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1、Claisen condensations involve a ester with -hydrogen and the carbonyl group of another ester. The Claisen condensation bears the same relationship to the aldol condensation that the addition of a nucleophile to an ester does to the addition to an aldehyde or ketone. If a ester contains -hydrogen, we
2、 can use the Claisen condensation to produce -keto ester.3. Claisen condensation ( Ester condensation )1H+Mechanism of Claisen condensation :2A Claisen condensation between two different esters both with -hydrogen is call a crossed Claisen condensation. Thus two products are possible. There are some
3、 simple ways to limit the possibilities in a crossed Claisen reaction. If one partner has no -hydrogen, it can function only as an acceptor, and not as the nucleophile partner in the reaction.3 Leaving group4Acetylacetic ester has some special chemical properties:NaHSO3H2N-YHCNAcetylacetic ester can
4、 react with Acetylacetic ester canmake bromine water depigmentreact with sodium to release hydrogen gasreact with ferric chloride cause color reaction5These special chemical properties are due to the tautomerism of acetylacetic ester. keto-form( 93 % )enol-form( 7 % )4. Keto-enol TautomerismP. 12861
5、) Simple ketones are almost keto-form.Summary of Keto-enol tautomerism:2) If the-hydrogens be substituted by or ,the stability of enol form will increase. Substituted by make the enol form more stable than substituted by .73) If the enol form cause the conjugate system become longer or form intramol
6、ecular hydrogen bond, the enol form is stable.8P. 128P. 133 9-14 (2)9Acidic cleavage :5.5.Cleavage reaction of acetylacetic ester 10Ketonic cleavage :11Chapter 12 Nitrogenous Compounds and AlkaloidsSection 1 Amine. Classification and Nomenclatureammoniaprimary aminesecondary aminetertiary amine12qua
7、ternary ammonium saltquaternary ammonium hydratetertiary amineQuaternary ammonium hydrates are strong base. The basicity of quaternary ammonium hydrates are similar to sodium hydroxide.季铵盐季铵碱13胺：有机非离子型胺：有机非离子型 (amine )铵：离子型铵：离子型 (ammonium ion )氨：氨水、氨气或有机基团氨：氨水、氨气或有机基团 ( ammonia，amino )14aliphatic am
8、ines:aromatic amines:15The systematic nomenclature names amines analogously to alcohol. Another method names amines as substituted alkanes. . The names of aromatic amines are base on the parent compound, called benzenamine（苯胺）（苯胺） by the official world and aniline (or aminobenzene) by everyone elseA
9、mines bearing different R are named by ordering the groups alphabetically16methylaminediethylaminetriethylamineBenzylethylmethylamine 甲乙苄胺甲乙苄胺N,N-dimethylaniline171-amino-3-methylbutanebenzyldodecyldimethyl ammonium bromide or bromo-geramine, 溴化二甲基十二烷基苄基铵溴化二甲基十二烷基苄基铵新洁尔灭，苯扎溴铵，新洁尔灭，苯扎溴铵，disinfector（消
10、毒剂）（消毒剂）18II. Structure of Amines19 ammoniamethylamineanilinetrimethylamine20. Preparation of Aromatic AmineFe/HCl can reduce nitro group but can not reduce carbon-carbon double bond.Ni, Pd, Pt21. Chemical Properties:1. Basicity and Salt FormingA strongly basic amine is a good competitor for H+ and
11、its ammonium ion is a relatively weak acid (more stable); a weakly basic amine is less effective competitor for H+, and its ammonium ion is a relatively strong acid.ammonium ion22Sequence of the basicity of amines23Procaine （普鲁卡因）（普鲁卡因）procaine hydrochloride, local anesthesia24盐酸双氯醇胺、盐酸克仑特罗盐酸双氯醇胺、盐酸
12、克仑特罗 Clenbuterol hydrochloride, Spiropent 瘦肉精瘦肉精252. Acylationamide 2627Acetanilide had been used as antifebric, but its toxicity is too high. Phenacetin非那西丁非那西丁AcetanilideParacetamol扑热息痛扑热息痛283. Sulfonylationbenzene sulfonyl chloridep-toluenesulfonyl chloride29crystal-I effectweak acidbenzene sulfo
13、namide30The above reaction is named Hinsberg Reaction（兴兴斯堡反应斯堡反应 ）. Using this reaction can distinguish primary, secondary and tertiary amines. The products of primary amines react with benzene sulfonyl chloride is weak acid, so can dissolve in sodium hydroxide solution. The products of secondary am
14、ines are crystal, and can not dissolve in sodium hydroxide solution. For tertiary amines, this reaction can not take place.314. React with nitrous acid (HNO2)(1) Primary amines32(2) Secondary aminesnitrosoamines (yellow oil)亚硝胺亚硝胺33(3) Tertiary aminesAliphatic tertiary amines do not react with nitro
15、us acid to give an isolable product.34emerald green solidActually, we use sodium nitrite/hydrochloric acid NaNO2/HCl instead of nitrous acid (HNO2).yellow solid35Because primary amines react with nitrous acid will give nitrogen gas; secondary amines will produce yellow oil and the products of aromat
16、ic tertiary amines are yellow solid. So it is easy to distinguish primary, secondary and tertiary amine by reacting with nitrous acid.36Something More:Nitrosoamines are important because many are known to be potent carcinogens. This finding has led to a controversy over the use of sodium nitrite (Na
17、NO2) as a preservative in foods because it might be a nitrosating agent under physiological conditions, or under the conditions in which food is prepared. The classic example is the frying of bacon, which generates nitrosoamines. However, the evidence is not definitive on this point. Many foods (spi
18、nach), even our own bodies, produce nitrites.37N-Nitrosodimethylamine 38white precipitation5. Special Reaction of Aniline39V. Important AminesCholine（胆碱胆碱）Acetylcholine（乙酰胆碱）（乙酰胆碱）40Dopamine (DA，多巴胺), the decrease of DA will cause parkinsonism.41瑞典阿尔维德卡尔松(Arvid Carlsson ) 美国保罗格林加德 (Paul Greengard )
19、奥地利埃里克坎德尔 (Eric Kandel ) The Nobel Prize in Physiology or Medicine 2000 425-Hydroxytryptamine (5-羟色胺羟色胺) , Serotonine (血清胺血清胺 )43Melatonin (MLT) 褪黑素褪黑素(又称松果体素或脑白金又称松果体素或脑白金) 44Fluoxetine (氟西汀氟西汀 )Prozac (百忧解百忧解) Are you prozac today?45Paroxetine，Seroxat（帕罗西汀，赛乐特）（帕罗西汀，赛乐特） 46(S)和(R)-西布曲明47epinephrin
20、enorepinephrineisoprenaline, synthetic medicine 48ephedrinedeoxyephedrine, “ice,” a popular pep pill.Phenylpropanolamine , PPA49deoxyephedrine, “ice,” a popular pep pill.How to synthesize deoxyephedrine from ephedrine?50Can we use Clemmensen Reaction to reduce the carbonyl group? Why?Route 1:51Clemm
21、ensen ReactionZn-Hg/HCl: zinc amalgam52Route 2:53Ecstasy, 3,4-methylenedioxymethamphetamine (MDMA) 爱它死爱它死, 3,4-亚甲二氧基甲基安非他命亚甲二氧基甲基安非他命, 快乐丸快乐丸, E仔仔, 摇头摇头丸丸5455Picture of Some MDMA (Ecstasy) pills 56 MDMA在2001年被美国食品药物管理局（Food and Drug Administration；FDA）批准用于创伤后应激障碍（post-traumatic stress disorder)患者的试验
22、。57Section 2 Diazo and Azo Compounds. Diazotization Reactionbenzene diazonium chloride0558. Reaction of Diazo Salt1. Substitution59H3PO2: hypophosphorous acid (次磷酸次磷酸)602) How to synthesize 1,3,5-tribromobenzene from benzene?Question: 1) How to synthesize 2-methyl benzoic acid from toluene?61051)622)0563
