华东理工大学有机化学课后答案

1、精品感谢下载载部分习题参考答案2-1顺-1,2-二澳环己烷(6)1,7,7-三甲基二环2.2.1庚烷5-甲基螺3.4辛烷(9)(10)CH3CH3IIH3CC-C-CH3(11)(CH3)2CHCH2CH2CH32-4(3)>(2)>(5)>(1)>(4)2-6(1)正丙基(n-Pr-)(2)异丙基(i-Pr-)2-72-82-92-102-112-132-15(4)叔丁基(t-Bu-)甲基(Me-)(3)CH3CH2CH(CH3)2(4)(CH3)4C(3)、(6)等同;(2)、(5)构造异构;(1)、(4)CH3ch3(3)异丁基(i-Bu-)(6)乙基(Et-)构

2、象异构(1)用Br2。因氢原子活性有差异，澳原子活性适中，反应选择性强,(2)用Cl2。只有一种氢，氯原子反应活性高。CH3CH2的稳定性大于CH3,-易于生成。2,3-二甲基丁烷有四个典型构象式,2,2,3,3-四甲基丁烷有二个;H3cH式为CH3由HhCHCH3CH3HH(2)H3c(顺CH(CH3)2CH3<>一CH)>.CH(CH3)2<CH3CH(CH3)2CH(CH3)2CH3主要得到JBr。前者最稳定的构象C2H5Cl1CH3Cl2-16(4)>(2)>(3)>(1)4-4CH3(CH3)2CHC = OCH3IBrO= CHCH3(8)

3、OO(CH3)2CHCCHCH3、OH3cCH2BrBrMJA(10)BrOCH3CH3(11)H2cCn'nCOOCH34-5(1)乙烯基CH3CH2CH2CH=CH2烯丙基CH3CH2pH=CHCH3有顺反异构丙烯基CH3CH3CH3CH2C=ch2CH3CHCH3异丙烯基CH2=CHCH(CH3)2乙烯基(2) 2,3-二甲基-2-丁烯2-甲基-2-戊烯反-3-己烯顺-3-己烯1-己烯(3) 2-甲基-1-丙烯快(形成叔碳正离子)快(形成叔碳正离子)4-6(1)亲电加成反应，中间体为碳正离子，有重排(CH3)2CHCH=CH2H+(CH3)2ChChCH3Br*(CH3)2CHC

4、HCH3Br重排4-B厂CH3C一CH2CH3*(CH3)2CCH2CH3CH3Br(2)甲醇与碳正离子结合；直接失去质子而形成醒+_H八八CH2CH2+CH3OH*CH2CH2”CH2CH2BrBr+OCH3BrOCH3H(3)BrBrH+H'CH3Br+BrCH3+HCH3BrHHCH3CF3CHCH2CF3CHCH3CF3cH2cH2（稳定）Cl"CF3cH2cH2clCH3OCH2CH2CH3OCHClCH3OCHC1CH3重排Cl4-7CHCHHCH3CH3OCHCH3（稳定）ch3hHTCH2CH3CCH2CH2cCH2CH2CCH3CCH3CCH3CH3HCH3

5、cHHCCH3CH2CH2CH3hCH2CH2CH3CH3cCH3CH3CCH3或5-9（1）Br2/CCl4；Ag（NH3”NO3(2)顺丁稀二酸酎;Ag(NH3)2NO35-11H3cH3cHCH3-CCH3H3cHCCH3CH3CH2CH2CHCH2CH2CH3Ch3H3cHHC1CC二CHCH3CH3H3cHHHHCe=eCH3H3cC-CHCHCH3HCH3C-CH5-12ACH3CHeCHCH3BCH3cHe三CCH2CH2CH3CH3cH3cH2cH2cOOHcH3chcOOHCh3CH3CHCCH3ch36-1(a)c3H7NO(b)C2H3OCl6-3CH3CH=CHCH2C

6、H2CH3a-CH2CH3m/z=84一CH2CH2CH3CH3CH=CHCH2CH3CHCHm/z=55重排上CH2CH=m/z=41ch26-4共轲，£(a)>db)6-5(a)227nm,(b)237nm,(c)227nm,(d)232nm6-6(a)>(b)6-8(2)(b)>(a)(a)>(b)30003100cm-1C=C-Hv,m28502950cm-1CH3,CH2v,s16201680cm-iC=Cv,mCH 31430cm-19101000cm-1C=CH6-9偶合常数不同，反式偶合常数较大7-97-107-14chch3ch3Er7-16

7、7-17CHaCHaOF7-188-11)1,4-二氯丁烷2)2-甲基-3-氯-6-澳-1,4-己二烯3) (R)-3-甲基-2-氯戊烷4) (S)-1-苯基-1-澳丙烷5) 4-甲基-3-澳苯磺酸6)3-对澳苯-1-丙烯CH3I8-51)(a)(CH3)3CBr>CH3CH2CHBr>CH3CH2CH2CH2Br2)CH3cH2cH2Br>(CH32CHCH2Br>(CH3)3CCH2BrCH3(b)CH3cH2cH2cH2Br>CH3cH2cHBr>(CH3)3cBr8-61)CH3CH2CH2CH2Br反应较快。因甲基支链的空间位阻降低了Sn2反应的速

8、度。2) (CH3)3Br反应较快，为Sn1反应。(CH3)2CHBr首先进行Sn2反应，但因水为8-88-98-108-118-158-179-39-41)2)3)9-51 )、弱的亲核试剂，故反应慢。3) SH-反应快于OH-,因S的亲核性大于O。4) (CH3)2CHCH2Br快，因为Br比Cl易离去。D>C>A>B1) >4)>2)>3),Sn2反应历程A>B>C,Sn1反应历程对于Sn2反应来说，新戊基卤因空间位阻较大，难以进行；对Sn1反应来说，新戊基卤是伯卤烷，Sn1反应困难。ch2=ch-chch3CH2CH-CHCH3CH2=C

9、H-CH=CH2BrBrBrBrABC1) A错，澳应加在第一个碳上。B错，-OH的活泼H会与格式试剂反应。2) B错，叔卤烷遇-CN易消除。3) B错，与苯环相连的澳不活泼，不易水解。CH=CH-CH2CH34)产物为，共轲双烯稳定。3)2)1)加水分层，得有机层异丙触，水层分储得异丙醇加入氧化钙吸水，过滤，蒸储加入氢氧化钠溶液分层，油层为苯甲醛，水层酸化，得苯酚2）、止醇、1,2丙一醇环己烷甲内醒NaH2J无气体放出r无气体放出AH2'正丁醇1,2一丙二醇不变色»正丁醇Pb（OAc）4变色加1,2丙二醇环己烷冷浓硫酸A环己烷甲内髓J不分层E.甲内醍分层3）、卢卡斯试剂，茉

10、醇反应快,苯甲醛和间甲苯酚不反应，加入碱，则间甲苯酚溶于水,苯甲醛不溶。9-7CH3CH2I0CH39-10（A）、（B）、（C）、（D）的构造式分别为：0HOCl66609-11（A）、（B）、（C）的构造式分别为:OCH3OHCH3I9-12A)、(B)的构造式分别为：(B)CH 3CH2CH(CH 3)CH 20H(A)(CH3)2CHCH2CH20H9-13（A）、（B）、（C）的构造式分别为OHOHO(2) CH3-CH=CHt =(4) CH3CH2CH-SO 3Na1OH(6) CH3CH2CH-CH-CHO 11OH CH3(8) CH3cH2cH20H(10) CH3CH-C

11、HO1Br(12) CH3CH2CH=N-OHa -H10-4.(1)CH3CH2CH20H(3)CH3CH2CH2OH(5)CH3CH2CH-CN1OH(7)CH3CH2C+C-CHOCH3O(9)CH3CH2CH；O(11)CH3CH2COOH(13) CH3CH2CH=N-NHC6H510-5.(6)(7)(10)不能反应，10-7.(1) CH3COCHO>CH3CHO>CH3COCH2CH3>(CH3)3CCOC(CH3)3(2) CH3COCCI3>C2H5COCH3(3) CICH2CHO>BrCH2CHO>CH2CHCHO>CH3CH2

12、CHO(4) CF3CHO>CH3CHO>CH3COCHCH2>CH3COCH310-10.共同点：在17001730cm-1左右有厥基的强吸收峰CH=CHCHO不同点：一的红外光谱中在14501650cm-1出现24个苯环的特征峰，同时在3020cm-1以及1660cm-1附近出现烯煌的特征峰。10-11.CH 3cH 2cH 2cH=CCHOCH2CH 3CH 3cH 2cH 2cH=CCH 20HCH2CH3(1)(3)I ' ' -OC2H51./ 、OC2H5(CH3)2C-CHO(CH3”CCH0(CH3)22-CH(OC2H5)2(CH3)2C-

13、CH(OC2H5)29H-0HBrBrMgBrCH(CH3)21)NaOH/EtOH2)B2H6/H2O2QHNNH-C-NH2110(6)(12)CH2CH2CH3(CH3)2CHCHCH3(CH3)2CHCCH3(CH3)2CHCCH 3IIIIOH B：O C：OH10-14 . A:OCH3CH2-C-CHCH3I10-16.CH3OIICH3-C-CH210-17. A:OCH3OCH3-C-CH2C:OHOHICH3CH CH2D:10-18.OCH3 -CCH2cH(OCH3)210-19.1）烯醇式（平面结构）酮式转化。2）格氏试剂的大基团难以接近厥基而夺取厥基“-H形成烯醇结

14、构。3）顺，反异构，R2C=N-OH11-11）丙酸乙酯2）甲酸3）a-氨基己酰胺4）邻氨基苯甲酸甲酯5）B-泰甲酸6）N,N-二乙基丙酰胺7）苯甲酰氯8）邻苯二甲酰亚胺9）2-甲基丁烯二酸酎10)反-2-甲基环己基甲酸11)”-乙基乙酰乙酸乙酯12)2-环己酮基甲酸甲酯13)对乙酰基苯甲酸乙酯14)甲酸节酯OCH2=C_C-OCH3ch3NHCOCH3(6)NH2cOOC2H5OhC.CHNCH，11-2II(8)och3Co(10)(12)CH3OC(11)1COill0+CH2CHbFOh11-3COOCH2CH2OHCoOCH2CH20H(13)OII。_c_CH3COOH(1) CH

15、3CH2C00H>CH3cH2cH2cH20H>ch3cH2cH2cHO>ch3cH20cH2cH3(2) CH3CH2COOH>CH3CONHCH3>CH3COOCH311-4(正)丁酸在水中溶解度大于丙酸甲酯，竣基中氢键作用11-51)竣酸质子氢81013,与-OCH383.54.0很大区别2)谈基特征吸收竣酸的羟基吸收峰更宽，常覆盖C-H伸缩振动3)酸酎的厥基吸收波数更高17507800cm-1,且出现两个峰11-6.(1)甲酸是液体，其余为固体甲酸 乙二酸 丙二酸 丁二酸AgNO3/NH3；：士双酸11-7CH2C1Cl11III(2) CH3CCI>

16、;CH3C-O-CCH3OO> CH3C-OCH2CH3>CH3JNH2-ICO2T丙二酸11-8(1) HCOOCH3>CH3c02cH3>CH3c02c2H5>CH3c02cH(CH3)2>CH3c02c(CH3)3,C02CH3(2) O2NC02cH3>ClC02cH3>C、C02cH3>CH3O_产11-9COClICO2cH2cH3(2)CH3cH2CON(CH3)3_0_O8_CH3Br0CH3(5)H-C-0-LHCH3C2H50I0IIJrCH30OC2H5(6)IO0c2H50OH(7)1rCH2COOC2H5(8)HO

17、CH2CH2CH2CH2CH20H(13)11-10CH3CH2CHC0(10)CH3l|0CCHCH2CH3NH20000(9)OCH3cH2c_CHCOC2H5(11)CN(12)C2H5C2H5O&NHONHO(16)OCH(14)CH3cHCOC2H5C=oCOOC2H5O(15)O.11COOC2H5(1)OOClCH2c_OH>CH3c_OH>CH3CH2OH_O_OO2N_COH>_COHO2N-OH>O>CH3CNH2O>COH节CH20HO>CH3OCOH草酸丙二酸甲酸乙酸苯酚11-11(1)'CH3CII-A1C13

18、CH3OII-COOHBr21COOHIFeIBr(2)CH3Cl2I光”CH2ClCN-分CH2CNH3O+oCH2C-OHMg干醛(CH3)2C=CH2一HBrv.(CH3)2C-CH3Br1)C02(CH3)2CCH3(CH3)3CCOOHMgBr2)H301)NaOC2H500NaBH40H0(4)2CH3CH2CO2CH2CH3CH3CH2CHC+COCH2CH3-CH3cH2cHCH-COCH2cH32)HCH3Ch3HC=CHHCNCH2=CHCNH20,H+CH3OHH+-CH2=CHC00CH3O(6)CH3OH/H+NaBH4HOCO2CH3(8)(9)(10)11-121

19、1-13OA1C13CO2HOOH1HBrCH3CHCH3CH3OOMg/®0HZn/HgHClHCNCHOCH3CH2CH2COOH_Cl2/P(2)OH1)CO22)H3O*CH3OIICH3CHCOOHCH3OHCHCNCH3CH2CHCOOHIClCN-1)C2HgONaCH3COCH2COOC2H525+一OHH2O,HCH3OCHCOOHH2O/H+CH3CH2CHCOOHCOOHCH3COCHCO2C2H5-CH2CH32)C2H5BrOCH3-CHCH210%NaOHHa+OA4-CO1)C2H50NaCH(CO2c2H5)21)C2H5ONa2)CH2cH3BrCH

20、2CH3CH3coec02c2H5CH2CH3CH2(C02c2H5)2一2)BrCH2CHBrCfCH(CO2c2H5)2h3+o-CO2COOHCOOH1)NaOC2H5OCH3c(CH2)3COC2H5514CH2cCH2cH2cH2COC2H5H+OOC2H5-C2H5OH笫环己酮甲酸乙酯含有活泼亚甲基,在碱性条件下与冉伊不饱和酮，先发生1,4加成（Micheal反应），再发生分子内的羟醛缩合,生成环状%3-不饱和酮（Robinsen增环反应）。CO2c2H5NaOC2H5OII-OCOOC2H5NaOC2H5NaOC2H5COOC2H5COOC2H5COOC2H5C2H5OH_C2H

21、5O-OfOO-COOC2H5(3)a-卤代酯在强碱作用下与酯、酮反应生成a吊环氧竣酸酯(Darzen反应)。OIIClCH2cOEtICHCOOEtCHCOOEt11-14CH3CH2OHOgCH3COOHC2H50HACH3c02c2H5Br2/PZn/醛-BrZnCH2COOC2H5H+“-vCH2COOHOHReformastsky 反应CH 2Clch2(co2ch2ch3)21CH3cH2ONa稀 OH-H 3+OA -CO2CH2CH2COOH分析O11CCH 3/.chMchO OII ICH3cCH2COC2H5+BrCH2cH2Br合成CH3CH2OHONaOC2H5BrC

22、H2CH2Br稀OH-O OC2H5OHNaOC2 H5CH3CO2c2H 5CH 3CCH 2coe 2H 5H+C2H50H+OOCH31.H3OOH-12/, co2 CH3C-CH2CH2CH2CH2CCH3OH*'OCCH3 分析：COOC 2H 5CHCH3COOC2H5COOC2H5己二酸COOC 2H 5CO2c2HCO2c2H合成：CO2HCO2HC2H50HH+CO 2c2H 5CO2c2H5NaOC2H5COOC2H5ch2= chCch3C2H50HCOOC2H5/ "IfO OOH-COOC2H5NaOC2H5CH3cH= PPh3COOC2H531

23、1-15A.CH3CH2COOCH2CH3;B.CH3CH2COCH(CH3)COOCH2CH3;C.CH3CH2COC(C2H5)(CH3)COOCH2CH3；D.CH3CH2COCH(CH3)CH2CH3。11-16BrCH 2CH2CH2BJNCCH 2CH 2CH 2CN ,HO2CCH2CH2CO2H ,11-17CH3COCH(CH3)OH。化合物溶在D2O中，一OH的质子被D取代，8=3.75的峰消失。12-3.bp:B>C>A.12-4.A:b>a>cB:b>c>aC:d>a>c>bD:a>b>cE:b>a

24、F:a>b>c>d12-5.HNOHC CHOolc CHO1. OH -:n - BuNH 22. H3O -不能有效的制备Me3CNH2,Me3CCH2NH2,Et2NH，所以此法反应为SN2历程Me3CNH2是叔碳,新戊基位阻大，不利SN2反应历程，Et2NH对消除有利。p-CH3c6H4Br难发生亲核取代，C=CX.12-6.PhSO2NHEtPhSOzNEtNa.PhSO2NEt2ABCPhS020H+Et2NH2DE12-7.A:CH3CH2CH2NH2,B:CH3CH2CH2NHEt,C:CH3cH2cH2MEtEt12-8.A:PhCH=NPh,B:PhCH2

25、NHPh,C:PhSO2NMe2,D:phCH2NHCHOCH3E+F：(CH3)2C=CH2+EtNMe2,G:PhCH2CH2NCH2CH3，CH3+H：PhCH2cH2NCH2CH3OH-,|：PhCH=CH2+NCH2cH3MeMeMeMeJ：1N(Me)2,K：I+N(Me)312-10.H2,Pd/BaSO4NH3C6H13COCI*C6H13CHOaC6H13CH2NH2H2/Pta. C6H13coel+C6H13cH2nh2C6H13CONHCH2c6H13LiAlH4C6H13CH2NHCH2c6H13b. C6H13COCINH3-C6H13CONH2MBr2»

26、C6H13NH2/,NaOHH2/PtC6H13CHO+C6H13NH2C6H13CH2NHC6H1312-11.a.CH3H3PO2CH3b.FeHClCH3HNO3H2SO4NO2CH3ClCH3Cl2FeCH3IClNO2Fe/HClNaNO2HCl”NO2(EtO)2OCH3Cl2水解FeNH2ClNHCOCH3CH3NaNO2H3PO2HClI'(b)ClN2Cl12-12.小混酸JO'n/HCl.NO2(CHS”。鲁3.：.-NO2.I1no2水解NaNO2NaNO2.f*HCl.NaHCO3,Cu2O".INO212-13.a.EtNO2EtSnAc2O

27、HClNH2EtClClCl21.OHFe2.HNO23.CuClb.NH2EtCl2ClEtuhClnh2NaNO2H3PO2HClEtClCl12-14.h2c一ch2NH34h2c一ch2HOCH2cH2NHCH2cH20HP2O512-15.COOHCH3混酸NO2CH3KMnONO2SOCl2Et2NCH2CH2OH12-16.NH2H2so412-18.Ni/H2COOCH2CH2NEt2Et2NHTVO-E2NCH2CH2OHnh2NHSO3HHNO2NNMe2HSO3N二NPH57LN(CH3)2A：NH9卜NHB：NHCOCH3C：NO2OOIIIJII1NHN.HNH2OC

28、OCH3D:CH3CH2CH2COOHE：CH3CH2NH2+HCOOHF:CH3CH2CH2NHCH3G：-COOCH3H+I：CH2CN+AgIJ:不反应AO2NCH3K：-NHfVNO2-12-23.用NaNO2/HCl分别反应，a.在低温时反应可见有氮气放出；b.低温时反应生成重氮盐，加入-蔡酚后得红色偶氮化合物；c.生成黄色对亚硝基N,N-二甲基苯胺盐酸盐，中和后成为绿色固体；d.生成黄色油状物。12-24.解答：加乙酰氯处理，二丁胺生成乙酰化物，可以与三丁胺分离。厂丁rNO"HLUHHO CH2- N= N-OH h j /-11,H2O 1HOCT重排二一飞飞扩坏11二

29、' 112-26.A可与HNO 2发生重氮化反应，故其为芳1所以A为五取代芳伯胺。又根据其1HNMRA xz51 cc-t*HO CH2- N三 NHO CH25、一 N2上 J l1 hOo-JU1 一 ) 、一,'白胺，又它不能发生芳环上的亲电取代反应， 数据推测A的结构为一(二:-NH2。从B的1HHO CH2NH2HO ch2- N-N=OHO CH2- N-N OH12-25.*NMR数据SH7.1(4H)看，B为二取代的芳胺，它不能发生重氮化反应，其不是芳伯胺，再结合1HNMR数据，推测B的结构为:CH3CH3CH 3IAg 2。，H 2Och3ch3CHCH3+

30、+NCH 3CH 3OH-CH3N(CH 3)212-27.1)OH3)OHCH20H0h 0>CH2OHOOh hOHOC2H5OPO3H22)4)OHCOOCH 3OCH2OHOHOHOHOHOHCH3I.Ag2)皿3N+H2/Pt13-1.1)3)HOH2CHOHOOHHOHI2CHOCH 20HOHOHoch3OH2)4)仁。与IICH20HOH HH(Ho2COHI Oj, HH 一 OH13-2.13-3.1)2)3)4)5)HC=NOHH-C-OHOH-C-HH_C-OHH-C-OHCh20HCOOHH-C-OHOH-C-HH-C-OHH-C-OHCh20HCH20H3CH

31、20HH_C-OHOH-&HH-C-OHH-C-OHCh20HC=NNHC6H5C=NNHC6H5OH-C-HH_LOHH-C-OHCh20H13-4.1）甲基葡萄糖甘葡萄糖果糖淀粉淀粉I2不显色甲基葡萄糖甘葡萄糖果糖2)甲基葡萄糖甘葡萄糖果糖菲林试剂葡萄糖果糖,Br2/H20j褪色一L不褪色葡萄糖一果糖无沉淀-甲基葡萄糖甘麦芽糖乳糖蔗糖甘露糖菲林试剂麦芽糖乳糖甘露糖,苯朋姬耿测熔点糖豚确定不同的糖蔗糖13-5.因为酸性条件不能发生差向异构化反应,故不能反应；而碱性条件可以发生差向异构化反应，通过烯二醇结果转化为酮糖（果糖），故可以反应。13-6.无还原性，为糖甘。能被麦芽糖酶水解，故

32、为“一糖甘，因而，其结构为CH20HOCH(CH3)2HOH13-7.CHOHO-C-HH-C-OHCH20H(A)CHOH-C-OHH-C-OHCH20H(B)13-8.HOHhcHOHH2OHCHOHOHHOHC1-4111HHOH(H0HHCNlOHHOH)H20HCH2OH+CNCOOHHOHCH2OH1HO-C-HHO-C-HHOII_HH2O.HOHCHcutHHHOHHOH一OHHOHCNCOOHH-C-OHH-C-OHCH2OHCH20H1)2)HO、.OC，H.,OC，HO.一OCH-C-OHHO-C-HH-C-OH溟水HO-C-H浓HNOH-C-OH3.HO-C-HH-C-OHH-C-OHH-C-OHH-C-OHCOOHH-C-OHCh2ohH-C-OHCH2OH3)4)HOCOO-OHOHOHCH20HCH20HC=OHO-C-HH-C-OHH-C-OHCH2OHCa2+COOHC=OCHOHOHHOHH2O2,Fe3+H0CH2OH-C02HOOHOHCH2OHCH20HCH2OH1H-C-OHHO-C-H1HO-C-HHO-C-H1Na-Hg-H-C-OH+H-C-OH1H2H-C-OHH-C-OH1CH2OHCH2OH13-9.CHOH-C-OHH-C-OHH-