2. Chapter 12. Carboxylic Acid Derivatives （ 羧酸衍生物） Text 1: chapter 21 Test 2: 第 13 章

3. esters 酯 acid anhydride 酸酐 acid halides 酰卤 amides 酰胺 nitriles 腈 Acid or base water Carboxylic acids

4. 12.1 Nomenclature Esters -yl (-oic acid)-ate × 酸 × 酯 ethyl acetate ethyl ethanoate 乙酸乙酯 vinyl acetate ethenyl ethanoate 乙酸乙烯酯 tert-butyl propanoate 丙酸叔丁酯 isopentyl acetate (used in synthetic banana flavor) 乙酸异戊酯 isopentyl pentanoate (used in synthetic apple flavor) 戊酸异戊酯

5. methyl benzoate 苯甲酸甲酯 methyl p-chlorobenzoate 对 - 氯苯甲酸甲酯 diethyl malonate 丙二酸二乙酯

6. Cyclic Esters Are Known as Lactones 6-methyl-tetrahydropyran-2-one 5-hydroxyhexanoic acid lactone

7. acid anhydrides 酸酐 --oic acid ——— --oic anhydride acetic anhydride 乙酐 醋酐 succinic anhydride 环丁酐 丁二酸酐 琥珀酸酐 maleic anhydride 环丁烯酐 顺丁烯二酸酐 马来酐 phthalic anhydride 邻苯二甲酸酐

8. acyl chlorides (acid chlorides 酰氯 ) Acyl group 酰基 acetyl chloride 乙酰氯 propanoyl chloride 丙酰氯 benzoyl chloride 苯甲酰氯 --ic acid ——--yl chloride

9. amides --ic acid——--amide acetamide 酰胺 propanamide 丙酰胺 benzamide 苯甲酰胺 N,N-dimethylformamide N,N- 二甲基甲酰胺 DMF N-phenylacetamide N- 苯基乙酰胺  primary amide 伯酰胺  secondary amide 仲酰胺  tertiary amide 叔酰胺

10. Cyclic Amides Are Known as Lactams( 内酰胺 )  -valerolactam  - 戊内酰胺  -butyrolactam  - 丁内酰胺  -propiolactam  - 丙内酰胺

11. Nitriles alkanenitrile ethanenitrile (acetonitrile) 乙腈 butanenitrile 丁腈 propenenitrile 丙烯腈 benzenecarbonitrile (benzonitrile) 苯甲腈 cyclohexanecarbonitrile 环己基甲腈

12. Functional groupName as main groupName as substituent carboxylic acids 羧酸 -oic acid carboxy( 羧基 ) esters 酯 -oate alkoxycarbonyl( 烷氧羰基 ) amides 酰胺 -amide amido( 酰氨基 ) nitriles 腈 -nitrile cyano( 氰基 ) aldehydes 醛 -al formyl( 甲酰基 ) ketones 酮 -one oxo( 氧代 ) alcohols 醇 -ol hydroxy( 羟基 ) amines 胺 -amine amino( 氨基 ) alkenes 烯 -ene alkenyl( 烯基 ) alkynes 炔 -yne alkynyl( 炔基 ) alkanes 烷 -ane alkyl( 烷基 ) ethers 醚 alkoxy( 烷氧基 ) halides 卤代烷 halo( 卤 ) Main groups in order of decreasing priority

13. 12.2 Structure and physical properties bp, mp: (Figure 21-2, p 948)  amide > acid > nitrile > alcohol > ester≈acid chloride ≈alkane  amide: primary > secondary > tertiary

14. Solubility: (Table 21-2) All are soluble in common organic solvents. Some are common organic solvents.  ethyl acetate (EtOAc ，乙酸乙酯， bp 77 ℃, 10% )  acetonitrile (CH 3 CN ， 乙腈， bp 82 ℃， misible with water )  DMF (N,N-dimethylformamide, N,N- 二甲基甲酰胺， bp 153 ℃, misible with water, )

15. IR 12.3 Spectroscopy CompoundsStretching frequency of C=O (cm -1 ) RCOCl (RCO) 2 O RCO 2 R RCONH 2 RC≡N 1815~1785 1850~1800 and 1780~1740 1735 1680~1630 2210~2260 Esters ， Carboxylic acid ， anhydrides 1310 ~1050 cm-1 C － O － C Amides3500 ~3200 cm-1 N–H

16. Ring strain in a lactone or lactam increases the carbonyl streching frequency. 1670 1700 1745 （ cm -1 ）. 1735 1770 1800 （ cm -1 ）.

17. 1743

18. 1827 1766

19. 3348 3173 1681

20. α - H δ: 2 ~ 3 ppm 1 H NMR 13 C NMR δ: ~120 ppm N - H δ: 5 ~8 ppm Amide: C=O δ: ~ 170 ppm

21. 1 H NMR: 13 C NMR: 1.25 2.05 4.15 171 60 20 14

22. 12.4 Interconversion of acid derivatives by nucleophilic acyl substitution ( 亲核酰基取代 ) Reactivity and interconversion of acid derivatives: More reactive Less reactive

23. transesterification 酯交换反应 ammonolysis 酯氨解反应 acid chlorides and anhydrides are used as acylation reagents.( 酰化 试剂 )

24. Mechanism: nucleophilic acyl substitution （亲核酰基取代） additioneliminationdeprotonation acid-catalyzed mechanism: protonation of carbonyl oxygen, addition, elimination base-catalyzed mechanism ： addition, elimination

25. Acid-catalyzed transesterification 酸催化的酯交换反应

26. Base-catalyzed transesterification 碱催化的酯交换反应

27. 12.5 Hydrolysis of acid derivatives Neutral hydrolysis Acid-catalyzed hydrolysis Base-catalyzed hydrolysis Mechanism: nucleophilic acyl substitution

28. 1. Hydrolysis of acid halides and anhydrides  Acid chlorides and anhydrides hydrolyze under neutral condition.

29. 2. Hydrolysis of esters  Acid–catalyzed hydrolysis of esters is the reverse of the Fisher esterification, is a equilibrium.  Base–catalyzed hydrolysis of esters is also called saponification ( 皂化反应 ), avoids the equilibrium of the Fisher esterification.

30. 3. Hydrolysis of amides  Acid–catalyzed hydrolysis of amides: 6 mol/L HCl

31.  Base–catalyzed hydrolysis of amides: 40% aqueous NaOH

32. 4. Hydrolysis of nitriles  Acid–catalyzed hydrolysis of nitriles amides Amides can be hydrolyzed to carboxylic acid under stronger conditions.

33.  Base–catalyzed hydrolysis of nitriles amides Amides can be hydrolyzed to carboxylic acid under stronger conditions.

34. 12.6 Reduction of acid derivatives 1. Reduction to alcohols esters acid chlorides carboxylic acid aldehydes1° alcohols LiAlH 4 2. Reduction to aldehydes LiAl(OC(CH 3 ) 3 )H acid chloridesaldehydes

35. 3. Reduction to amines amides nitriles amines LiAlH 4

36. 12.7 Reaction of acid derivatives with organometallic reagents esters: acid chlorides: tertiary alcohols 三级醇 nitriles: amides:NO reaction.

37. 1. Synthesis of acyl chlorides 12.8 The chemistry of acyl chlorides

38. 2. Reactions of acyl chlorides Acid chloride is important acylation reagent ( 酰化试剂 )

40. 1. Synthesis of carboxylic acid anhydrides 12.9 The chemistry of acid anhydrides

41. 2. The reactions of acid anhydride

42. Useful anhydrides: acetic anhydrides( 醋酐 )acetic formic anhydrides （甲乙酐） cyclic anhydrides （环状酸酐）

43. 12.10 The chemistry of esters 1. Synthesis of esters

44. 2. The reactions of esters

45. 12.11 The chemistry of amides 1. Synthesis of amides

46. 2. The reactions of amides only primary amides Hoffmann rearrangement ( 霍夫曼重排，霍夫曼降解 ) only primary amides

47. Polyamides （聚酰胺） Nylon 6 Nylon 6,6

48. 12.12 The chemistry of Nitriles 1. Synthesis of nitriles

49. 2. The reactions of nitriles

50. 12.13 Thioesters ( 硫酯 ) 21-15, p 988 thiol 硫醇 thioesters 硫酯 Reactivity as acylating reagents: acid chlorides > acid anhydrides > thioesters > esters Thioesters are common acylating reagents in living systems. 常用来代替在水中不稳定的酰氯和酸酐作酰化试剂。

51. 12.14 Derivatives of carbonic acid （碳酸的衍生物） carbonic acid 碳酸 carbonyl dichloride phosgene 碳酰氯，光气 carbonate esters 碳酸酯 urea 尿素，脲 carbamic acid 氨基甲酸 unstable carbamate ， urethane 氨基甲酸酯

53. Assignments Text 1: 48, 49, 50, 53, 55, 57