[材料科学与工程][有机化学][第3章有机化合物的构造构型和构象2][孙芳]

1、同 分 异 构构 造 异 构 立 体 异 构碳链（ 骨架 ）异构官能团位置异构官能团异构互变异构构 象异 构构 型异 构顺反异构光学异构CH3CH2CH2CH3CH3CHCH3CH3CH3CH3CH3CHOCHOCH3CH2CH2CH3CH3CHCH3CH3CH3CH3CH3CHOCHOCH3CH2CH2CH3CH3CHCH3CH3CH3CH3CH3CHOCHOC H3C H3C H3C H3B rC O O HB rC O O HOOC H3C H3C H3C H3B rC O O HB rC O O HOOC H3C H3C H3C H3B rC O O HB rC O O HOOCH3O

2、CH3CH3CH2OHCH3CH2CHOCH3COCH3CH3CH2COOHCH3COOCH3CH3COClClCH2CHOCH3OCH3CH3CH2OHCH3CH2CHOCH3COCH3CH3CH2COOHCH3COOCH3CH3COClClCH2CHOCH3OCH3CH3CH2OHCH3CH2CHOCH3COCH3CH3CH2COOHCH3COOCH3CH3COClClCH2CHOCH3OCH3CH3CH2OHCH3CH2CHOCH3COCH3CH3CH2COOHCH3COOCH3CH3COClClCH2CHOCH3CCH2COOEtOCH3CCCOOEtOHHCH3CCH2CCH3OOC

3、H3CCCOCH3OHH酮式烯醇式酮式烯醇式构型构型CCAABBCCABBACCCCHCH3CH3HCH3CH3HHb p ( )mp ( )41- 1 3 9- 1 0 5CCCCHCH3CH3HCH3CH3HHbp( )mp( )41- 139- 105HCOOHHOOCH井冈山风景桂林风情生活中的对映体生活中的对映体镜象镜象左右手互为镜象左右手互为镜象生活中的对映体生活中的对映体镜象镜象CCHClClHCClClHCH3COOHHOHHOHCOOHHFHClClHHFCH2CH2CH2CH2ClClNHHH C3CH3CH3C2CH3CH3HHHHC2COOHCOOHHOHHOHC2（无

4、） （有） （无） （有）化学性质：仅在手性环境下表现出差别化学性质：仅在手性环境下表现出差别 旋光性：对偏振光的作用不同旋光性：对偏振光的作用不同 同 分 异 构构 造 异 构 立 体 异 构碳链（ 骨架 ）异构官能团位置异构官能团异构互变异构构 象异 构构 型异 构顺反异构光学异构CH3CH2CH2CH3CH3CHCH3CH3CH3CH3CH3CHOCHOC H3C H3C H3C H3B rC O O HB rC O O HOOCH3OCH3CH3CH2OHCH3CH2CHOCH3COCH3CH3CH2COOHCH3COOCH3CH3COClClCH2CHOC H3C C H2C O O

5、 E tOC H3CC C O O E tO HHC H3C C H2C C H3OOC H3CC C O C H3O HH酮式烯醇式酮式烯醇式CH3CH3CH3CH3BrCOOHBrCOOHOOHCOOHHOOCHCCAABBCCABBACO HH O O CC H3HCC O O HC H3O HHCC O O HH OC H3HCC O O HC H3H OH( S ) - ( S ) - ( R ) - ( R ) -CO HH O O CC H3HCC O O HC H3O HHCC O O HH OC H3HCC O O HC H3H OH( S ) - ( S ) - ( R )

6、 - ( R ) -CC O O HC H3O HHCC O O HC H3H OHS -(+ )-乳 酸R -(-)-乳 酸CC O O HC H3O HHCC O O HC H3H OHS -(+ )-乳 酸R -(-)-乳 酸H COOHHOOC HHCOOHHOOCHHC O O HH O O CHH COOHHOOC HCCOOHH3CHOHCCOOHCH3HHOHOHCOOHCH3（前）（前）（后）（后）交叉点 手性碳（位于纸平面上）投影式的转换规则投影式的转换规则v 不能离开纸面翻转。翻转不能离开纸面翻转。翻转180。，变成其对映体。，变成其对映体。v 在纸面上转动在纸面上转动9

7、0。, 270 。，变成其对映体。，变成其对映体。v 在纸面上转动在纸面上转动180。构型不变。构型不变。v 保持保持1个基团固定，而把其它三个基团顺时针或个基团固定，而把其它三个基团顺时针或逆时针地调换位置，构型不变。逆时针地调换位置，构型不变。v 任意两个基团调换偶数次，构型不变。任意两个基团调换偶数次，构型不变。6. 任意两个基团调换奇数次，构型改变。任意两个基团调换奇数次，构型改变。COHHOOCCH3HCCOOHCH3OHHCCOOHHOCH3HCCOOHCH3HOH(S)- (S)- (R)- (R)-基团大小顺序：OH COOH CH3 H SCH3CHOCH2CH3HCH3CH

8、OCH2CH3HCCH2CH3HOCH3H SRRC H3C H C O O HO H*CN H2C O O HHC H3C H C O O HO H*CN H2C O O HHCCOOHCH3OHHCCOOHCH3HOHS-(+)-乳酸R-(-)-乳酸 D D2020= +3.8= +3.8o o( (水水) ) D D2020= -3.8= -3.8o o( (水水) )HOOC-CH-CH-COOH*OH ClC-2: -OH CHCOOH COOH HC-3: Cl COOH CHCOOH HClOHHOHClHCOOHCOOHCOOHHOHHClCOOHHOHHClCOOHCOOHH

9、OHClHCOOHCOOH 2R3R 2S3S 2R3S 2S3R dl-dl-HOHClHCOOHCOOHCOOHHOHHClCOOHHOHHClCOOHCOOHHOHClHCOOHCOOH 2R3R 2S3S 2R3S 2S3R dl-dl-HOOC-CH-CH-COOHOHOH* 酒石酸 OH COOH CHCOOH HOH *C2 *C3 ：HOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHHOHHOHCOOHCOOHCCCABABsp2sp

10、C=C=CClHClH（有手性）HHCH3ClHCOOHHHOOCHCOOHHOOCHCOOHHHHOOC螺环型和环与双键相连的化合物。螺环型和环与双键相连的化合物。NO2HOOCCOOHO2NO2NHOOCCOOHNO2O2NHOOCClClOHOHN+C6H5 O H-C H3C H3C H2C H2C6H5P+C6H5C H2C H2C H3C H3 B r-C H2C6H5HCOOHHOOCHH C O O HH O O C HH C O O HH O O C HH COOHHOOC HH COOHHOOC HHCOOHHOOCHHCOOHHOOCHH COOHHOOC HH C O

11、O HH O O C HH COOHHOOC HH COOHHOOC HHCOOHHOOCH1，2 顺式内消旋反式外消旋1，2写写单环化合物的立体异构体单环化合物的立体异构体时，可将环看作平面来对待，思时，可将环看作平面来对待，思路：路：先顺反先顺反后判断后判断再照镜再照镜BrClClBr顺顺RSRSRSBrClClBr反反RSBrCl当两个取代基不同时：当两个取代基不同时：反 式外 消 旋顺 式内 消 旋反 式1， 21， 21， 3顺 式1， 3BrClRSClBrClSRBrRSClClSRBrBr1，2 顺式内消旋1，3 顺式内消旋反式外消旋1，2反式外消旋1，31，2 顺式内消旋反式

12、外消旋1，2反式外消旋1，31，3 顺式内消旋反式1，4顺式1，4CC O O HC H3O HHCC O O HC H3H OHS -(+ )-乳 酸R -(-)-乳 酸CC O O HC H3O HHCC O O HC H3H OHS -(+ )-乳 酸R -(-)-乳 酸H COOHHOOC HHCOOHHOOCHHC O O HH O O CHH COOHHOOC HCOHHOOCCH3HCCOOHCH3OHHCCOOHHOCH3HCCOOHCH3HOH(S)- (S)- (R)- (R)-基团大小顺序：OH COOH CH3 H S （1） C lO HHC H3B rB rB rB

13、 rHHHHB rHHB r(2)(3)C H3O H(4)P hP hC lHH H（1） C lO HHC H3B rB rB rB rHHHHB rHHB r(2)(3)C H3O H(4)P hP hC lHH H（1） C lO HHC H3B rB rB rB rHHHHB rHHB r(2)(3)C H3O H(4)P hP hC lHH H123456123456CH2231564CH2CH2CH2231564TC = twist chairB = boatTB = twist boatC = chairTC = twist chairB = boatTB = twist bo

14、atC = chair123456654321531246612345123456CH2HRCH2HR123456CH2CH2234561 R 键（）键（） -CH3 95 -CH(CH3)2 97 -C(CH3)3 99.99 1，3 顺式内消旋反式外消旋1，3反式1，4顺式1，412121212CH3CH(CH3)21212121212CH3CH(CH3)22131313131ClBr31313131ClBr(1 ) C lC l(2 ) C H3C HC HC HC HC H3C H2(3 ) C lC l(4 ) C H OH OC H3C H3OC H3HC l(5 )(6 )(7

15、)(8 )薄 荷 醇CC H3C H3CCCCC H3C H3HHO HHO HCH3HCH3OHOHHHCH3HOHOHCH3HCH3HOHOHCH3(A)(B)(C)C H3C H3B rHO HHHB rHO HHH( 6 ) CCH OC H3HHC H3O HCCC H3O HH OHHC H3( 7 ) C H3C H3N H2HO HHN H2HHH3CO HH3C( 8 ) HC H3C H3HC H3HHC H3( 9 ) C H3C H3C H3C H3( 1 0 ) C lC lHHC lHC lH( 5 )C H3C H3B rHO HHHB rHO HHH( 6 )

16、CCH OC H3HHC H3O HCCC H3O HH OHHC H3( 7 ) C H3C H3N H2HO HHN H2HHH3CO HH3C( 8 ) HC H3C H3HC H3HHC H3( 9 ) C H3C H3C H3C H3( 1 0 ) C lC lHHC lHC lH( 5 )CH3CH3BrHOHHHBrHOHHH(6) CCHOCH3HHCH3OHCCCH3OHHOHHCH3(7) CH3CH3NH2HOHHNH2HHH3COHH3C(8) HCH3CH3HCH3HHCH3(9) CH3CH3CH3CH3(10) ClClHHClHClH(5)CH3CH3BrHOH

17、HHBrHOHHH(6) CCHOCH3HHCH3OHCCCH3OHHOHHCH3(7) CH3CH3NH2HOHHNH2HHH3COHH3C(8) HCH3CH3HCH3HHCH3(9) CH3CH3CH3CH3(10) ClClHHClHClH(5)(1) COOHCOOHBr(2) NO2COOHNO2HOOC(3) CH3CHCC(CH3)2(4) C6H5CHCCHC6H5(5) O(6) CH3CH3CHCH3 CH3CHBrCH3HHCH3HHHHH Br BrClClClCH3CH3Cl CH3 CH3 CH3ClClClClHHHCHBr ( ) ( ) ( ) ( ) 2R

18、3R,2S , 3S2R ,3r, 4S2R , 3s ,4SA B C D1C H C lC lC HH232O HB rHC H33HHHC lC lC l4(C H ) C HCCHHCHC H23 25HC HC HHC lC l336C H S HHHC lC HB r37HHC lO H8HC H31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCH