)鏈的取代反應-鏈引發(fā)，鏈增長和鏈引發(fā)，鏈增長和 鏈中止鏈中止 (3 steps).b. Electrophilic: 苯環(huán)的硝化、鹵化、磺化、烷基化苯環(huán)的硝化、鹵化、磺化、烷基化( (鹵代烴，烯烴和醇鹵代烴，烯烴和醇 為烷基化試劑為烷基化試劑) )和酰基化和?；?親電質(zhì)點的產(chǎn)生、親電質(zhì)點的產(chǎn)生、- - 絡合物的生成，失去質(zhì)子恢復苯環(huán)結(jié)構(gòu)絡合

26、物的生成，失去質(zhì)子恢復苯環(huán)結(jié)構(gòu)(3 steps).c. Nucleophilic: 鹵代烴和醇的的鹵代烴和醇的的SN1 (C+ 的重排）的重排）, , 苯基鹵代烴苯基鹵代烴親核取代（鄰對位有強的吸電子取代基親核取代（鄰對位有強的吸電子取代基- - 加成加成- -消除機理消除機理或強堿條件下或強堿條件下( (NaNH2,NH3(l)-消除消除- -加加 成機理成機理. .Final Review(2) Elimination reaction (消除反應消除反應)E1消除：醇失水（酸催化）；鹵代烷失鹵化氫（堿催化或消除：醇失水（酸催化）；鹵代烷失鹵化氫（堿催化或Ag 鹽催化）鹽催化） - - C

27、+ 重排重排, 1,2- 二醇的二醇的頻哪醇重排生成酮頻哪醇重排生成酮(3) Addition reaction (加成反應加成反應)a. Electrophilic: （碳碳雙鍵、碳碳叁鍵）（碳碳雙鍵、碳碳叁鍵）-鹵素鹵素(溴溴鎓鎓離子離子)，鹵代氫，鹵代氫 （C+ 重排重排)，次鹵酸次鹵酸(溴溴鎓鎓離子離子) 碳碳叁鍵和水的加成碳碳叁鍵和水的加成（HgSO4 / H2SO4, 烯醇和酮的烯醇和酮的 互變異構(gòu)）互變異構(gòu)） 碳碳雙鍵和水的加成碳碳雙鍵和水的加成（H+ ， C+ 重排重排) b. Nucleophilic: （碳碳叁鍵）（碳碳叁鍵）Final Review+HBrBrHHBrBr

28、6. Synthesize the following target molecules from corresponding starting organic compounds and any inorganic compounds you need. Final Review有機合成的三大要素有機合成的三大要素1. 1. 透徹理解各種反應透徹理解各種反應; ;2. 2. 掌握建造分子的基本方法掌握建造分子的基本方法; ;3. 3. 建立正確的思維方式建立正確的思維方式逆合成原理。逆合成原理。建造分子的基本方法建造分子的基本方法1.1. 官能團的引入和轉(zhuǎn)化：官能團的引入和轉(zhuǎn)化：如烷烴的鹵化

29、；烯烴，炔烴和不同親電試劑如烷烴的鹵化；烯烴，炔烴和不同親電試劑的加成；芳香烴和不同親電試劑的反應（的加成；芳香烴和不同親電試劑的反應（磺化反應磺化反應的占位和可逆，的占位和可逆，定位規(guī)律）；芳烴側(cè)鏈的引入；鹵代烴和不同親核試劑的反應，鹵定位規(guī)律）；芳烴側(cè)鏈的引入；鹵代烴和不同親核試劑的反應，鹵代烴的消除；醇和酚的成醚，成酯，成鹵代烴以及醇的選擇性氧化代烴的消除；醇和酚的成醚，成酯，成鹵代烴以及醇的選擇性氧化等。等。Final Review2. 2. 碳架的改造和拼搭：碳架的改造和拼搭： 炔鈉和鹵代烴炔鈉和鹵代烴-碳鏈增長的炔烴；碳鏈增長的炔烴；芳烴側(cè)鏈的引入芳烴側(cè)鏈的引入-付克的烷基化，付克?；犊说耐榛犊缩；?+ Zn-Hg 還原，還原， 鹵代烴和有機金屬試劑的偶聯(lián)鹵代烴和有機金屬試劑的偶聯(lián)a.a. 碳鏈的增長碳鏈的增長: :2 HCCHCuCl-NH4Cl80-85oCCH2CHCCHRX+NaCNRX+RMgXRRRX+R2CuLiRRRX+2 Na+RXRRFinal