有机化学ChapDerivativesofCarboxylicAcidsY

1、有机化学ChapDerivativesofCarboxylicAcidsY2Section 1RCO Acyl 酰基酰基3Esters 酯酯R COORAcid halides 酰卤酰卤 R COXAnhydrides 酸酐酸酐R COO CORAcidamide 酰胺酰胺R CONH2Classification41.1 Nomenclature and Preparation1.1.1 NomenclatureEstersR COOR1 NomenclatureFor small ester (RCOOR), the R group is named first and the “ic”

2、of the parent acid is replace with the suffix “ate.” The R group is named as a alkyl group put on ahead. The carbonyl group get up priority in the naming scheme and substituents are numbered with respect to the carbonyl as position 1.51.1 Nomenclature and Preparation1.1.1 NomenclatureEstersR COOR1 N

3、omenclature一元羧酸和一元醇生成的酯称为“某酸某醇酯”, “醇”字常省略; 酸在前, 醇在后;6Ethyl acetate乙酸乙酯Phenyl formate甲酸苯酯tert-Butylbutyrate丁酸叔丁酯Ethyl benzoate苯甲酸乙酯CH3COOC2H5H COOCH3CH2CH2COO C(CH3)3COO CH2CH3COOCH3CH2CHCH2CH3CH2CH3Ethyl 3-methylpentanoate3-甲基戊酸乙酯1 Nomenclature71.1.2 PreparationR-COOHROH/H+R-COORC2H5COOHCH3CH2OH /H+

4、C2H5COOCH2CH3+ H2OC6H5COOHCH3OH /H+C6H5COOCH3+ H2O1 NomenclatureCOHROH+ORHCOROR+ H2O81.2.1 NomenclatureAcid halidesR COX )(R-R-XOC1 NomenclatureAcid halides are named systematically by replacing the final “e” of the parent alkane with “yl halide” . In practice, the names for the smaller acid halides

5、 are based upon the common names for the related acids.91.2.1 NomenclatureAcid halidesR COX )(R-R-XOC1 Nomenclature酰卤的的命名是根据酰基和卤素的名称, 称“某酰卤”;10Formyl chloride甲酰氯Carbonic dichloride, Phosgene氯代甲酰氯，碳酰氯(光气)Acetyl chloride乙酰氯Benzoyl chloride苯甲酰氯COHClCOClClCOClCH3COClCOCH3CH2BrPropanoyl bromide丙酰溴1 Nomen

6、clature111.2.2 Preparation1 NomenclatureCROOHPX3CROX + H3PO3CROOHPX5CROX + POCl3 + HClSOCl2CROOHCROCl + SO2 + HCl氯化亚砜氯化亚砜亚磷酸三氯氧酸121.3.1 NomenclatureAnhydridesR COO COR1 NomenclatureAnhydrides are named by reference to the acid from which they are formally derived by loss of water.131.3.1 Nomenclatur

7、eAnhydridesR COO COR1 Nomenclature酸酐的名称是在羧酸名称后加“酐”字, 称某(酸)酐, 且 “酸”字常省略;若为不同羧酸形成的酸酐, 命名时将简单的羧酸写在前面,复杂的羧酸写在后面;14COO COCH2CH2CH3Benzoic butanoic anhydride 苯甲丁(酸) 酐 OOOPhthalic anhydride邻苯二甲(酸) 酐1 NomenclatureCOCH3O COCH3Ethanoic anhydride 乙(酸) 酐COCH3O COCH2CH3Ethanoic propanoic anhydride 乙丙(酸) 酐151.3.2

8、 PreparationR-R-HO COCOOHR-R-+P2O5R-R-COOR-R-COR-R-COONaR-R-+R-R-COOR-R-COCOCl1 Nomenclaturephosphorus pentoxide Dehydrant161.4.1 NomenclatureAmides are systematically named by dropping the final “e” of the parent alkane and adding the suffix “amide.” As usual the smaller members of the class have r

9、etained their common names, which are base on the common names for smaller carboxylic acids. Substitution on nitrogen is indicated with a prefix N, as in N-methyl, N,N-diethyl, and so on. 1 Nomenclature AmideR CONH2171.4.1 Nomenclature1 Nomenclature将相应羧酸的 “酸”字换为 “酰胺”;若酰胺的N原子上连有烃基, 则需在烃基前加字母“N”, 表示 烃

10、基连在N原子上; AmideR CONH218Ethanamide 乙酰胺 Acetamide3-Methylbutanamide3-甲基丁酰胺Benzamide苯甲酰胺OC NH2CH3OC NH2CH2CHCH3CH3OC NH2OCHN(CH3)2N,N-dimethylformamide (DMF)N,N-二甲基甲酰胺A all-purpose solvent1 Nomenclature19NHO -propiolactam-丙内酰胺1 Nomenclature环状的酰胺被称为内酰胺;内酰胺命名与内酯类似, 在酰胺前加“内”字, 并用数字或希腊字母标明原氨基位置, 且省略“氨基”二字;

11、Cyclic amides are known as lactam.20CH2CONHNSOCH3CH3COOH- 内酰胺抗生素 ( -Lactam Antibiotics) 青霉素G ,盘尼西林(Penicillin G) 头孢唑啉, 先锋V(Cefazoline) NSCH2CONHCOOHCH2SHHONNNNNNSCH3211.4.2 Preparation R COOHNH3R CONH2R COClNH3R CONH2NH3R CONH2R COOCORCOORR-R-NH3R-R-CONH21 Nomenclature22Section 2 232 Chemical Proper

12、ties2.1 ReductionLiAlH4R-R-CH2OHCOR-R-COOR-R-R-R-+CH2OH+ R-R-R-R-COOR-R-CH2OHR-Na,C2H5OHOH1 Physical PropertiesR-R-COXLiAlH4R-R-CH2OH+ HXCORNH2LiAlH4RCH2NH224L=X,OR,OCR,NH2,NHR,NR2ONu=OH,OR,NH2,NHR,NR2 Nucleophilic reagent Leaving group2.2 Nucleophilic Substitution2 Chemical Propertiessp2sp3sp2COL L

13、Nu+AdditionR C L LONuEliminationR CONu + LR252.2.1 Hydrolysis2 Chemical PropertiesH2O+ R-R-R-R-COOR-R-COR-R-COOHCOOHH2OR-R-COOHCOXR-R-26The hydrolysis of esters in alkali is called Saponification(皂化反应皂化反应).2 Chemical PropertiesCOOHR-R-+ R-R-R-R-COOR-R-H2O,OHOH-CCHHCCHHCHHHHCCHHCCHHCHHHHHHHOOPolar gr

14、oup(hydrophilic)Non-polar group(hydrophobic)OOOOOOA fat moleculeNaOHOONaOONaOONaSoap moleculesOHOHOHGlycerol+How Soap Is Made亲水头部亲水头部疏水尾部疏水尾部28How Soap Is Made292.2.2 Alcoholysis2 Chemical PropertiesR-R-COXCOORR-R-ROHCOORR-R-ROHCOR-R-COOR-R-30OCOOHC CH3O乙酰水杨酸Aspirin 阿司匹林, 醋柳酸, 巴米尔 antipyretic analge

15、sics(解热镇痛药) OHCOOHAc2OSalicylic acid水杨酸AcCH3CO2 Chemical PropertiesAc2OCH3C 2OO31How Does Aspirin Work?Acetylsalicylic acid 阿司匹林本格特萨米尔松苏恩伯格斯特龙约翰范恩OHOOOOHOOHSalicylic acid水杨酸OHOArachidonic acidArachidonic acid花生四烯酸花生四烯酸Cyclooxygenase环氧合酶环氧合酶ProstaglandinsProstaglandins前列腺素前列腺素OHOOOOOHPGG2PGG2How Does

16、 Aspirin Work?COOOHCyclo-oxygenaseHOActive enzymeCyclooxygenase环氧合酶环氧合酶COOOOAcetylsalicylic acid 阿司匹林阿司匹林How Does Aspirin Work?Cyclo-oxygenaseOAcylated enzyme inactiveO34This reaction also know as Transesterification Reaction(酯交换反应酯交换反应). ROH+R-R-COORCOORR-R-R-OHHigh-boilingesterHigh-boilingalcoholH

17、igher-boilingester Lower-boiling alcohol2 Chemical Properties35CH3COOCH2CH3(CH3)2CHOH /H+CH3COOCH(CH3)22 Chemical Properties乙酸异丙醇酯CH2CH COOCH3+CH3CH2CH2CH2OHH+CH2CH COOCH2CH2CH2CH3CH3OH+丙烯酸丁酯36H2NCOOC2H5HOCH2CH2N(C2H5)2H2NCOOCH2CH2N(C2H5)2Procaine 普鲁卡因局麻药物2 Chemical Properties对氨基苯甲酸乙酯N,N-二乙基乙醇37Beta

18、-Lactam Antibiotics亚历山大弗莱明 霍华德弗洛里 恩斯特鲍里斯钱恩 Penicillin盘尼西林NSNOOCOOHRHNSNOOCOOHHNH2Ampicillin氨苄青霉素NSNOOCOOHHNH2HOAmoxicillin羟氨苄青霉素NO Penicillin盘尼西林NSNOOCOOHRH-内酰胺类抗生素内酰胺类抗生素( -Lactam Antibiotics)Beta-Lactam AntibioticsNSNOOCOOHRHNSNRCOOHOHtrans-PeptidaseOOOHAcylated enzyme inactiveBeta-Lactam Antibiot

19、icstrans-PeptidaseOHActive enzyme转肽酶转肽酶NNOORHSCOOHCephalosporins头孢菌素类头孢菌素类NSCH2CONHCOOHCH2SHHONNNNNNSCH3Cefazoline 头孢唑啉（先锋V）Beta-Lactam AntibioticsNHO -LactamaseH2OONOHH+412.2.3 Ammonolysis 2 Chemical PropertiesNH3R-R-CONH2COXR-R-COR-R-COOR-R-NH3R-R-CONH2COORR-R-NH3R-R-CONH242R C XOR COORR COO CORAc

20、id halides, anhydrides and esters are acylating agents(酰基化试剂酰基化试剂). The start material react with these acylating agents can introduce acyl group.ROHNH3H2O+ +2 Chemical PropertiesR COOHR COORR CONH2RCOHOcarboxylic acidAcid chloride酰氯RCClOEster酯RCOROAmide酰胺RCNH2OAnhydrides酸酐RCOOCRO2.2 Nucleophilic Su

21、bstitution2 Chemical Properties反应活泼性愈弱442.3 酯缩合反应酯缩合反应(Ester condensation) Claisen condensations involve a ester with -hydrogen and the carbonyl group of another ester. Ethyl acetate, for exemple, reacts with sodium ethoxide to give the -keto ester. CH3COOC2H5C2H5ONaCOOC2H5CH3COCH22 Chemical Propert

22、iesacetylacetic ester乙酰乙酸乙酯(-丁酮酸乙酯)-酮酸酯酮酸酯2.3.1 Claisen condensation (克莱森缩合克莱森缩合)452 Chemical PropertiesMechanism of Claisen condensation:H+(1)(2)(3)C OC2H5OCH3C CH2OCH3C OC2H5O-CH2COOC2H5CH2C OC2H5O+CH3C OC2H5OCH2C OC2H5OC2H5ONaCH3C OC2H5O46Why Meat from Younger Animals Is SofterNH3CollagenOHCollag

23、enOHCollagenCollagenAldol condensationOxidative deaminationWhy Meat from Younger Animals Is Softer48A Claisen condensation between two different esters both with -hydrogen is call a crossed Claisen condensation(交叉克莱森缩合交叉克莱森缩合). Thus four products are possible. If one partner has no -hydrogen, it can

24、 function only as an acceptor, and not as the nucleophile partner in the reaction.2 Chemical Properties49NaHCOOC2H5+CH3CH2COOC2H5COCHCCH3OOC2H5C2H5ONaCH2COOC2H5+HCOOC2H5CHCHOCOOC2H52 Chemical Properties苯甲酰化物苯甲酰化物-甲酰化物甲酰化物502.3.2 酮酮-烯醇互变烯醇互变(Keto-enol Tautomerism)CH3COCH2COOC2H5How to synthesize acet

25、ylacetic ester?CH3COCH2COOC2H5H+C2H5OH/COOHCH3COCH2Can we use the following route? Why?2 Chemical Properties51Acetylacetic ester has some special chemical properties:NaHSO3H2N-YHCNCH3CO2 Chemical PropertiesCH3COCH2COOC2H5CCOHCCOH乙酰乙酸乙酯(-丁酮酸乙酯)Br2 / CCl4FeCl3Na H252These special chemical properties a

26、re due to the tautomerism(互变异构互变异构) of acetylacetic ester. CH3C CH2OC OC2H5OC OC2H5OCH3COHCHketo-form(93 %)酮型酮型enol-form(7 %)烯醇型烯醇型2 Chemical Properties531) Simple ketones are almost keto-form.Keto-enol tautomerism(酮酮-烯醇互变异构烯醇互变异构):2) If the-hydrogens be substituted by or ,R COCOO Rthe stability of

27、enol form will increase. Substituted by make the enol form more stable than substituted by .R COCOO R2 Chemical Properties543) If the enol form cause the conjugate system become longer or form intramolecular hydrogen bond, the enol form is stable.C C COOHCCOHCOH2 Chemical Properties55CH3C CH C CH3OO

28、HCH3C CH C OCH3OOHCH3C CH C CH3OOHCH3C CH3OCH3C CH2C OCH3OOCH3C CH2C CH3OOCH3C CH C CH3OOHCH3C CH C OCH3OOHCH3C CH C CH3OOHCH3C CH3OCH3C CH2C OCH3OOCH3C CH2C CH3OO2 Chemical PropertiesCH3C CH C CH3OOHCH3C CH C OCH3OOHCH3C CH C CH3OOHCH3C CH3OCH3C CH2C OCH3OOCH3C CH2C CH3OO乙酰丙酮乙酰乙酸乙酯丙酮56C OC2H5OCH3C

29、CH2O+C2H5OH40%NaOHCH3COONa2酸式分解酸式分解(Acidic cleavage) 分解反应分解反应(Cleavage reaction of acetylacetic ester )2 Chemical Properties57H+CH3C CH3OC2H5OH+CH3C CH2COONaOdilute OH-CH3C CH2OC OC2H5O酮式分解酮式分解(Ketonic cleavage)2 Chemical PropertiesH+CH3C CH3OC2H5OH+CH3C CH2COONaOdilute OH-CH3C CH2OC OC2H5OH+CH3C CH3OC2H5OH+CH3C CH2COONaOdilute OH-CH3C CH2