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1、用中文或英文系统命名法命名下列化合物或根据名称写出结构式。注意R,S以及Z,E命名（本题共8小题，每小题1分，共8分） 简略回答问题。（本题共8小题，每小题3分，共24分） 完成反应写出主要产物。（本题共12小题，每小题2分，共24分） 用化学方法区别各组化合物。（本题共12分） 推测化合物的结构。（本题共2小题，每小题6分，共12分） 以指定原料合成化合物（本题共4小题，每小题5分，共20分）,命名 醛、酮、羧酸、羧酸衍生物、胺简答 一些化合物的沸点比较,Chap 19 Synthesis Review,Oxidation 2 alcohol + Na2Cr2O7 ketone 1 alco
2、hol + PCC aldehyde Ozonolysis of alkenes.,Synthesis Review (2),Friedel-Crafts acylation Acid chloride/AlCl3 + benzene ketone CO + HCl + AlCl3/CuCl + benzene benzaldehyde (Gatterman-Koch) Hydration of terminal alkyne Use HgSO4, H2SO4, H2O for methyl ketone Use Sia2BH followed by H2O2 in NaOH for alde
3、hyde.,Ketones from 1,3-Dithiane,After the first alkylation, remove the second H+, react with another primary alkyl halide, then hydrolyze.,Aldehydes from Acid Chlorides,Use a mild reducing agent to prevent reduction to primary alcohol.,与金属有机试剂的加成,Grignard试剂,有机锂试剂,炔钠,与醛或酮加成后,水解,制得醇。,Reformasky反应,反应机理
4、：,19-9 Addition of Alcohol,缩醛,缩酮,Formation of Imines亚胺,Nucleophilic addition of ammonia or primary amine, followed by elimination of water molecule. C=O becomes C=N-R,羟氨 肼 苯肼 2,4-二硝基苯肼 氨基脲 肟 腙 苯腙 2,4-二硝基苯腙 缩氨脲,H2NY,产物 肟、腙、苯腙、缩氨脲等大多为白色晶体，有固定的晶型和熔点，可用于鉴定醛酮；晶体易分离，可用于提纯醛酮（产物在稀酸作用下分解成原来的醛酮）。,Phosphorus Y
5、lides磷叶立德,Prepared from triphenylphosphine and an unhindered alkyl halide.三苯基膦和卤代烃反应合成季磷盐 Butyllithium then abstracts a hydrogen from the carbon attached to phosphorus.,Mechanism for Wittig,The negative C on ylide attacks the positive C of carbonyl to form a betaine. Oxygen combines with phosphine t
6、o form the phosphine oxide.,羰基化合物亲核加成的活性次序：,Tollens Test Tollens试剂,Add ammonia solution to AgNO3 solution until precipitate dissolves.银氨溶液 Aldehyde reaction forms a silver mirror.,(b) Fehling 试剂:,砖红色,用于鉴别脂肪族醛和芳香族醛,硫酸铜溶液和酒石酸钠钾的混合碱溶液,19-15 Reduction Reagents,Sodium borohydride, NaBH4, reduces C=O, but
7、 not C=C. Lithium aluminum hydride, LiAlH4, much stronger, difficult to handle. Hydrogen gas with catalyst also reduces the C=C bond.,Clemmensen Reduction,Wolff-Kisher Reduction,Form hydrazone, then heat with strong base like KOH or potassium t-butoxide. Use a high-boiling solvent: ethylene glycol,
8、diethylene glycol, or DMSO.,(3) Cannizzaro 反应(歧化反应),无-H的醛与浓碱共热，发生自身的氧化还原反应，生成等量的酸和醇。,分子间发生两种性质相反的反应 歧化反应 (disproportionation),醛：HCHO, R3CCHO, ArCHO,NaOH脂肪胺NH3 带供电子基苯胺苯胺带吸电子基苯胺,Chap 20 碱性强弱：,R对N供电子碱性增大,苯基对N吸电子碱性减小,Hofmann elimination, the product is commonly the least-substituted alkene.,（1）脂肪胺,用于鉴别三
9、种不同结构的脂肪胺,小结:,（2）芳香胺,重氮盐，重要的有机合成中间体,N-亚硝基化合物(黄色固体),绿色片状固体(亲电取代产物),用于鉴别三种不同结构的芳香胺,Synthesis of Amine,Reductive Amination Acylation-Reduction Direct Alkylation Gabriel Synthesis Azide Reduction N3 Nitrile Reduction Hofmann Rearrangement,SnCl2 的选择性还原：,3硝基苯甲醛 3氨基苯甲醛,Chap 21 取代基诱导效应对酸性的影响,_,_,吸电基使负离子稳定,供
10、电基使负离子不稳定,酸性增强,酸性减弱,Synthesis of acid,Oxidation of primary alcohols and aldehydes with chromic acid. Alkyl benzene oxidized to benzoic acid by hot KMnO4 or hot chromic acid. Grignard Synthesis Hydrolysis of Nitriles,21-9 Diazomethane重氮甲烷,CH2N2 reacts with carboxylic acids to produce methyl esters qu
11、antitatively. Very toxic, explosive. Dissolve in ether.,22-2 Boiling Points,Even 3 amides have strong attractions.,Reactivity,Reactivity decreases as leaving group becomes more basic.,Synthesis of Nitriles,1 amide,alkyl halide,diazonium salt,Interconversion of Derivatives 羧酸及其衍生物的相互转化,More reactive
12、derivatives can be converted to less reactive derivatives.,Chap 23 Acidity of -Hydrogens,pKa for -H of aldehyde or ketone 20. Much more acidic than alkane or alkene (pKa 40) or alkyne (pKa = 25). Less acidic than water (pKa = 15.7) or alcohol (pKa = 16-19). In the presence of hydroxide or alkoxide i
13、ons, only a small amount of enolate ion is present at equilibrium.,卤仿反应还用于制备某些羧酸：,黄色结晶,1. 用于结构鉴定； 2. 制备少一个碳的羧酸。,23-7 Aldol Condensation 羟醛缩合：两分子含有-H的醛在稀碱或稀酸催化下发生缩合反应生成羟基醛,Enolate ion adds to C=O of aldehyde or ketone. Product is a -hydroxy aldehyde or ketone. Aldol may lose water to form C=C.,23-10
14、Aldol Cyclizations,1,4-diketone forms cyclopentenone. 1,5-diketone forms cyclohexenone.,23-11 Claisen Condensation,Two esters combine to form a -keto ester.酮酸酯,Claisen 酯缩合反应,无-氢,有-氢,交错酯缩合,自身酯缩合,23-14 Syntheses Using -Dicarbonyl Compounds,More acidic than alcohols. Easily deprotonated by alkoxide ions and alkylated or acylated. At the end of the synthesis, hydrolysis removes one of the carboxyl groups.,malonic ester, pKa = 13 丙二酸二乙酯,A Michael Reaction,Enolates can react with ,-unsaturated compounds to give a 1,5-diketo product.,Homework19-42, 19-46, 19-47,20-25, 21-18,22-19,23-35,23-36,23-32,
