[材料科學(xué)與工程][有機(jī)化學(xué)][第3章有機(jī)化合物的構(gòu)造構(gòu)型和構(gòu)象1][孫芳]

1、同 分 異 構(gòu)構(gòu) 造 異 構(gòu) 立 體 異 構(gòu)碳鏈（ 骨架 ）異構(gòu)官能團(tuán)位置異構(gòu)官能團(tuán)異構(gòu)互變異構(gòu)構(gòu) 象異 構(gòu)構(gòu) 型異 構(gòu)順反異構(gòu)光學(xué)異構(gòu)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構(gòu)型構(gòu)型CCAABBCCABBACCCCHCH3CH3HCH3CH3HHb p ( )mp ( )41- 1 3 9- 1 0 5CCCCHCH3CH3HCH3CH3HHbp( )mp( )41- 139- 105HCOOHHOOCH井岡山風(fēng)景桂林風(fēng)情生活中的對映體生活中的對映體鏡象鏡象左右手互為鏡象左右手互為鏡象生活中的對映體生活中的對映體鏡象鏡象CCHClClHCClClHCH3COOHHOHHOHCOOHHFHClClHHFCH2CH2CH2CH2ClClNHHH C3CH3CH3C2CH3CH3HHHHC2COOHCOOHHOHHOHC2（無

4、） （有） （無） （有）化學(xué)性質(zhì)：僅在手性環(huán)境下表現(xiàn)出差別化學(xué)性質(zhì)：僅在手性環(huán)境下表現(xiàn)出差別 旋光性：對偏振光的作用不同旋光性：對偏振光的作用不同 同 分 異 構(gòu)構(gòu) 造 異 構(gòu) 立 體 異 構(gòu)碳鏈（ 骨架 ）異構(gòu)官能團(tuán)位置異構(gòu)官能團(tuán)異構(gòu)互變異構(gòu)構(gòu) 象異 構(gòu)構(gòu) 型異 構(gòu)順反異構(gòu)光學(xué)異構(gòu)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）交叉點 手性碳（位于紙平面上）投影式的轉(zhuǎn)換規(guī)則投影式的轉(zhuǎn)換規(guī)則v 不能離開紙面翻轉(zhuǎn)。翻轉(zhuǎn)不能離開紙面翻轉(zhuǎn)。翻轉(zhuǎn)180。，變成其對映體。，變成其對映體。v 在紙面上轉(zhuǎn)動在紙面上轉(zhuǎn)動9

7、0。, 270 。，變成其對映體。，變成其對映體。v 在紙面上轉(zhuǎn)動在紙面上轉(zhuǎn)動180。構(gòu)型不變。構(gòu)型不變。v 保持保持1個基團(tuán)固定，而把其它三個基團(tuán)順時針或個基團(tuán)固定，而把其它三個基團(tuán)順時針或逆時針地調(diào)換位置，構(gòu)型不變。逆時針地調(diào)換位置，構(gòu)型不變。v 任意兩個基團(tuán)調(diào)換偶數(shù)次，構(gòu)型不變。任意兩個基團(tuán)調(diào)換偶數(shù)次，構(gòu)型不變。6. 任意兩個基團(tuán)調(diào)換奇數(shù)次，構(gòu)型改變。任意兩個基團(tuán)調(diào)換奇數(shù)次，構(gòu)型改變。COHHOOCCH3HCCOOHCH3OHHCCOOHHOCH3HCCOOHCH3HOH(S)- (S)- (R)- (R)-基團(tuán)大小順序：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）HHCH3ClHCOOHHHOOCNO2HOOCCOOHO2NO2NHOOCCOOHNO2O2NHOOCClClOHOHN+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 O HH O O C HH COOHHOOC HH COOHHOOC HHCOOHHOOCH1，2

11、順式內(nèi)消旋反式外消旋1，2反 式外 消 旋順 式內(nèi) 消 旋反 式1， 21， 21， 3順 式1， 31，2 順式內(nèi)消旋1，3 順式內(nèi)消旋反式外消旋1，2反式外消旋1，31，2 順式內(nèi)消旋反式外消旋1，2反式外消旋1，31，3 順式內(nèi)消旋反式1，4順式1，4 （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 H（1） C lO HHC H3B rB rB rB rHHHHB r

12、HHB r(2)(3)C H3O H(4)P hP hC lHH H123456123456CH2231564CH2CH2CH2231564TC = twist chairB = boatTB = twist boatC = chairTC = twist chairB = boatTB = twist boatC = chair123456654321531246612345123456CH2HRCH2HR123456CH2CH2234561 R 鍵（）鍵（） -CH3 95 -CH(CH3)2 97 -C(CH3)3 99.99 212121122121211，3 順式內(nèi)消旋反式外消旋1，

13、331313131反式1，4順式1，41212121212121212CH3CH(CH3)2213131313131313131ClBr(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 )(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 H

14、3O 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 ) 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

15、lHC lH( 5 )CH3CH3BrHOHHHBrHOHHH(6) CCHOCH3HHCH3OHCCCH3OHHOHHCH3(7) CH3CH3NH2HOHHNH2HHH3COHH3C(8) HCH3CH3HCH3HHCH3(9) CH3CH3CH3CH3(10) ClClHHClHClH(5)CH3CH3BrHOHHHBrHOHHH(6) CCHOCH3HHCH3OHCCCH3OHHOHHCH3(7) CH3CH3NH2HOHHNH2HHH3COHH3C(8) HCH3CH3HCH3HHCH3(9) CH3CH3CH3CH3(10) ClClHHClHClH(5)(1) COOHCOOHB

16、r(2) NO2COOHNO2HOOC(3) CH3CHCC(CH3)2(4) C6H5CHCCHC6H5(5) O(6) CH3CH3CHCH3 CH3CHBrCH3HHCH3HHHHH Br BrClClClCH3CH3Cl CH3 CH3 CH3ClClClClHHHCHBr ( ) ( ) ( ) ( ) 2R3R,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 r

17、37HHC lO H8HC H31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHBr37HHClOH8HCH31CH ClClCHH232OHBrHCH33HHHClClCl4(CH ) CHCCHHCHCH23 25HCHCHHClCl336CH SHHHClCHB