上海交通大学试卷（B卷）2006至2007年第1学期班级号：____________________ 学号：__________________ 姓名：_________ 课程名称：Organic Chemistry II (Jan.26，2007)You have 120 minutes to answer all of the following 10 questions. The total value of them is 100 points. Good Luck!1.(5 points) In your mind, what are the five key points you learned in organic chemistry?Why?2.(10 points) What are the differences between aryl halides and alkyl halides in thesubstitution reactions? Why?RX : SN1 and SN2ArX : SNAr XEWGaddition-eliminationElimination – addition : BengyneNH22NH2H Eliminationaddition Explaination:a)No reaction SN2 Steric hindrance+anstable no SN1b)sp2C-X shorter and strongerresonanceX X3.(10 points) How about the reaction of phenol with concentrated sulfuric acid? Explainits mechanism and performance in detail.AnswerOHconcd2425度100度3HOH3H度Major. Under kinetic controlMajor. Under thermodynamic controlStable:OH3HOHSO3H >Reaction Rate: OHSO3HOHSO3H>Machanism: electrophilic aromatic substitutiona)2H2SO4SO3H3O HSO4++b)S OHOOOHStableOther Resonace Structure c)SO3OHH2SO4+d)OH+O HHSO 3HOH+H 2O4.(10 points) What are the named reactions as follows? (Give examples)(a)The Diels-Alder reaction+(b)The Friedel-Crafts alkylationCH2CHClCH3+AlCl(c)The Claisen condensation2CH32H5O3CCHCOC2H5O ONaHClCH322H5O O+C2H5OH(d)The Michael additionC2H5OH3CH3CCH22H5COC2H5O+C2H5ONaC2H5OH25°CH3C CH2C OC2H5CH32C2H5)O5. (11 points) What is aldol reaction? Give its mechanisms in the presence of acid and baserespectively?Answer2CH 3O 10% NaOH,25度CH 3CCHCH 2OH O2-CH 3CH CH C HOAcid:CH 3C3O3C2ClCH 3CH2OHHCl+CH 3C2C CH 3H 3C C CH 2C OHCH 33OHCH 3C CH C O HOCH 33ClCH 3CCH CCH 3O CH3HClH 2O++Base(a)HOH 2C HOC HO CH 2C HO H 2Oenolate anion(b)CH 3C O CH 2C HO CH 3CH CH 2C HOO(c)CH 3CH 2C OH O HCH 3CH CH 2C HOOH +OH6.(10 points) Outline a route to prepare the following compound from benzene and otherneeded reagents:N NOHAnswerCl OHOrNO2NH2N2OH NH23ONHCCH3SO3HONHCCH3SO3HOClNH2Cl ClN2ClClN2Cl+OHClN N OH7. (10 points) Preparation of the following compound from ethylene.CH 32CH 2CH 2CH 2CCH 3OAnswerCH 2CH 2CH 2BrCH 2Br CH 2CH 2CH 3CH 2OHCH 2COOHCH 3COOHC 2H 5OH+CH 3COC 2H 5O CH 3COC 2H 5OCH 3C CH 2C OC 2H 5OOCH 3C CH 2C OC 2H 5OO2+CH 2BrCH 2BrOO CO 2C 2H 5CO 2C 2H 5OOCOOHCOOH OO8.(9 points) Give three different methods for converting carbonyl groups of aldehydes andketones to –CH2- groups.answera)The Clemmensen ReductionO Zn(Hg)HCl,refluxArCH2Rb)C ORR'+HSCH2CH2SHBF3CSSRR'+H2OCSSRR'Rarey Ni2R CH2R'C2H6NiS++c)Wolff-Kishner reductionO RR'+H2N NH2NaOHTriethylene glycol200°R CH2R'N2+9. (15 points) Explain the following items using examples: (a) Markovnikov addition vs anti-Markovnikov addition (b) Zaitev rule vs. Hofmann rule (c) Oxidation vs reduction Answera) Markovnikov additionCH 3CH CH 2H BrCH 3CHCH 3CH 3CHCH 3Br BrAnti- Markovnikov additionBrCH 3CH CH 2CH 32BrCH 3CH 2CH 2Brb) Zaitev ruleTo form the more stable alkeneB+CH 3CH 2CBrCH 3CH 3CH 3CH C CH 33majorHofmann rulesTo form the least substituted alkeneCH 3CH 2CHCH 3OHN(CH 3)3150°CH 3CH 2CH CH 2majorc) Oxidation : to increase its oxygen content (decrease its H content) or its content of anyelement more electronegative than cabon.ArCH 3[H]ArCH 2ClArCHCl 2ArCCl3Reduction : the opposite of oxidationRCH 3RCH 2OHO[O]O10. (10 points) Describe the impotance and limitations of Grinard reagents in organicsynthesis.AnswerRX+Mg 2RMgX ArX +Mg2ArMgX Grignard ReagentsR X R MgX as base and nuclephileto form new C-C bonds or C-X bonds (X=O)with 1. componds containing acidic hydrogen 2. O O RLimitations: sensitive to H2O and –OH, -NH2, -NHR, -COOH, -SO3H, -SH, -CH (acid) and C H O C R O C OR O C NH 2O C NO 2O CN O ,,,,,,。