有机化学Chap 10 aldehydes and ketones20140413-7Y.ppt

1、Chapter 10 Aldehydes and Ketones,Undecanal 十一醛,2-Heptanone 2-庚酮,trans-2-Hexenal 反-2-庚醛,Civetone 香猫酮,Vanillin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）,Progesterone 孕酮,Testosterone 睾酮,甲醛 丙酮,Carbonyl g

2、roup 羰基,Aldehyde 醛,Ketone 酮,Common names(普通命名法) are normally used for the aldehydes containing four carbons or fewer.,1 Nomenclature,1.1 分类,芳香醛（酮）,脂肪醛（酮）,1.2 普通命名法,丙醛,甲(基)乙(基)酮,甲(基)环己(基)酮,二苯(基) 酮,苯乙醛,1 Nomenclature,For systemic names(系统命名法), the “e” of the parent alkanes name is dropped and the suff

3、ix “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,Aldehyde 醛,1 Nomenclature,formaldehyde,acetaldehyde,2-methylpentanal 2-甲基戊醛,3-chloropropanal 3-氯丙醛,(甲醛 mathanal ),( 乙醛ethanal ),5 4 3 2 1,3 2 1,1 Nomenclature,3

4、-methylbenzaldehyde 3-甲基苯(基)甲醛,(Z)-3-chloro-3-phenyl-2-propenal (Z)- 3-苯基-3-氯-2-丙烯醛,3 2 1,1 Nomenclature,The “e” of the parent alkane is dropped, and the suffix “one” is appended. The number of the carbon atom bearing the carbon-oxygen double bond begins the name. Give the carbonyl group the smalles

5、t number as far as possible. Aromatic ketones are often named by treating the benzene ring as a phenyl group.,Ketone 酮,1 Nomenclature,propanone,3-methyl-2-pentanone 3-甲基-2-戊酮,4-methoxycyclohexanone 4-甲氧基环己酮,1,4-cyclohexanedione 1，4-环己二酮,(acetone丙酮),1 2 3 4 5,2 3,1 Nomenclature,methyl phenyl ketone 苯

6、(基) 甲(基) 酮 甲(基)苯(基) 酮,cyclopropyl phenyl ketone 苯基环丙基酮,( phenylethanone 苯乙酮 ),( 2,2-dimethyl-1-phenylpropanone, 2,2-二甲基-1-苯基-丙酮),t-butyl phenyl ketone (苯基叔丁基酮),1 Nomenclature,2 Preparing Aldehydes and Ketones,2.1 Oxidation of alcohols,Collins reagent: CrO32C5H5N,2. Ozonization of alkenes,Ozonide 臭氧化

7、物,2 Preparing Aldehydes and Ketones,Show the major product of the following reaction:,Exercise:,3. Friedel-Crafts Acylation Reaction,Acyl chlorides or acid anhydrides react with benzene under the influence of an equivalent (not a catalytic amount) AlCl3 to form aromatic ketones.,acyl acyl chloride a

8、cid anhydride 酰基 酰氯 酸酐,2 Preparing Aldehydes and Ketones,2 Preparing Aldehydes and Ketones,3. Structure and Physical Properties,FIGURE. Structure of acetaldehyde 乙醛,3.1 羰基的结构,Alkene Carbonyl group 烯烃 羰基,3. Structure and Physical Properties,Ethylene Formaldehyde 乙烯 甲醛,1-Butene Propanal 1-丁烯 丙醛,Dipole

9、 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 97,1-Butene Propanal 1-Propanol,3.2 物理性质,4. Chemical Properties,燃烧热： (Heat of Combustion),Formaldehyde,Butanal 2-Butanone,2475kJ/mol 2442kJ/mol,电效应(Electronic effects) Recall that alkyl groups are electro

10、n donating. 空间位阻效应(Steric effects),4. Chemical Properties,Ketone酮,has two electron-donating alkyl groups that stabilize the partial positive charge,has only one electron-donating alkyl groups that stabilizes the partial positive charge,Aldehyde醛,亲核加成反应(Nucleophilic Addition),碳及氢的反应(Reactions at the

11、-position),氧化和还原反应(Oxidation and Reduction),4. Chemical Properties,+ -,4.1 亲核加成反应(Nucleophilic Addition),4. Chemical Properties,sp2 sp3,Arrhenius concept of acids and bases,Brnsted-Lowry concept of acids and bases,Lewis concept of acids and bases,4. Chemical Properties,Acid-base concept,4.1.1 与氢氰酸加成

12、(Addition of Hydrocyanic Acid),Cyanohydrin 氰醇(-羟基腈),Alcohol Acid -羟基酸,4. Chemical Properties,Aldehyde,Hydrogen cyanide,All aldehydes include aliphatic and aromatic aldehydes.,Aliphatic methyl ketones.,Cyclic ketones which the rings contain eight or less carbon atoms.,n8,反应物的结构要求：,Cyclohexanone,4. Ch

13、emical Properties,4.1.1Addition of Hydrocyanic Acid,Cyanohydrin Derivatives in Nature,Amygdalin 苦杏仁苷,Mandelonitrile 苯乙醇酰(扁桃腈),Benzaldehyde 苯甲醛,Toxic,cyanohydrin,alcohol acid,氰醇， -羟基腈,醇酸,H2O / H+, H ,-hydroxy amine,-羟基胺,4.1.1 与氢氰酸加成(Addition of Hydrocyanic Acid),4. Chemical Properties,4.1.2 与亚硫酸氢钠的加成

14、(Addition of sodium bisulfite),White Crystal,4. Chemical Properties,The 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 Properties,4.1.2Addition of s

15、odium bisulfite,All aldehydes include aliphatic and aromatic aldehydes.,Aliphatic methyl ketones.,Cyclic ketones which the rings contain eight or less carbon atoms.,n8,反应物的结构要求：,4. Chemical Properties,4.1.2Addition of sodium bisulfite,Example ：Point out which compounds of the following molecules can

16、 react with sodium bisulfite:,Exercise:,4.1.2Addition of sodium bisulfite,4.1.3 与水的加成(Addition of water),Geminal Diol 偕二醇,4. Chemical Properties,Chloral Hydrate, Ataractic 水合三氯乙醛，镇静剂,Chloral 三氯乙醛,Hemiacetal 半缩醛,Acetal 缩醛,4. Chemical Properties,4.1.4 与醇的加成(Addition of Alcohols),Aldehyde,Acetals(缩醛) o

17、r ketals(缩酮) are stable to base, oxidants and reducer. So carbonyl compounds can be protected by converting them into their acetal or ketal forms, and then regenerating as needed.,4. Chemical Properties,4.1.4 Addition of Alcohols,Ketals 缩酮,Acetals as Prodrugs,Prodrug(前药)pharmacologically inactive co

18、mpounds that are converted by the body into active compounds.,Fluocinolone Acetonide Acetate 醋酸氟轻松,Active drug,Exercise:,10-12 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:,(3),4.1.5. 与格氏试剂的加成(Addition of Grignard Reagents),4. Chemical Properties,伯醇,仲醇,叔醇,甲醛,醛,酮,4.1.6 与氨衍生物的加成(Addition of der

19、ivatives of ammonia),Carbinolamine 醇胺,Imine N-取代亚胺,Schiff s base 希夫碱,4. Chemical Properties,4. Chemical Properties,4.1.6 Addition of derivatives of ammonia,2,4-dinitrophenyl hydrazone 2,4-二硝基苯腙,Yellow precipitation,Formation of 2,4-dinitrophenyl hydrazone can diagnose the presence of a carbonyl grou

20、p.,4. Chemical Properties,4.1.6 Addition of derivatives of ammonia,2,4-dinitrophenyl hydrazine 2,4-二硝基苯肼,Imines as Prodrugs,hydrolysis,Progabide,-氨基丁酸,羸 赢,在“ ”中找到“ ”,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赢羸羸羸羸 羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸

21、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,vitamin A (retinol) 视黄醇(维生素A),h,+,H2N-protein,retinal 视黄醛,11-cis-retinal,rhodopsin视紫红质,vitamin A (retinol) 视黄醇(维生素A),4.2 碳及氢的反应(Reactions at the -position),4. Chemical Properties,- 共轭效应,4.2.1 醇醛缩合(Aldol Condensation),Aldol 醇醛,4. Chemical Properties

22、,-hydroxyaldehyde(-羟醛),-unsaturated aldehyde (, -羟醛),Mechanism of aldol condensation :,Carbanion 碳负离子,Intermediate,Aldol,4. Chemical Properties,4.2.1 Aldol Condensation,Like most intermolecular reaction(分子间反应), the aldol condensation has an intramolecular version. Particularly favorable are intramol

23、ecular condensation that form the relatively strain-free five- and six-membered rings.,4. Chemical Properties,4.2.1 Aldol Condensation,交叉醇醛缩合(Crossed Aldol Condensation),4. Chemical Properties,4.2.1 Aldol Condensation,克莱森-斯密特反应(Claisen-Schmidt),4.2.2 卤代反应(Haloform Reactions),4. Chemical Properties,H

24、aloform 卤仿,4. Chemical Properties,4.2.2 Haloform Reactions,卤仿反应,4. Chemical Properties,4.2.2 Haloform Reactions,Yellow solid,Cuprous Oxide Brick red color,Fehlings reagent: A + B A: CuSO4 (Copper Sulfate), B: the solution of potassium sodium tartrate(酒石酸钾) and sodium hydroxide(氢氧化钠).,Fehlings reagen

25、t,4. Chemical Properties,4.3 氧化和还原反应(Oxidation and Reduction),4.3.1 Oxidation,Tollens reagent can react with all aldehydes (aliphatic and aromatic), but Fehlings reagent only can react with aliphatic aldehydes. You can use Fehlings reagent to distinguish aliphatic aldehydes and aromatic aldehydes.,4

26、. Chemical Properties,4.3.1 Oxidation,Aldehydes 醛 Ketones 酮,Tollens reagent,Fehlings reagent,Aliphatic aldehydes Aromatic aldehydes,(1),A B C,ABC,I2 / NaOH,不产生黄色沉淀,BC,A,Ag(NH3)2NO3,产生银镜,B,不产生银镜,C,产生黄色沉淀,P146,10-14 试用简便的化学方法鉴别下列各组化合物,Exercise:,A B C D,ABCD,托伦试剂,不产生银镜,AB,CD,斐林试剂,产生砖红色沉淀,A,不产生砖红色沉淀,B,产

27、生银镜,I2 / NaOH,不产生黄色沉淀,C,产生黄色沉淀,D,Exercise:,(3),Lithium aluminium hydride,Sodium borohydride,4. Chemical Properties,4.3.2 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

28、hydrides only reduce the carbonyl group but not carbon-carbon double bond.,4. Chemical Properties,4.3.2 Reduction:,Zn-Hg/HCl:锌汞齐(zinc amalgam),克莱门森反应(Clemmensen Reaction),DEG: Diethylene glycol, 二聚乙二醇(HOCH2CH2)2 O TEG: Triethylene glycol, 三聚乙二醇(HOCH2CH2OCH2)2O,乌尔夫(Wolff)-凯惜纳(Kishner)-黄鸣龙 Reduction,4

29、. Chemical Properties,Methylene 亚甲基,4.3.2 Reduction:,If the start material contains acid sensitive groups, Wolff-Kishner-黄鸣龙 Reduction is applied to reduce the carbonyl group. Clemmensen Reaction is used to those carbonyl compounds which contain base sensitive groups.,4. Chemical Properties,4.3.2 Re

30、duction:,康尼查罗反应(Cannizzaro Reaction),When a no -hydrogen aldehyde react 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 Properties,4.3.2 Reduction:,The reductive ability o

31、f formaldehyde is stronger than most other 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(crossed Cannizzaro Reaction),4.3.2 Reduction:,5. 重要的醛酮与醌类,5.1