DerivativesofCarboxylicAcids羧酸衍生物的定義、分類和表現(xiàn)

1、Derivatives of Carboxylic Acids羧酸衍生物的定義、分類和表現(xiàn) 15.1 Structure & Nomenclature 15.2 Physical Properties & Spectrum Data 15.3 Chemical Reactions 15.4 Fats, Was and Synthetic detergent (learn by yourself) 15.5 Preparation 15.6 Derivatives of carbonic Acid 15.7 Derivatives of Ortho-Acid 15.8 peroxy acid 1

2、5.9 Isonitrile 15.10 Sources and Usages of important Carboxylic Acid DerivativesContent 15.1 羧酸衍生物的結(jié)構(gòu)與命名 15.2 羧酸衍生物物理性質(zhì)和波譜學性質(zhì) 15.3 化學性質(zhì) 15.4 油脂、蠟和合成洗滌劑 15.5 羧酸衍生物的制備 15.6 碳酸衍生物 15.7 原酸衍生物 15.8 過酸和二?；^酸 15.9 異腈 15.10 重要的羧酸衍生物及羧酸衍生物的來源與用途ContentCarboxylic Acid Derivatives 羧酸衍生物羧酸衍生物在結(jié)構(gòu)上的共同特點是都含有酰基。-CN

3、 可以被水解成羧酸, 所以將腈也歸入羧酸衍生物。15.1 Structure & Nomenclature15.1.1 Structure15.1.2 Nomenclature15.1.1 Structure 結(jié)構(gòu)?；c其所連的基團都能形成p-共軛體系。C-L 具有部分雙鍵性質(zhì)，雙鍵的程度取決于C的穩(wěn)定性，C的穩(wěn)定性隨L的變化而不同。Acyl halide: L=Cl 電負性大Anhydride:Ester: L=O 電負性略小Amide: L=N 電負性更小15.1.2 Nomenclature15.1.2.1 Acyl Halide and Amide 15.1.2.2 Anhydride

4、 and Nitrile15.1.2.3 Ester 15.1.2.1 Acyl Halide and Amide 酰鹵與酰胺 中文命名 根據(jù)分子中?；奶荚訑?shù)命名為“某酰鹵”或“某酰胺”。環(huán)狀酰胺：內(nèi)酰胺己內(nèi)酰胺5-甲基己內(nèi)酰胺注意：編號沿用羧酸的編號15.1.2.2 Anhydride and Nitrile 酸酐與腈中文命名 根據(jù)水解所得的酸命名為“某酸酐”或“某腈”。COCOOH3CH3CCOCOOPhPhCH3CNPhCN乙(酸)酐苯甲(酸)酐乙腈苯甲腈注意計入氰基上的碳原子！若-CN作為取代基，則稱為“氰基”。間氰基苯甲酸3-氰基丁磺酸中文命名 根據(jù)水解所得的酸、醇，命名為“

5、某酸某酯”。15.1.2.3 Ester 酯 乙酸乙酯丙二酸二乙酯乙二醇二乙酸酯丙三醇三硝酸酯丁內(nèi)酯4-甲基丁內(nèi)酯123415.2 Physical Properties and Spectrum Data15.2.1 Physical Properties 15.2.2 Spectrum DataBoiling Points 熔點Even 3 amides have strong attractions. 15.2.1 Physical Properties 物理性質(zhì)Melting Points 熔點Amides have very high melting points. Melting

6、points increase with increasing number of N-H bonds.m.p. -61Cm.p. 28Cm.p. 79C胺的熔點很高, 且隨著N-H鍵的增多而上升. Acyl Halide To be irritating and decompose in water strongly. 具有刺激性，遇水劇烈分解。 Anhydride To decompose in water. 遇水分解。 Nitrile Highly polarized High dipole moment and high boiling point. 高度極化，高的偶極矩與沸點其它性質(zhì)

7、： Esters 酯 Esters tend to have sweet smells. 酯一般有芬芳的氣息。EsterFormulaFlavour/fragranceMethyl butyrateCH3CH2CH2COOCH3AppleEthyl butyrateCH3CH2CH2COOCH2CH3PineapplePropyl acetateCH3COOCH2CH2CH3PearPentyl acetateCH3COOCH2CH2CH2CH2CH3BananaPentyl butyrateCH3(CH2)2COOCH2(CH2)3CH3ApricotOctyl acetateCH3COOC

8、H2(CH2)6CH3OrangeMethyl benzoateC6H5COOCH3Ripe kiwiEthyl formateHCOOCH2CH3RumMethyl salicylateHOC6H4COOCH3WintergreenBenzyl acetateCH3COOCH2C6H5jasmineAmides 胺M. W. 5 73 87M. P. /0C 82 28 -20B. P. /0C 221 204 165 CH3CNH2OCH3CNHCH3OCH3CN(CH3)2OMany amides can form intermolecular hydrogen bond.許多胺類化合物

9、可以形成分子間氫鍵。15.2.2 Spectrum Data (Learn on your own) IR Spectroscopy.2 1H NMR Spectroscopy.3 13C NMR Spectroscopy IR Spectroscopy 紅外光譜 =15.2.2.2 1H NMR Spectroscopy 1H NMR 譜15.2.2.3 13C NMR Spectroscopy 13C NMR 譜 15.3 Chemical Reactions15.3.1 Hydrolysis of Derivatives of Carboxyl Acid15.3.2 Alcoholysi

10、s of Derivatives of Carboxyl Acid15.3.3 Ammonolysis of Derivatives of Carboxyl Acid15.3.4 Acidolysis of Derivatives of Carboxyl Acid15.3.5 Reactions with Organometallic Compounds15.3.6 Reduction of Carboxyl Acid Derivatives15.3.7 Other Reactions15.3.1 羧酸衍生物的水解15.3.2 羧酸衍生物的醇解15.3.3 羧酸衍生物的氨解15.3.4 羧酸衍

11、生物的酸解15.3.5 與金屬有機化合物的反應(yīng)15.3.6 與羧酸衍生物的反應(yīng)15.3.7 其它反應(yīng)水解、氨解、醇解和酸解反應(yīng)總論：Nu- = -OH, H2O 水解反應(yīng)Nu- = HOR 醇解反應(yīng)Nu- = NH3 氨解反應(yīng)Nu- = RCOOH 酸解反應(yīng) 含 義Acyl halide: L=Cl 電負性大Anhydride:Ester: L=O 電負性略小Amide: L=N 電負性更小反應(yīng)性1011 107 1.0 RCOOCOR RCOOR RCONH2 RCONR2Relative Rate 1011 107 1.0 10-2L = X, OCOR, OR, NH2Acyl Hali

12、des 酰鹵Hydrolysis of acyl halides with low molecular weight occurs quickly, even in moist air with no acid or base catalyst.Reagents must be protected from moisture.Rate of the reaction slows down with the increase of molecular weight of acyl halides.Mechanism: Nucleophilic acyl substitution 機理：酰基的親核

13、取代Anhydrides 酸酐Reacts faster than esters but more slowly than halides.Hydrolysis occurs in neutral, acidic and alkaline solutions.Under room temperature hydrolysis rate is slow.Esters 酯 Reverse of Fischer esterification. Reaches equilibrium. Reacts more slowly than acyl halides and anhydrides. Gener

14、ally needs catalysis: H+, OH- “皂化”Hydrolysis Mechanisms (In Alkaline Solution) of Ester酯的水解機理（堿性溶液中）QUESTIONS TO BE ANSWERED:Cleave at acyl-oxygen bond or at oxygen-alkyl bond. “酰氧” ？ “烷氧”？Single molecular mechanism or double molecular mechanism? 單分子？ 雙分子？SN2 mechanism or addition-elimination mechan

15、ism? SN2？ 加成消去？Evidence 1:Evidence 2:Evidence 3:18O-labeling experiments 18O同位素標記Possible Mechanism 可能機理Proton Exchange質(zhì)子交換ANSWERS TO THOSE QUESTIONS:Cleave at acyl-oxygen bond.Bimolecular mechanism.Addition-elimination mechanism.BAc2堿催化酰氧鍵斷裂雙分子歷程Hydrolysis Mechanisms (In Acidic Solution) of Ester:酯

16、的水解機理（酸性溶液中）Three possible mechanisms are involved in acid-induced ester hydrolysis.AAl1AAc2AAc1酸催化酯的水解有三種可能的機理：AAc2 （酸催化的雙分子酰氧斷裂） 適用于一般的一元羧酸與伯醇或仲醇形成的酯 AAc1 （酸催化的單分子酰氧斷裂） 適用于羰基附近有空阻因素的情況AAl1 （酸催化的單分子烷氧斷裂） 適用于三級醇形成的酯。Amides 酰胺 Reacts more slowly than acyl halides, anhydrides and esters. Strong acid o

17、r strong base is required. Prolonged heating is required.Nitriles 腈Heating with aqueous acid or base will hydrolyze a nitrile to an acid.Under mild conditions, nitriles hydrolyze to an amide. 15.3.2 Alcoholysis of Derivatives of Carboxyl Acid 羧酸衍生物的醇解15.3.2.1 Alcoholysis of Acyl Halide15.3.2.2 Alcoh

18、olysis of Anhydride15.3.2.3 Alcoholysis of Ester15.3.2.4 Alcoholysis of Amide15.3.2.5 Alcoholysis of NitrileReaction 反應(yīng)15.3.2.1 Alcoholysis of Acyl Halide 酰鹵的醇解Application: To prepare esters.Pyridine 15.3.2.2 Alcoholysis of Anhydride 酸酐的醇解分步! 兩類不同的反應(yīng) 15.3.2.3. Alcoholysis of Ester 酯的醇解Cat. : HCl H2S

19、O4 TosH etcNote: Reversible reactions 酯交換反應(yīng)1. 合成難以合成或者不能直接酯化合成的酯。酯交換的結(jié)果產(chǎn)物不變2. 二酯化合物的選擇性水解Applications 應(yīng)用:3.工業(yè)用途先酯交換，再聚合。eg: 滌綸的合成15.3.2.4. Alcoholysis of Amide 酰胺的醇解 Catalyzed by acidic catalysts. Heating to high temperature is required.15.3.2.5. Alcoholysis of Nitrile 腈的醇解 Acidic condition. (eg, HC

20、l, H2SO4)無合成應(yīng)用價值亞胺酯鹽酸鹽（無水時可分離得到）有水時可直接得到酯15.3.3.1 Ammonolysis of Acyl Halide15.3.3.2 Ammonolysis of Anhydride15.3.3.3 Ammonolysis of Ester15.3.3.4 Ammonolysis of Amide15.3.3.5 Ammonolysis of Nitrile15.3.3 Ammonolysis of Derivatives of Carboxyl Acid 羧酸衍生物的氨解 Reaction 反應(yīng)酰化劑15.3.3.1 Ammonolysis of Acyl

21、 Halide 酰鹵的氨解Eg.15.3.3.2. Ammonolysis of Anhydride 酸酐的氨解Eg. 15.3.3.3. Ammonolysis of Ester 酯的氨解Eg. 肼、羥氨亦可反應(yīng) A strong base is not usually a leaving group unless its in an exothermic step （放熱過程）. 15.3.3.4 Ammonolysis of Amide 酰胺的氨解N-acylimidazole is always used as acylation reagent. N酰基咪唑為優(yōu)良的?；瘎?。15.3.

22、3.5. Ammonolysis of Nitrile 腈的胺解高壓釜中咪 鹽15.3.4 Acidolysis of Derivatives of Carboxyl Acid 羧酸衍生物的酸解15.3.4.1 Acidolysis of Acyl Halide15.3.4.2 Acidolysis of Anhydride15.3.4.3 Acidolysis of Ester15.3.4.4 Acidolysis of AmideReactions 反應(yīng)酰基轉(zhuǎn)移反應(yīng)一般均需采取一定的手段使平衡右移15.3.4.1 Acidolysis of Acyl Halide 酰鹵的酸解 得到平衡混和

23、物，生成新的酸及酰鹵15.3.4.2 Acidolysis of Anhydride 酐的酸解 制備混酐15.3.4.3 Acidolysis of Ester 酯的酸解 得到平衡混和物，生成新的酸及酯15.3.4.4 Acidolysis of Amide 酰胺的酸解 得到平衡混和物，生成新的酸及酰胺ReactivityFor a carboxylic acid derivative to undergo a nucleophilicacyl substitution reaction, the incoming nucleophilemust not be a much weaker ba

24、se than the group that is to be replaced.A carboxylic acid derivative can be converted into a less reactive carboxylic acid derivative, but not into one that is more reactive.Only esters and amides are commonly found in nature. Acid halides and acid anhydrides undergo nucleophilic attack by water su

25、ch that they cannot exist in living organisms.15.3.5 Reactions with Organometallic Compounds 與金屬有機化合物的反應(yīng) 15.3.5.1 Reactions with Grignard Reagents and Lithium Alkyl 與格氏試劑和烷基鋰的反應(yīng)15.3.5.2 Reactions with Lithium Dialkylcuprate 與二烷基銅鋰的反應(yīng)15.3.5.1 Reactions with Grignard Reagents and Lithium Alkyl 與格氏試劑、烷

26、基鋰反應(yīng)Acyl Halides 酰鹵Step 1Step 2Step 1Equal molar RMgXAnhydrous FeCl3Low temperatureStep 2 For R and R with large space hindrance, reaction may stop at step 1.Anhydrides 酸酐Esters 酯 For R and R with large space hindrance, reaction may stop here.合成上用處不大Amides 酰胺 NO H is allowed in N atom合成上用處不大Nitriles

27、 腈亞 胺RCuLiCl15.3.5.2. Reactions with Lithium Dialkylcuprate 只與活潑的酰鹵反應(yīng)，生成酮，產(chǎn)率很高 15.3.6 Reduction of Carboxyl Acid Derivatives 羧酸衍生物的還原 15.3.6.1 Reduction of Acyl Halide15.3.6.2 Reduction of Anhydride 15.3.6.3 Reduction of Ester15.3.6.4 Reduction of Amide15.3.6.5 Reduction of Nitrile15.3.6.1 Reduction

28、 of Acyl Halide 酰鹵的還原LiAlH4AlLi(t-BuO)3HRosenmund ReductionAcyl Halide Can be reduced to alcohols or aldehydes.15.3.6.2 Reduction of Anhydride 酸酐的還原二元酸的環(huán)酐可還原成內(nèi)酯15.3.6.3. Reduction of Ester 酯的還原Mechanism 機理Bouveault-Blanc Reaction 玻沃布蘭反應(yīng)可用于大量制備15.3.6.4. Reduction of Amide 酰胺的還原1 mol0.25 mol過量過量N,N-二烴

29、基取代酰胺與還原劑反應(yīng)可得醛15.3.6.5 Reduction of Nitrile 腈的還原Short Review：Reactions of Acyl Halides Short Review：Reactions of Anhydride Short Review：Reactions of Ester with Grignard RMgXHydrolysis H2OAlcoholysis ROHAminolysis RNH2Reduction by LiAlH4Acid Halide R1COClR1RRCOH 3o alcoholR1COOHR1COORR1COONHRR1CH2OHA

30、nhydride R1COOCOR1R1RRCOH 3o alcoholR1COOHR1COORR1COONHRR1CH2OHEster R1COOR2R1RRCOH 3o alcoholR1COOH-R1COONHRR1CH2OHAmide R1CONH2-R1COOH-R1CH2NH2Nitrile R1CNR1CORR1COOH-R1CH2NH2Carboxylic acid R1COOHRH-R1CH2OH15.3.7 Other Reactions 羧酸衍生物的其它反應(yīng)15.3.7.1 Halogenation of Acyl Halide on -H 酰鹵的-H鹵化15.3.7.2

31、 Other Reactions of Ester 酯的其它反應(yīng)15.3.7.3 Other Reactions of Acyl Amide 酰胺的其它反應(yīng)15.3.7.4 Hydrolysis of Nitrile 腈的水解Acyl Halide Undergoes Halogenations on -H easier than carboxyl acids. -H鹵化比羧酸容易的多。 15.3.7.1 Halogenation of Acyl Halide on -H 酰鹵的-H鹵化 15.3.7.2. Other Reactions of Ester 酯的其它反應(yīng)1. Claisen C

32、ondensation Claisen酯縮合反應(yīng)CH3COC2H5OCH3COC2H5O+C2H5ONaCH3CCH2COC2H5OOpKa = 11pKa = 17Irreversible Cross Clasien condensation 交叉Clasien酯縮合解決方法之一：無-H的酯四個可能產(chǎn)物Carbonyl group conjugates with the aromatic ring, making this substrate less active. Often stronger base is required (e.g. NaH). 羰基與苯環(huán)共軛，不太活潑，縮合時需要

33、較強的堿。Induction effect activates one of the carbonyl groups, and this reaction is relatively easier. +誘導效應(yīng)使得羰基活潑，容易反應(yīng)。Which one is easier to lose its -H ?解決方法之二：酯與酮的縮合酮的-H 酸性更強Dieckmann Reaction 狄克曼反應(yīng)： 分子內(nèi)酯縮合，生成環(huán)酯合成五、六元環(huán)的方法2. Acyloin Condensation 酮醇縮合ReactionMechanismBimolecular reduction 雙分子還原-羥基酮Ap

34、plications 應(yīng)用Synthesis of catenaneSynthesis of Micro-reactor 索 烴Synthesis of catenane 索烴的合成Product of a random cross成環(huán)反應(yīng)的策略！p- conjugationp-共軛Higher acidity 強酸性15.3.7.3. Other Reactions of Acyl Amide 酰胺的其它反應(yīng)Lower alkalescency 弱堿性Acidity 酸性Alkalescency 微堿性Shows no acidityReact with NaOEtReact with Na

35、OH or KOH1. Acidic and Alkaline Properties 酸堿性 2. Dehydration 脫水 3. Hoffmann degradation of amides 霍夫曼降級反應(yīng)Often used when synthesizing a primary amine which contain 1 carbon less than the reactant. 用于制備少一個碳的一級胺15.3.7.4 Hydrolysis of Nitrile 腈的水解 Nu：接受親核試劑的進攻Strong Electrophilic reagents 接受強親電試劑進攻+ A

36、cid+ Base酸性條件下堿性條件下Ritter Reaction 里特反應(yīng)用途：特殊胺的制備強酸性溶液中，由叔醇生成的碳正離子類似于質(zhì)子，可進攻氰基氮原子。15.4 Fats、 Wax and Synthetic Detergents 油脂、蠟和合成洗滌劑 （Learn on your own）15.4.1 油脂 （一）分類 （二）化學性質(zhì)15.4.2 肥皂與合成洗滌劑 （一）結(jié)構(gòu)特點 （二）洗滌原理15.4.3 磷脂與生物膜15.4.4 蠟油脂 油 脂皂化 油的干性 碘值 酸敗肥皂 合成洗滌劑 磷脂 蠟15.5 Preparation 羧酸衍生物的制備 （Learn on your ow

37、n）15.6 Derivatives of Carbonic Acid 碳酸衍生物15.6.1 Acyl Halide of Carbonic Acids15.6.2 Amide of Carbonate Acid15.6.3 Ester of Carbonate AcidCarbonic AcidH2CO3Stable穩(wěn)定Unstable不穩(wěn)定羥基甲酸共用一個羰基的二元酸15.6.1 Acyl Halide of Carbonic Acids 碳酸的酰氯15.6.1.1 Carbonic Acid Monochloride 單酰氯Unstable 不穩(wěn)定15.6.1.2 Carbonic A

38、cid Dichloride 二酰氯Phosgene光氣6/15/2004 Fujian Institute of Research on the Structure of MatterPhosgene leaking caused 1 death and 260 injury. 氯代甲酸窒息性，劇毒，引起肺水腫Preparation 制備Lab：CCl4與80發(fā)煙H2SO4（發(fā)煙H2SO4中含80游離的SO3）Industrial 工業(yè)方法Phosgene generator性質(zhì)：類似于羧酸的酰氯，可水解、氨解及醇解氯代甲酸酯 碳酸二酯尿素 異氰酸Usage 用途It often works

39、 as an active reagent,or starting material in organic synthesis. 是一種活潑試劑，也是有機合成中的起始原料。15.6.2 Amide of Carbonate Acid 碳酸的酰胺15.6.2.1 Carbonate Acid Monoamides 單酰胺“滅菌靈”氨基甲酸Unstable氨基甲酸鹽氨基甲酸酰氯氨基甲酸酯Preparation 制備15.6.2.2 Carbonate Acid Diamides 二酰胺（尿素）Carbamide(urea), is one of the final products of prot

40、ein metabolizm. About 30g of Carbamide per day is discharged from a healthy adult. Whls ReactionIndustrial 工業(yè)上Properties 性質(zhì)In microorganism土壤中In organism 生物體系中In Lab 實驗室1. Hydrolysis 水解2. Nitrogen releasing reaction 放氮反應(yīng) This reaction is often used to measure the carbamide content in urea by measuri

41、ng the volume of N2 produced.測氮氣的體積可知尿液中尿素的含量。 This reaction is often used to destroy oxides of nitrous acid, and nitrogen oxides. 用于破壞亞硝酸及氮的氧化物。3. Biuret Reaction 雙縮脲反應(yīng)堿CuSO4溶液紫紅色溶液凡化合物中含不止一個酰胺片段NHCO ，均發(fā)生此反應(yīng)。這個反應(yīng)因此也用來進行多肽的鑒別。Ala-His-Ser雙縮脲15.6.3 Ester of Carbonate Acid 碳酸的酯15.6.3.1 Carbonate Acid Monoester 碳酸一酯Preparation 制備CO2+CH3ONaOOONaH3Csodium methyl carbonateH+CO2+CH3OH碳酸甲酯鈉15.6.3.2 Carbonate