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1、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
2、.(10 points) What are the differences between aryl halides and alkyl halides in the substitution reactions? Why? RX : SN1 and SN2ArX : SNAr addition-eliminationXEWGElimination addition : BengyneBrHNH2BrNH2NH2HElimination addition Explaination: a)XNuNo reaction SN2 Steric hindrance+anstable no SN1b)s
3、p2C-X shorter and stronger resonanceXXXXX3.(10 points) How about the reaction of phenol with concentrated sulfuric acid? Explain its mechanism and performance in detail. AnswerOHconcdH2SO425100OHSO3HOHSO3H100Major. Under kinetic controlMajor. Under thermodynamic controlStable:OHSO3HOHSO3H Reaction R
4、ate: OHSO3HOHSO3HMachanism: electrophilic aromatic substitutiona)2 H2SO4SO3H3OHSO4+b)OHSOOO+SlowSOHOOOHStableOther Resonace Structurec)HSO4SOOOHOHFastSO3OHH2SO4+d)SO3OH+HOHHFastSO3HOH+H2O4.(10 points) What are the named reactions as follows? (Give examples) (a) The Diels-Alder reaction+(b) The Fried
5、el-Crafts alkylationCH2CHClCH3+AlCl3(c) The Claisen condensation2CH3COC2H5ONaOC2H5CH3CCHCOC2H5OONaHClCH3CCH2COC2H5OO+C2H5OH(d) The Michael additionCCHCOC2H5OH3CH3CCH2COC2H5COC2H5OO+C2H5ONaC2H5OH25CH3CCH2COC2H5CH3CH(CO2C2H5)O5.(11 points) What is aldol reaction? Give its mechanisms in the presence of
6、 acid and base respectively?Answer2CH3CHO 10% NaOH,H2O5CH3CCHCH2CHOHO H2O-CH3CHCHCHOAcid:CH3CCH3O +HClCH3CCH2HOHClCH3CCH2OHHCl+CH3CCH2OHCOCH3CH3+H3CCCH2COHCH3CH3OHCH3CCHCOHHOCH3CH3HClCH3CCHCCH3OCH3HClH2O+Base(a)HO+HCH2CHOCH2CHO CH2CHO H2Oenolate anion(b)CH3CHOCH2CHOCH3CHCH2CHOO(c)CH3CHCH2CHOOHOHCH3C
7、HCH2CHOOH +OH6.(10 points) Outline a route to prepare the following compound from benzene and other needed reagents:NNOHAnswerClOHOrNO2NH2N2ClOHNH2NHCCH3O NHCCH3SO3HONHCCH3SO3HOClNH2ClClN2ClClN2Cl+OHClNNOH7.(10 points) Preparation of the following compound from ethylene.CH3CCH2CH2CH2CH2CCH3OOAnswerC
8、H2CH2CH2BrCH2BrCH2CH2CH3CH2OHCH2COOHCH3COOHC2H5OH+CH3COC2H5OCH3COC2H5OCH3CCH2COC2H5OOCH3CCH2COC2H5OO2+CH2BrCH2BrOOCO2C2H5CO2C2H5OOCOOHCOOHOO8.(9 points) Give three different methods for converting carbonyl groups of aldehydes and ketones to CH2- groups.answer a)The Clemmensen ReductionArCROZn(Hg)HCl
9、,refluxArCH2Rb)CORR+HSCH2CH2SHBF3C SSRR+H2OC SSRRRarey NiH2RCH2RC2H6NiS+c)Wolff-Kishner reductionCORR+H2NNH2NaOHTriethylene glycol200RCH2RN2+9.(15 points) Explain the following items using examples: (a) Markovnikov addition vs anti-Markovnikov addition (b) Zaitev rule vs. Hofmann rule (c) Oxidation
10、vs reduction Answera)Markovnikov additionCH3CHCH2HBr CH3CHCH3CH3CHCH3Br BrAnti- Markovnikov additionBrCH3CHCH2CH3CHCH2BrHBrCH3CH2CH2Brb)Zaitev rule To form the more stable alkeneB+CH3CH2CBrCH3CH3CH3CHCCH3CH3majorHofmann rules To form the least substituted alkeneCH3CH2CHCH3OHN(CH3)3150CH3CH2CHCH2majo
11、rc)Oxidation : to increase its oxygen content (decrease its H content) or its content of any element more electronegative than cabon.ArCH3OHArCH2ClOHArCHCl2OHArCCl3Reduction : the opposite of oxidationRCH3OHRCH2OHOHRCHO OHRCOHO10. (10 points) Describe the impotance and limitations of Grinard reagent
12、s in organic synthesis. AnswerRX+MgEt2ORMgXArX+MgEt2OArMgXGrignard ReagentsRXRMgXas base and nuclephileto form new C-C bonds or C-X bonds (X=O)with 1. componds containing acidic hydrogen2. CO ORLimitations: sensitive to H2O and OH, -NH2, -NHR, -COOH, -SO3H, -SH, -CH (acid) and CHOCROCOROCNH2OCNO2OCN O,
