章羧酸和取代羧酸PPT学习教案

1、会计学1 章羧酸和取代羧酸章羧酸和取代羧酸 第1页/共46页 第2页/共46页 H3C H C Cl C O OH H3C H C NH2 H2 C 41 3 C O OH 2 3 2 1 common name: 2-chloropropanoic acid IUPAC name: -chloropropionic acid common name:-aminobutyric acid 3-aminobutanoic acidIUPAC name: 第3页/共46页 two carboxy group HO C O C O OHHO C O H2 C C O OH oxalic acid m

2、alonic acid aromatic caroxylic acid COOH COOH COOH COOH O2N COOH OH phthatic acid benzoic acid 4-nitrobenzoic acid p-nitrobenzoic acid 2-hydroxybenzoic acid salicylic acid 第4页/共46页 C C H HOOC H COOH CH3CHCH2COOH OH CC O H3C O OH CC H H COOH CH3CO- acetyl group ArCO- benzoyl group RCO- acyl group HCO

3、- formyl group cis-butenedioic acid3-hydroxybutanoic acid trans-phenyl-propenoic acid pyruvic acid 2-oxopropanoic acid 第5页/共46页 第6页/共46页 第7页/共46页 Resonance theory C O R OH H2OC O R OH C O R O C O R O H3O (1) (4) (3) (2) carboxylate anion + + phenol H2CO3 RCOOH (CH3)2CH CH3CH2 CH3H -I: NO2 CN F Cl Br

4、 I C=C OCH3 C6H5 CH=CH2 H 周期表中位置、基团结构 -I: F Cl Br I -OR -SR F OH NH2 CH3 -I: -C=CR-CR=CR2-CR2-CR3 R=H , 烃基 -I:-NR3-N O R SR O O +I:-O-S COO C O H2C OH OH C O H3CCH2C OH O C O H2C OH COO C O H2C OH N(CH3)3 pKa3.833.58 1.83 pKa1 5.85 第11页/共46页 -C: -NO2, -CN, -COOH, -CHO, -COR etc +C: -NH2, -NHR, -OH,

5、-OR, -OCOR, -Cl, Br etc para- COOH COOH NO2 COOH OCH3 -C+C pKa 4.173.44.47 meta- COOH COOHCOOH -I-I NO2 OCH3 pKa 4.173.494.09 第12页/共46页 ortho - （ortho effect） -NH2 酸性降低 -CH3, X, OH, NO2, OCH3 酸性增加 COOH COOH COOH H3C CH3 C(CH3)3 CH3 COOH Cl pKa3.213.46 3.912.89 hydrogen bond COOH CCOOH NO2 COOH O OH

6、NO2 NO2 pKa 4.172.213.463.40 field effect C O O C H2 CO HO 6.07 Cl Cl H H HO O H H Cl Cl OH O pKa 5.69 第13页/共46页 COH O H R halogenated reaction reduction salt formation decarboxylation replacement 第14页/共46页 NaOHCOH O R H2OCONa O R acid + salt base + （一）Salt Formation OH NaHCO3/ether COH O R COH O R

7、CONa O R OH H water phase ether phase 第15页/共46页 acyl halidesestersanhydrides amides 1.Formation of Acyl Halides RC O OHPCl5 RC O Cl POCl3HCl RC O OH SOCl2 RC O Cl SO2HCl + + + + RC O OHHX RC O X H2O PBr3 benzoyl bromidebenzoic acid C OH O H3PO3 C Br O + + + + 第16页/共46页 H3CC O OH (CH3CO)2O 2 C OH O C

8、O O 2 + RC O ONa (CH3CO)2O COOH COOH O O O RC O ClRC O ORC O + 第17页/共46页 H3C C O O(CH2)4CH3 ethyl buryrate pineapples bananas n-amyl acetate C OCH3 NH2 O C3H7C O OC2H5 R C O OH H ROHR C O OH OR H R C O ORH2O+ mechanism (1o, 2o alcohols) oranges methyl anthranilate 第18页/共46页 30 Mechanism H2SO4 H2O C

9、O OH CH3 H3C CH3 C O OH2 CH3 H3C CH3 CH3OH C O CH3 H3C CH3 C O CH3 H3C CH3 C O OCH3 CH3 H3C CH3 H + activity alcohol:CH3OH RCH2OH R2CHOH acid: CH3COOH RCH2COOH R2CHCOOH R3CCOOH 第19页/共46页 + H2O RC O OH amide NH3 RC O ONH4 RC O NH2 RC O NH2R C O NH2 (三)、Reduction b H3O C O OH a LiAlH4, Et2O CH3 CH2OH

10、CH3 CO OH b H3O a LiAlH4, Et2O CH2OH 第20页/共46页 CH3(CH2)3CH2COOH alc. KOH PCl3Br2 / H2CCH COOH CH3(CH2)3CHCOOH HBr Br CH3CHCOOH Br H2CCH2COOH Br mechanism PCl3 Br +RCH2C O OH RCH2C O ClRCH2C O Cl + HBr+ P(OH)3+RCH2C OH Cl Br RCH2C OH Cl H C C O Cl R Br H C C O Cl R Br+ +RCH2C O OHBrCH COOH R RCH2C O

11、Cl 第21页/共46页 R C O H2C C O O H CO2 R C OH CH2R C O CH3 COOH NO2 O2N NO2 H2O + CO2 NO2 O2N NO2 第22页/共46页 H3CCH COOH COOH + CO2 + CO2 1. H3C H2 C COOH HOOC COOHHCOOH 第23页/共46页 (H2C)n COOH COOH (CH3CO)2O 3. 4. + H2O + CO2 O 5个C以上 n=2,3 2. Ba(OH)2 (H2C)n C C O O O CH2CH2COOH H3C O CH2CH2COOH H2C CH2CH2C

12、OOH Ba(OH)2 + H2O + CO2 分子间脱水，高分子酸酐 CH CH2COOH H3C 第24页/共46页 KMnO4 + CHX3 O Ketones C O NaOH/X2 (H2C)4 C C O O OH R KMnO4 Aromatic Hydrocarbon OH CH3 C O ROH CH3 Cl COOH Cl 第25页/共46页 H or OH ClCH2COONa R-CN + H2O NaCN 二元酸 H2C CH2Br CH2Br R-COOH + H2O H2C CH2COOH CH2COOH H3O NaCNH3O HOOCCH2COOH 一元酸 第

13、26页/共46页 H3O Mg R-MgX + CO2 co2Br2 R-COOMgX Fe dry, ether H3O R-COOH H3O Ar-MgX + CO2 Ar-COOMgXAr-COOH CH3 CH3 H3C CH3 CH3 H3C Br CH3 CH3 H3C MgBr CH3 CH3 H3C COOH 第27页/共46页 R-XH2C NaOC2H5 a. OH/H2O b. H/ NaOC2H5 CO2C2H5 CO2C2H5 HC CO2C2H5 CO2C2H5 CH CO2C2H5 CO2C2H5 R RCH2COOH C CO2C2H5 CO2C2H5 R R-

14、X C CO2C2H5 CO2C2H5 R R a. OH/H2O b. H/ H CCOOHR R 第28页/共46页 H3O CO2 Br 1. CHCH2ClH2C CuCN Mg ether CN COOH CHCH2CNH2C CHCH2COOHH2C MgBr H3O COOH 第29页/共46页 + Knoevenagel CHO Perkin (CH3CO)2O 5h 55% CH3COONa 180oC OCH3 Py H C CHCOOH O CHO +(CH3CO)2O 7h CH3COONa 150oCO C H CHCOOH CHO CH3 +H2C COOH COO

15、H ref. H C CHCOOH OCH3 H3C 第30页/共46页 + (3) - RCHCOOH (1) -halogenated acid H2O (2) - dil. OH NaCO3 / H2O X RCHCOOH OH halogenated acid RCHCHCOOH HX dil. OH CHCOOHRHC halogenated acid CH2CH2CH2COOH X O O 第31页/共46页 + (3) - CH (1) -OH (2) - + H2O - H2O C OH CHCOOH H CHCOOHRHC OH CH2C CH2CH2O O O -H2O O

16、H H3C OOH CH C HO CH3 O HO O OH3C O CH3 O RCH HO H O OH (4) -OH CH2CH2C CH2CH2 O H O OH O O + H2O 第32页/共46页 (1) -OH (2) - + CO2 OH CHCOO H H CH2COOHRC -COOH CH C OH R O OH RCH HO KMnO4 H CH O R KMnO4 C OH O R KMnO4 OH O CH3RC O 第33页/共46页 (S)-2-溴丙酸 (R) -乳酸 CH C x R O OH SN2 a. dil. OH b. H con. NaOH

17、CH C OH R O OH H C Br HOOC H3C H C Br OOC CH3 HO HC OOC CH3 HO H HC COOH CH3 HO 第34页/共46页 (S)-2-溴丙酸 H dil. OH Ag2O Mechanism H C Br HOOC H3C -AgBr H C OH OOC H3C H C OH HOOC H3C (S) -乳酸 CH3 C Br CH O O Ag CH3 CC H O O CH3 C OH CH O O H (S) -乳酸 C L C G -L CC G Nu b a a b C G C Nu C Nu C G OH 第35页/共46

18、页 CHO a NaHSO3 b NaCN CHCN OH H3O CHCOOH OH HOCl OH Cl OH COOH OH CN H3O NaCN 第36页/共46页 (R)H Mechanism + C O R BrCH2CO2R a Zn/ether b H3O (R)H C OH R CH2CO2R 第37页/共46页 (CH3)2CHCH 2CHO + + CH3CHCO 2C2H5 a Zn/ether b H3O (H3C)2CH2CH HO CHCO2C2H5 BrCH2CO2CH3 Br CH3 O CO2CH3 H3C a Zn/ether b H3O OH CO2CH3 H3C CH2CO2CH3 第38页/共46页 HOOCCH2C O COOH 脱羧酶 或加热 H3CCH2C O COOH + CO2 RC O CH2COOH con NaOH heat +CH3COONaRC O ONa 第39页/共46页 COOH C O (CH2)2COOH + COOH C CH3 H2NH