北京化工大学：《有机化学》课程教学资源（试卷习题）习题3（答案）

第3章有机化合物的构造、构型和构象 3-1 (CH3CH2CH2CH2CH2CI CH3CH2CH2CHCH3 CH3CH2CHCH2CH (2)CH2=CHCH2CH2CI CH2=CHCHCH3 CH2=CCH2CH3 CH=CHCH2CH3 (6) CH,CI CH C-CH ◇CH CH.CHCICHCHCHCHCHS CCH.CH (s)CH3CHCH2CHCH2CHCH2CI CH:CHCH2CHCH2CCHs CH3CH3CH3 CH3 CH3 CH3 C CH3CHCH2CHCHCHCH3 CH3CHCH2CCH2CHCH3 CH3 CH3 CH3 CH3 CH3 CH3 CH;CHCH2CHCH2CHCH3 CH3 CH2CI CH3 行黄简并构，浪紧子农置的 Br CHa CH3 CH3CH2CH2CH2Br CH3CH2CHCH3 CH:CHCH2Br CH3CCHs Br (2)直链烯（双键位置异构，碳链异构），环烷 CH2=CHCH2CH2CH3 CH3CH=CHCH2CH3 cH,H CH2-CHCHCH cH,c思， Q口 v以F

1
3     3-1 (1 ) CH3CH2CH2CH2CH2Cl CH3CH2CH2CHCH3 Cl CH3CH2CHCH2CH3 Cl (2) CH2=CHCH2CH2Cl CH2=CHCHCH3 Cl CH2=CCH2CH3 Cl Cl CH=CHCH2CH3 (3 ) CH2Cl CH3 Cl Cl CH3 CH3 Cl (4) CH2CH2Cl CHCH3 Cl CH2CH3 Cl CH2CH3 Cl CH2CH3 Cl (5 ) CH3CHCH2CHCH2CHCH2Cl CH3 CH3 CH3 CH3 CH3 CH3 CH3CHCH2CHCH2CCH3 Cl CH3 CH3 CH3 CH3 CH3 CH3 CH3CHCH2CHCHCHCH3 Cl CH3CHCH2CCH2CHCH3 Cl CH3CHCH2CHCH2CHCH3 CH3 CH2Cl CH3 3
2     CH3CH2CH2CH2Br CH3CH2CHCH3 Br Br CH3CHCH2Br CH3 CH3CCH3 CH3    CH2=CHCH2CH2CH3 CH3CH=CHCH2CH3 CH3CH=CCH3 CH3 CH3 CH2=CHCHCH3 CH3 CH3CH2C=CH2

(3)醇异构（羟基位置异构，碳链异构），醚异构 CH3 CH3 CHCH-CH-CHOH CH CH-CHCH3 CH CHCH,OH CH3CCH3 OH OH CH:CH2OCH2CH3 CH;OCH2CH2CH3 CHOCH(CH3)2 (④醛、酮，直链烯醇，环醚异构 OH CH2=CHCHCH3 CH3CH=CHCH2OH CH2=CCH2OH ◇-oH △ 9。 (⑤)羧酸异构，酯异构 0 CH3CH2CH2COOH CH3CHCOOH CH3CH2COCH3 CH:COCH2CH3 0 HCOCH2CH2CH3 HCOCH-CHs CH3 (⑥)芳烃（丙基，异丙基，乙基和甲基（邻间对），三个甲基) CH3 CH3 CH2CH2CH3CH(CH3)2C2Hs C2Hs CH3 CH3 CH3C2Hs O一CH CH3 3-3 )无 (2)无 (3)无 ④有 H

2    CH3 CH3CH2CH2CH2OH CH3CH2CHCH3 CH3CHCH2OH CH3CCH3 CH3CH2OCH2CH3 CH3OCH2CH2CH3 CH3OCH(CH3 )2 OH OH CH3  OH CH3 CH3CH2CH2CH CH3CH2CCH3 CH2=CHCH2CH2OH CH3CH=CHCH2OH CH2=CCH2OH O O CH2=CHCHCH3 OH OH OH OH O O O O O CH3 CHCHO CH3 O !"# CH3CH2CH2COOH CH3CHCOOH CH3CH2COCH3 CH3COCH2CH3 O O HCOCH2CH2CH3 O HCOCH O CH3 CH3 $%&''()*+,-./* CH2CH2CH3 CH3 C2H5 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 C2H5 CH(CH3 )2 CH3 C2H5 3
3 0  0  0  1 Cl H Cl Cl H H H Cl

(5)有 6)HC大CCH *CH3 CH3 、 CH3 H 3-4 1) H CH2=CH-CH3 CH2=CH-CH3 (R)-3-氯-1-丁烯 (S)一3-氯-1-丁烯 (2) H(CH3)2 H C=C C2Hs H C2Hs CH(CH3)2 (Z)或顺式 (E成反式 (3) c-CCH3 Br (E)或顺式 (R或反式 (4)2一甲基一1,4-一二氯一1一戊烯 H CH3 CH (Z.R) H H H -CH ci- CH3 CH3 (E.R) (E,S)

3 1 CH3 C=C H C=C H C=C H C=C H CH3 CH3 CH3 H H H H H H H H H H H H CH3 CH3 CH3 CH3 CH3 H3C CH3 (6 ) CH3 CH3 H H H CH3 CH3 CH3 H H H CH3 CH3 CH3 H H H CH3 CH3 CH3 H H H CH3 3
4 (1) CH3 H H CH2=CH Cl Cl CH3 CH2=CH 2
3
4
5
6 7
3
4
5
6 8 C=C H H C2H5 CH(CH3 )2 C=C H H C2H5 CH(CH3 )2 ( Z) ￾✂✁☎✄ ( E)￾✝✆✞✄ 3 Br CH3 C=C H (E) ( R) ✟✂✠☎✡ ✟✝☛✞✡ CH3 Br CH3 C=C H CH3 (4) 2
*
14
94
1
: H H C Cl l CH3 H C=C Cl Cl H CH2 CH3 CH3 H Cl C=C Cl H CH2 CH3 CH3 H C=C Cl CH2 CH3 CH3 H Cl C=C CH2 CH3 ( Z,R) (Z,S) (E,R) (E,S)

(⑤)35-二甲基环己烯 CH3 CH3 HH 顺式(3S,5R)(3R,5S) 反式(3S,sS (R.sR) (6)1一甲基一3一氯-5一溴环己烷 CH Br Br (R.3S.sR)(1S.3R.sS) (iR.3S.sS)(iS.aRsR) 山 (R,3R.sR)(S,3S,sS) (S,3S,sR)(R,3R,5S) 3-5 )CH,CHDC,Hs (CHCHC.Hs ()s无(4)无 CI (s)CH;CHCH(CH3)2 Ch,-CC-CHC o李6a (s) ★CHO 3-6 (1)R(2)S(3)R(4)R(⑤)S (6)R (7)2R,3R(8)2S.3R(9)2S,3R0m1S,2RqD2S.3R(内消旋体)22S,3S,4R 3-7 COOH OH (1)H- 一OH (H2NH2C- -CH2OH

4 (5) 3,5-9*; CH3 CH3 H H H H H H CH3 CH3 CH3 H H CH3 CH3 CH3
3S,5R) ( 3R, 5S) 3S,5S) (3R,5R) 6 1
*
3
4
5
; H H H Br Cl CH3 CH3 H H Cl Br H H H H Br Cl CH3 CH3 H H Cl Br H ☞ 1R,3S,5R) ☞ 1S,3R,5S) ☞ 1R,3S,5S) ☞ 1S,3R,5R) H H H ClBr CH3 CH3 H H Cl Br H H H H Br Cl CH3 CH3 H H Cl Br H ✌ 1R,3R,5R) ✌ 1S,3S,5S) ✌ 1S,3S,5R) ✌ 1R,3R,5S) 3-5 Cl (1 ) CH3CHDC2H5 (2 ) CH3CHC2H5 (3 )
4
CH3 CH3 Br CH3CHCH(CH3)2 (5) (6) CH2=CHCHCH=CHCH3 (7) Cl OH (8) CHO 3
6 R  S  R  R S $ R 2S,3R ? 1S,2R @ 2S,3R(ABCD) E 2S,3S,4R 3-7 COOH CH3 (1) H OH (2 ) OH H2NH2C CH2OH H

C2Hs () CH2=CH- -CH2C=CH >=0 CN (s)C4 -H 一 CH CH 38 C三CH HO -CH=CHCH CH2OH CHCH3 H、 H CH2OH ()原式等于CH2OH一 H HO- 下Br H (s) CH3 CH3 OH H R OH (④)原式等于HO一S C..-H CH3 CH3 H SOH CHa COOH CHO (6) CH3 H HO RC--H NH CH2OH CH D ) C-H HOCH - CHCH \CHCH H H

5 CH2=CH CH2C CH C2H5 H (3) (4) O H CN H H CH3 Cl C2H5 C2H5 (5) (6 ) Br H C2H5 H (7 ) H CH3 H CH3 (R) (S) (8 ) CH3 H H CH3 3-8 HO H CH3 CH2OH (1 ) (2) CH=CHCH3 C CH CH2CH3 CH3 R S (3 )
 ✍ Br C H C OH H CH3 (s) (s) Br HO H CH2OH CH3 H S S (4 )   C H CH3 C CH3 OH H OH OH CH3 CH3 H H R S (5) C H COOH NH2 CH3 (6 ) C H CHO CH2OH HO S R (7) C CH3 H Cl C H Br CH2OH (8 ) C C CH3 CH3 Br D CH2CH3 H C C Cl CH3 H Br HOCH2 H R S S

3-9 CH2Br H -CH3 一Br CH3 (2R.3S) (2S.3S),(3R3R),(2S,3R) 3-10 C(CH3)3 C(CH3)3 C(CH3)3 H CH3 CH3 CH H H CH2 CH 一H H一 CH3 C(CH3)3 C(CH3)3 C(CH3)3 (3S4S (3R.4R) (内消旋体) (构象能量图与正丁烷相似) C(CH3)3 C(CH)3 C(CH3)3 CH3 CH3 人cH CH3C(CH3)3 H C(CH3)3 3-11 (1)不正确消旋体分子内也有手性碳原子，但分子不旋光。 (2)不正确丙二烯分子有的有旋光，但却不含手性碳。 (3)不正确R/S命名与与（±）无关，没有对应关系。 3-12 对映体(1)，(3)，（⑤），(8) 非对映体(6)，(7)，G0 同一化合物(2)，(4)，（⑨） 3-13 相同(2，(3)，(4)，（⑤，（， 对映体() 3-14 设R构型的摩尔分数为X,S构型的摩尔分数为(1-X) X*(-13.52)+(1-X0(+13.52)=6.72 X=75% (1-X)=25% 6

6 3-9 CH3 Br CH2Br CH3 H H (2R,3S) (2S,3S) , (3R,3R) , (2S,3R) 3-10 C(CH3)3 H CH3 C(CH3)3 H CH3 C(CH3)3 CH3 C(CH3)3 H CH3 H (

  C(CH3 )3 C(CH3 )3 CH3 H H CH3 (3S,4S) (3R,4R) CH3 CH3 CH3 CH3 C(CH3 )3 C(CH3)3 C(CH3)3 H C(CH3 )3 C(CH3 )3 C(CH3 )3 H H H H CH3 H CH3 3-11 (1)
  
 (2)

  (3)
R/S   !"# $ 3%12 "& '()* ,"& -./ 01234 56 78 9: 3%13 ;0 5(?@ABCD EF?@ABCDGHE EI6 HGJK LM8 N6 GHE8 6 NGJK LM8 OHPK QM EOQLR (1-X)=25%

3-15 (0②)3)0同)（⊙（①8） 手性碳数212334 03 异构体数438 48 0 注意：解此类型体要考虑分子是否有对称面或对称中心，有多少个手性碳原子， 有没有桥头碳原子的影响，有没有顺反异构体等因素。在(5)，(6)这类桥环化合 物中，如两个桥头碳原子均为手性，计算异构体时只按一个计。 3-16 整个分子无旋光性，是因为通过C及C上的H和Br三原子所在的平面， C和C,的构型互为镜像，所以C有称为假不对称碳原子。 CH3 C -CI CL H CHBr CHBr H CI CHH HBr BrH H CH3 (2R,3R) S,3S) (2R,3,4S) (2R,3s,4S A B 0 在A,B中，C3因为所连接的C,和C均是相同的，故分子中只有C,和 C,两个不对称碳原子。 3-17 无对映体(1)(3)（⑤）(6) 有对映体(2)(4) 3-18 CH

7 3%15 ✎ ✏ ✑ ✒ ✓ ✔ ✕ ✖ ✗✙✘✛✚✢✜ 2 1 2 3 3 4 0 3 ✣✢✤✢✥✛✜ 4 3 8 4 8 1 0 8 STUVWX@YZ[\]"^_`"^abcde  !fghi!jkl?mnop5,(6)qXfr23 4astefguD vwl?xyz1ev 3%16 {e \nD|}~✦ ~✦ € ‚ƒ„…†p‡_ ~✧ ‚~★ ?@ˆD‰Š†‹ ~✦ ^DŒ
"^ CH3 CHBr CH3 H H CH3 H H H H Br Br H Cl Cl Cl CH3 CH3 Cl CH3 CH3 CH3 Cl Cl Cl Cl H H H CHBr ( ) ( ) ( ) ( ) 2R , 3R 2S , 3S 2R ,3 r, 4S 2R , 3s ,4S A B C D p A,B aC3 nD†Ž ~✧ ‚~★ u\;0ay~✧ ‚ ~★ te
"^ 3%17 "& ' ( ) - "& 5 < 3%18
1 Cl H OH CH3 Br Br Br Br H H H H Br H H Br (2 ) (3 ) CH3 OH (4 ) Ph Ph Cl H H H

3-19 在2一氯代环已烷中有两个手性碳原子，应有2”=4个异构体 年年 在3一氯代环己烷中有两个手性碳原子，应有2=4个异构体 子君 在4一氯代环己烷中的顺式或反式构型中都有一个对称面 顺式 3-20 CH C(CH3)

8 3%19 p 2%‘r’ate # 2 2 =4 el? OH H Cl OH H H H Cl OH H Cl OH H H Cl p 3%‘r’ate # 2 2 =4 el? OH H Cl OH H H Cl OH H Cl OH H H Cl H H p 4%‘r’aj`k?@a•1e"^_ OH OH Cl Cl H H H
3-20 (1 ) Br H Cl H (2) H Br (CH3 )3C H Br H Cl ✩✂✪ H (CH3)3C H H Br ✩✂✪ ✫✝✪ ✫✝✪ C(CH3)3 (3 ) (4) Br H CH3 H CH3 H H CH3 H H CH3

CH3 (5) H CHCH2CH (6) (CH3)3G CH3 CH3 C(CH3)3 H H C(CH3)3 () (8) (9) C(CH3)3 3-21 CH.CHCH.CH-CHs CHCHCH(CH3)2 C2Hs C2Hs CH2CH3 CH2CH3 H CH3 H CH3 CH2CH2CH3 CH2CH2CH3 CH2CH3 CH2CH3 H CH3 H CH3 CH(CH3)2 CH(CH3)2 3-22 QH 或 QH CH; H H H CH3 CH3 9

9 (5 ) CH3CH2C H2 CH3 (6) H CH3 H CH3 (CH3)3C H H H H (7 ) (8) H C(CH3 )3 H H C(CH3 )3 (9 ) C(CH3 )3 H H H 3-21 CH3CHCH2CH2CH3 C2H5 CH3CHCH(CH3)2 C2H5 CH2CH3 CH3 CH2CH2CH3 H CH2CH3 CH3 CH2CH2CH3 H CH2CH3 CH3 CH(CH3 )2 H CH2CH3 CH3 CH(CH3)2 H 3-22 H H H OH CH3 CH3 H OH CH3 H H CH3