有机化学Chap 10 aldehydes and ketones20140413-7Y

1、Chapter 10 Aldehydes and Ketones HOUndecanal十一醛OO2-Heptanone2-庚酮trans-2-Hexenal反-2-庚醛Civetone香猫酮HOOVanillin香草醛(Vanilla flavor 香草味)Cinnamon flavor 肉桂醛(Cinnamaldehyde 桂皮味)(R)-Carvone R-香芹酮(Spearmint flavor 薄荷味)Benzaldehyde 苯甲醛(Almond flavor 杏仁味）HOH3COHOOHHOProgesterone 孕酮Testosterone 睾酮OHHOH3CCH3OHOHH

2、OHOHHH甲醛 丙酮Carbonyl group 羰基羰基Aldehyde 醛Ketone 酮ORRORHCommon names(普通命名法普通命名法) are normally used for the aldehydes containing four carbons or fewer. 1 Nomenclature1.1 分类分类芳香醛（酮）脂肪醛（酮）1.2 普通命名法普通命名法 CH3CH2CHOCH3CCH3OCHOCCH3O丙醛甲(基)乙(基)酮甲(基)环己(基)酮二苯(基) 酮苯乙醛CH3CH2CHOCH3CC2H5OCCH3OCH2CHOO1 NomenclatureFo

3、r systemic names(系统命名法系统命名法), the “e” of the parent alkanes name is dropped and the suffix “al” is added.In the priority system the aldehyde group is always number 1, and higher numbers are given to any substituents.1.3 系统命名法系统命名法 Aldehyde 醛醛 1 NomenclatureH C HOformaldehydeH COCH3acetaldehydeC HOCH

4、3CH2CH2CHCH32-methylpentanal2-甲基戊醛C HOClCH2CH23-chloropropanal3-氯丙醛(甲醛 mathanal )( 乙醛ethanal )5 4 3 2 13 2 11 NomenclatureClHOHCHOCH33-methylbenzaldehyde3-甲基苯(基)甲醛(Z)-3-chloro-3-phenyl-2-propenal(Z)- 3-苯基-3-氯-2-丙烯醛3 24 15 63 2 11 NomenclatureThe “e” of the parent alkane is dropped, and the suffix “o

5、ne” is appended. The number of the carbon atom bearing the carbon-oxygen double bond begins the name. Give the carbonyl group the smallest number as far as possible. Aromatic ketones are often named by treating the benzene ring as a phenyl group.Ketone 酮酮1 NomenclatureCOCH3CH3propanoneCOCH3CHCH2CH3C

6、H33-methyl-2-pentanone3-甲基-2-戊酮OOOOCH34-methoxycyclohexanone4-甲氧基环己酮1,4-cyclohexanedione1，4-环己二酮(acetone丙酮)1 2 3 4 51 42 36 52 31 NomenclatureCOCH3COmethyl phenyl ketone苯苯(基基) 甲甲(基基) 酮酮甲(基)苯(基) 酮cyclopropyl phenyl ketone 苯基环丙基酮( phenylethanone 苯乙酮 )OCH3CH3CH3( 2,2-dimethyl-1-phenylpropanone, 2,2-二甲基

7、-1-苯基-丙酮)t-butyl phenyl ketone (苯基叔丁基酮)1 Nomenclature1 232 Preparing Aldehydes and Ketones2.1 Oxidation of alcoholsRCHORCH2OHCrO3C5H5N2Collins reagent: CrO32C5H5NR C ROR CH ROHK2Cr2O7/H+KMnO4/H+or2. Ozonization of alkenesR COH +COR1R2CCHRR1R2O3O OCCORR1R2HZn/H2OOzonide臭氧化物臭氧化物2 Preparing Aldehydes a

8、nd KetonesShow the major product of the following reaction:Exercise:H3CO3Zn /H2OCOH3CCH2CH2CH2CHO3. Friedel-Crafts Acylation ReactionAcyl chlorides or acid anhydrides react with benzene under the influence of an equivalent (not a catalytic amount) AlCl3 to form aromatic ketones. R CO2)( R COOR COCl

9、acyl acyl chloride acid anhydride 酰基 酰氯 酸酐2 Preparing Aldehydes and KetonesR C ClO/AlCl3C RO(RCO)2O/AlCl3C RO2 Preparing Aldehydes and KetonesH3CO(CH3CO)2O /AlCl3H3COCOCH33. Structure and Physical PropertiesFIGURE. Structure of acetaldehyde乙醛乙醛3.1 羰基的结构羰基的结构CCHOHHHAlkene Carbonyl group烯烃烯烃 羰基羰基3. St

10、ructure and Physical PropertiesEthylene Formaldehyde乙烯 甲醛CH3CH2CHCH2CH3CH2CHOCH3CH2CH2OH1-Butene Propanal1-丁烯 丙醛Dipole moment: 0.3D 2.5D沸点：水溶性：(g/100 mL)不溶性 20 任意比混合3. Structure and Physical Properties-6 49 97CH3CH2CHCH2CH3CH2CHOCH3CH2CH2OH1-Butene Propanal 1-Propanol3.2 物理性质物理性质4. Chemical Properti

11、es燃烧热：燃烧热： (Heat of Combustion)FormaldehydeORHORRButanal 2-Butanone2475kJ/mol 2442kJ/molCH3CH2CH2CHOCH3CH2CCH3O电效应电效应(Electronic effects) Recall that alkyl groups are electron donating. 空间位阻效应空间位阻效应(Steric effects) 4. Chemical PropertiesKetone酮酮has two electron-donating alkyl groups that stabilize t

12、he partial positive chargehas only one electron-donating alkyl groups that stabilizes the partial positive chargeAldehyde醛醛CO(H)RCH 亲核加成反应亲核加成反应(Nucleophilic Addition) 碳及碳及 氢的反应氢的反应(Reactions at the -position)氧化和还原反应氧化和还原反应(Oxidation and Reduction)4. Chemical Propertieso + + - -4.1 亲核加成反应亲核加成反应(Nucl

13、eophilic Addition)4. Chemical Propertiessp2 sp3Lewis basesLewis acidsArrhenius concept of acids and basesBrnsted-Lowry concept of acids and basesLewis concept of acids and bases4. Chemical PropertiesAcid-base conceptAcid-base concept4.1.1 与氢氰酸加成与氢氰酸加成(Addition of Hydrocyanic Acid)Cyanohydrin氰醇(-羟基腈)

14、Alcohol Acid-羟基酸4. Chemical PropertiesAldehyde HydrogencyanideR COCH3HCNC CH3OHCNR+HR C CH3OHCOOHketoneR-COHHCNC HOHCNR-+HR-C HOHCOOH All aldehydes include aliphatic and aromatic aldehydes.COHR-Aliphatic methyl ketones.R COCH3 Cyclic ketones which the rings contain eight or less carbon atoms.(CH2)nO

15、n8反应物的结构要求：反应物的结构要求：CyclohexanoneHCNOOHCN+HOHCOOH4. Chemical Properties4.1.1Addition of Hydrocyanic AcidCyanohydrin Derivatives in NatureAmygdalin苦杏仁苷Mandelonitrile苯乙醇酰(扁桃腈)Benzaldehyde苯甲醛COHNHOHCN+ToxicOOOOHHOHOOHHOOOHOHCNcyanohydrinalcohol acid氰醇， -羟基腈醇酸(Ar) RCOHHCN(Ar) RCOHHCN(Ar) RCOHHCOOHH2O /

16、H+ H (Ar) RCOHHCH2NH2-hydroxy amine-羟基胺4.1.1 与氢氰酸加成与氢氰酸加成(Addition of Hydrocyanic Acid)4. Chemical Properties4.1.2 与亚硫酸氢钠的加成与亚硫酸氢钠的加成(Addition of sodium bisulfite)-H2O/OH+H2O/HorR-COHWhite Crystal4. Chemical PropertiesR-COHC HSO3HONaR-R-C HOHSO3NaNaHSO3-H2O/OH+H2O/HorCOCH3RNaHSO3C CH3ONaSO3HRR C CH3

17、SO3NaOHCOCH3RWhite Crystal-H2O/OH+H2O/HorONaHSO3SO3HONaOHSO3NaOThe product of bisulfite(亚硫酸氢盐) addition is often a nice isolable solid. So it is also a distinguish reaction. But more important, via this reaction we can purify aldehydes and some ketones. 4. Chemical Properties4.1.2Addition of sodium

18、bisulfite All aldehydes include aliphatic and aromatic aldehydes.COHR- Aliphatic methyl ketones.R COCH3 Cyclic ketones which the rings contain eight or less carbon atoms.(CH2)nOn8反应物的结构要求：反应物的结构要求：4. Chemical Properties4.1.2Addition of sodium bisulfiteExample ：Point out which compounds of the follow

19、ing molecules can react with sodium bisulfite:COCH3(1)COCH3CH2(2)(3)COHCH3CH2CH2CH2CH3O(4)CH3CH2C CH2CH3O(5)Exercise:4.1.2Addition of sodium bisulfite4.1.3 与水的加成与水的加成(Addition of water)R C H(R)OH2OR C H(R)OHOHGeminal Diol偕二醇4. Chemical PropertiesH2OC H(R)OCl3CC H(R)OHOHCl3CChloral Hydrate, Ataractic

20、水合三氯乙醛，镇静剂Chloral三氯乙醛H+CORH + ROHHemiacetal半缩醛Acetal 缩醛4. Chemical Properties4.1.4 与醇的加成与醇的加成(Addition of Alcohols)AldehydeROHCORHdry HClCRHOHORdry HClROHCRHORORAcetals(缩醛) or ketals(缩酮) are stable to base, oxidants and reducer. So carbonyl compounds can be protected by converting them into their ac

21、etal or ketal forms, and then regenerating as needed.OOOCH2CH2HOCH2CH2OH/H+4. Chemical Properties4.1.4 Addition of AlcoholsKetals缩酮缩酮Acetals as ProdrugsProdrug(前药前药)pharmacologically inactive compounds that are converted by the body into active compounds.Fluocinolone Acetonide Acetate醋酸氟轻松OHHOFFHOHO

22、OOHO+OActive drugOHHOFFHOOOOOExercise:OOHOHOOOHHOO10-12 根据下列环状半缩醛或缩醛的结构，推测其原来的开链羟基醛或羟基酮的结构(2)(1)Exercise:H3COOCH3H3CHOHOCH3OHOHOCH3H3CO(3)HCHORMgXHCHROMgXH+RCH2OH4.1.5. 与格氏试剂的加成与格氏试剂的加成(Addition of Grignard Reagents)4. Chemical PropertiesRMgXH+CHORCHROMgXRRCHROHRMgXH+CORR1CROMgXRR1RCR1ROH伯醇仲醇叔醇甲醛醛酮4

23、.1.6 与氨衍生物的加成与氨衍生物的加成(Addition of derivatives of ammonia)Carbinolamine醇胺ImineN-取代亚胺Schiff s base 希夫碱4. Chemical PropertiesCORR1CRR1OHNH YR C N-YR1H2N YH2O-Primary amine 伯胺4. Chemical PropertiesOxime肟 (w)Hydroxy amine羟胺Hydrazine 肼Hydrazone腙4.1.6 Addition of derivatives of ammoniaCORR1R CR1N OHH2N OHH

24、2N NH2R CR1N NH2CORR1Phenyl hydrazine苯肼Phenyl hydrazoneH2N NHCORR1R CR1N NH2,4-dinitrophenyl hydrazone2,4-二硝基苯腙Yellow precipitationFormation of 2,4-dinitrophenyl hydrazone can diagnose the presence of a carbonyl group.4. Chemical Properties4.1.6 Addition of derivatives of ammoniaCORR1H2N NHNO2NO2R C

25、R1N NHNO2NO22,4-dinitrophenyl hydrazine2,4-二硝基苯肼Imines as ProdrugsH2NOHONOOHHHhydrolysisH2NOHOProgabideOHFNClNH2O-氨基丁酸羸羸 赢赢在“ ”中找到“ ”哈雷望远镜级别哈雷望远镜级别羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸

26、羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸赢羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸赢羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸-carotene-胡萝卜素胡萝卜素OHvitamin A (retinol)视黄醇视黄醇(维生素维生素A)OHOOHOHhH2NproteinNHproteinNHproteinOH+H2N-proteinH2Oretinal 视黄醛视黄醛 11-cis-retinalrhodopsin视紫

27、红质视紫红质vitamin A (retinol)视黄醇视黄醇(维生素维生素A)4.2 碳及碳及 氢的反应氢的反应(Reactions at the -position)4. Chemical PropertiesCOCH+-. . - 共轭效应共轭效应4.2.1 醇醛缩合醇醛缩合(Aldol Condensation)COHRCH22dilute OH-COHCHCHRCH2ROHAldol 醇醛4. Chemical Properties -hydroxyaldehyde(-羟醛羟醛) , -unsaturated aldehyde( , -羟醛羟醛)COHCRCH2CHRMechanis

28、m of aldol condensation :COHRCH2 OH-R CH CHOR CH CHOCOHRCH2+COHRCH2COHCHCHRCH2RO-COHCHCHRCH2ROHH2OCarbanion碳负离子IntermediateAldol4. Chemical Properties4.2.1 Aldol CondensationCCH2CH3CHOCH3CH2CH2CHLike most intermolecular reaction(分子间反应), the aldol condensation has an intramolecular version. Particula

29、rly favorable are intramolecular condensation that form the relatively strain-free five- and six-membered rings.NaOH,H2OCH3CH2CH2CHO4. Chemical Properties4.2.1 Aldol CondensationNaOH,H2OCOCH3CH2CH2CH2CH2COCH3CH3CCH3OCH3OHOCH3COHCHCCH3交叉醇醛缩合(Crossed Aldol Condensation)4. Chemical Properties4.2.1 Aldo

30、l CondensationCOHCHCHCH3OH+COHCH3CH2NaOH,H2OCHO克莱森克莱森-斯密特反应斯密特反应(Claisen-Schmidt)4.2.2 卤代反应卤代反应(Haloform Reactions)4. Chemical PropertiesCORCH2H(R)X2, H+COH(R)RCHXCORCH2H(R) OH-X2,COH(R)CRXXCOR(H)CH3X2,NaOHCOR(H)OH + CHX3Haloform卤仿X2+ NaOHNaOXCOR(H)CH3COR(H)CX3NaOXNaOHCHX3+COR(H)OH4. Chemical Proper

31、ties4.2.2 Haloform Reactions卤仿反应卤仿反应NaOHCOCH3I2,COOH + CHI3IodoformYellow solidCHI3CH3CH R(H)OHI2,NaOHR(H)COOH +NaOICOCH3R(H)4. Chemical Properties4.2.2 Haloform ReactionsYellow solidCuprous OxideBrick red colorFehlings reagent: A + B A: CuSO4 (Copper Sulfate), B: the solution of potassium sodium ta

32、rtrate(酒石酸钾酒石酸钾) and sodium hydroxide(氢氢氧化钠氧化钠).R CHOR COOHFehlings reagentCu2O+COOHR-H+KMnO4/CHOR-Silver mirror reaction银镜反应银镜反应Tollens reagentAg+Ag(NH3)2OHCOOHR-CHOR-4. Chemical Properties4.3 氧化和还原反应氧化和还原反应(Oxidation and Reduction)4.3.1 OxidationTollens reagent can react with all aldehydes (alipha

33、tic and aromatic), but Fehlings reagent only can react with aliphatic aldehydes. You can use Fehlings reagent to distinguish aliphatic aldehydes and aromatic aldehydes.4. Chemical Properties4.3.1 OxidationAldehydes 醛Ketones 酮Tollens reagentFehlings reagentAliphatic aldehydesAromatic aldehydes(1) A B

34、 CABCI2 / NaOH不产生黄色沉淀不产生黄色沉淀BCAAg(NH3)2NO3产生银镜产生银镜B不产生银镜不产生银镜C产生黄色沉淀产生黄色沉淀P14610-14 试用简便的化学方法化学方法鉴别下列各组化合物OHCHO CH3CHOExercise:CH3(CH2)4CHOCHOCH2OHCOCH3 A B C DABCD托伦试剂托伦试剂不产生银镜不产生银镜ABCD斐林试剂斐林试剂产生砖红色沉淀产生砖红色沉淀A不产生砖红色沉淀不产生砖红色沉淀B产生银镜产生银镜I2 / NaOH不产生黄色沉淀不产生黄色沉淀C产生黄色沉淀产生黄色沉淀DExercise:(3)R-CHOR-H2,PtCH2OH

35、R-COH2,PtR-R-CHOHR-CH2OHR-CHOR-LiAlH4Lithium aluminium hydrideCH2OHR-CHOR-NaBH4Sodium borohydride4. Chemical Properties4.3.2 Reduction:Metal hydrides can reduce aldehydes and ketones to give alcohols. 伯醇仲醇醛酮Compare with hydrogenation reaction, application of metal hydrides is more selective. Metal h

36、ydrides only reduce the carbonyl group but not carbon-carbon double bond.H2,PtNaBH4CH2CH CH2CH2CHOCH3CH2CH2CH2CH2OHCH2CH CH2CH2CH2OH4. Chemical Properties4.3.2 Reduction:COHR-R-( )R-Zn-Hg/HClCH2H R-( )Zn-Hg/HCl:锌汞齐锌汞齐(zinc amalgam)克莱门森反应克莱门森反应(Clemmensen Reaction)COHR-R-( )R-CH2H R-( )85% H2NNH2H2O/

37、NaOHDEG or TEGDEG: Diethylene glycol, 二聚乙二醇二聚乙二醇(HOCH2CH2)2 OTEG: Triethylene glycol, 三聚乙二醇三聚乙二醇(HOCH2CH2OCH2)2O乌尔夫乌尔夫(Wolff)-凯惜纳凯惜纳(Kishner)-黄鸣龙黄鸣龙 Reduction4. Chemical PropertiesMethylene亚甲基4.3.2 Reduction: If the start material contains acid sensitive groups, Wolff-Kishner-黄鸣龙黄鸣龙 Reduction is app

38、lied to reduce the carbonyl group. Clemmensen Reaction is used to those carbonyl compounds which contain base sensitive groups.4. Chemical Properties4.3.2 Reduction:OHCOCH3Zn-Hg/HClOHCH2CH3康尼查罗反应康尼查罗反应(Cannizzaro Reaction)HCHOconc.NaOHHCOOH + CH3OHCHOconc.NaOHCOOH+CH2OHWhen a no -hydrogen aldehyde r

39、eact with concentrated sodium hydroxide solution, some of the aldehyde has been oxidized to carboxylic acid and some reduced to alcohol. This is the Cannizzaro Reaction.4. Chemical Properties4.3.2 Reduction:HCHOHCOOHCHOconc.NaOH+CH2OH+The reductive ability of formaldehyde is stronger than most other

40、 aldehydes. When excessive formaldehyde react with another no -hydrogen aldehyde in concentrated sodium hydroxide solution, formaldehyde will become formic acid and the another aldehyde will become alcohol. This is the crossed Cannizzaro Reaction.4. Chemical Properties交叉康尼查罗反应交叉康尼查罗反应(crossed Cannizzaro Reaction)4.3.2 Reduction:5. 重要的醛酮与醌类重要的醛酮与醌类5.1 甲醛甲醛(Formaldehyde)Formaldehyde has antiseptic properties and can be employed in the treatment of urinary tract infections(尿路感染尿路感染) due t