文稿大二有機下final

1、Final ReviewGive IUPAC names to the following compounds:2. Draw structures corresponding to the following IUPAC names:3. Predict the major product(s), or fill in the missing substrates in the following reactions:4. Short answer questions:5. Propose reasonable mechanisms to the following reactions:6.

2、 Synthesize the following target molecules from corresponding starting organic compounds and any inorganic compounds you need. 7. Structure determination (15%)Final ReviewChapter Ten Ethers and EpoxidesChapter Ten Ethers and Epoxides1. Chemical Properties of Ether(1). Oxonium Salts Formation of Ethe

3、rsApplication？(2). Acidic Cleavage of Ethers哪里斷？2. Preparation of EthersChapter Ten Ethers and EpoxidesWilliamson Ether Synthesis混合醚的合成用相應的醇鈉和鹵代烴的親核取代反應，用醇的分子間脫水的方法易得到混合物。醇的分子間脫水只適合用來合成簡單的單醚。Chapter Ten Ethers and Epoxides3. Chemical Properties of EtherSN2SN1(1) Acid-Catalyzed Epoxides Opening(2) Ba

4、se-catalyzed Epoxides OpeningSN1?哪里開環(huán)？哪里開環(huán)？Chapter Ten Ethers and Epoxides4. Claisen Rearrangement Reactions of EthersRearrangement +Isomerization 合成增加兩個碳原子的方法，關注有取代基的環(huán)氧乙烷此反應在哪里開環(huán)？Chapter Ten Ethers and Epoxides No Isomerization occurs5. Mechanism:Acid-CatalyzedEpoxides OpeningC+RearrangementElectro

5、phileChapter Eleven Aldehydes and KetonesFinal Review1. Nucleophilic Addition Reactions of Aldehydes and KetonesChapter Eleven Aldehydes and KetonesThe influencing factors of the reaction:(a) Electronic effect:+ Relative reactivity(b) Steric effectSteric hindrance Relative reactivity重要的中間體，多一個碳原子部分醛

6、酮的分離提純，現(xiàn)象？2，4-二硝基苯肼的反應，用于醛酮的鑒定，制備烯烴的好方法反應的可逆性，可在反應中對羰基進行保護Witting 反應醛、甲基脂肪酮、C8以下環(huán)酮格式試劑和醛酮，生成各種結構的醇制備醇的好方法，注意反應有加成和酸性水解兩步，寫完整條件通常用二元醇，乙二醇pH = 4-5 ?可以轉換成COOH, CH2NH2,條件？RLi, Organozinc Reagent? Chapter Eleven Aldehydes and Ketones2. Reactions of -H(a) The Aldol Reactions (羥醛縮合反應)The carbon chain incre

7、ase doubled.A good method to prepare ,-unsaturated aldehydes.(1)-H; (2) base COOHCH2OH產物通過選擇性的氧化還原，可得多種化合物，關注！Chapter Eleven Aldehydes and KetonesMixed Aldol ReactionClaisen-Schmidt condensationsKnoevenagel condensationsPerkin Condensation(2) Alpha Halogenation(鹵代) of Aldehydes and KetonesIntramolec

8、ular Aldol ReactionsCyclic compoundsApplication?3. Oxidation of Aldehydes and KetonesChapter Eleven Aldehydes and Ketones4. Reductions of Aldehydes and KetonesChapter Eleven Aldehydes and Ketones關注不同還原劑的選擇性Chapter Eleven Aldehydes and KetonesThe Cannizzaro Reaction5. Preparation of Aldehydes and Ket

9、onesChapter Eleven Aldehydes and Ketones(1). Oxidative Cleavage of Alkenes. (2). Hydration of Alkynes (3). Oxidation of alcohols(4). Friedel-Crafts Acylation and Gattermann-koch reaction(5). Partially Reduction of Certain Carboxylic Acid Derivatives6. Conjugated Nucleophilic Addition to ,-Unsaturate

10、d Aldehydes and KetonesChapter Eleven Aldehydes and Ketones1, 2-additonStrongly basic nucleophiles: RMgX or RLi 1, 4-additonWeakly basic nucleophiles: RNH2 , HCNChapter Eleven Aldehydes and KetonesChapter Eleven Aldehydes and KetonesThe mechanism of acid-catalyzed reaction of an aldehyde or ketone w

11、ith an alcohol.7. Mechanism: (2) The mechanism of aldol reaction(3) The mechanism of Cannizzaro ReactionIR:1850-1700 cm-1Stretch：1H NMR: = 910 ppm= 22.5 ppmChapter Eleven Aldehydes and Ketones8. Spectroscopy of Aldehydes and KetonesChapter Eleven Aldehydes and Ketones 9. To distinguish of aldehydes

12、and ketone NaHSO3, Tollens reagent，F(xiàn)eling reagent,NaOH + I2常見的鑒別試劑，鑒別對象是什么？Chapter Twelve Carboxylic AcidsFinal ReviewChapter Twelve Carboxylic Acids1. Preparation of Carboxylic Acids選擇性氧化Get the carboxylic acid with one more carbon：Chapter Twelve Carboxylic Acids-羥基酸的合成底物的要求？底物的要求？Chapter Twelve Ca

13、rboxylic AcidsGet the carboxylic acid with two more carbon：Iodoform reaction，-unsaturated carboxylic acidChapter Twelve Carboxylic AcidsReformatsky reactionAldol reaction2. Acidity of Carboxylic AcidsChapter Twelve Carboxylic AcidsChapter Twelve Carboxylic AcidsComparing the relative acidity substit

14、uted carboxylic acids12343. Nucleophilic Acyl (?；?) Substitution ReactionsChapter Twelve Carboxylic Acids4. Reduction of Carboxylic Acids4. Decarboxylation (脫羧) of Carboxylic AcidsChapter Twelve Carboxylic Acids什么樣的羧酸容易脫羧？4. Heating Reactions of Dicarboxylic AcidsChapter Twelve Carboxylic AcidsDecar

15、boxylationIntramolecular dehydration兩個羧基相對位置不同，產物不同5. Halogenation of Carboxylic AcidsChapter Twelve Carboxylic Acids-NH2, -CN, -OHmultifunctional molecules X6. Dehydration of Hydroxyl Carboxylic Acids (羥基酸) :Chapter Twelve Carboxylic Acids羥基和羧基的相對位置決定了產物！Chapter Twelve Carboxylic Acids7. Spectrosco

16、py of carboxylic acidsIR:Stretch：1710 cm-1Stretch：3000-2500 cm-11H NMR: = 1013 ppm= 22.5 ppm8. Mechanism:Esterification with acid as catalystChapter Thirteen Carboxylic Acids DerivativesFinal Review1. Nucleophilic Acyl Substitution ReactionAddition reactionElimination reactionRelative reactivity of

17、Nucleophilic Acyl Substitution Reaction:Acid halides Acid anhydride Esters AmidesChapter Thirteen Carboxylic Acids DerivativesHydrolysis, 水解Acoholysis, 醇解PyridineAminolysis, 氨解R2CuLi ?Chapter Thirteen Carboxylic Acids DerivativesChapter Thirteen Carboxylic Acids DerivativesNot often usedEither by aq

18、ueous base or by aqueous acid.Try to propose the mechanism常用來合成連有兩個相同取代基的叔醇Chapter Thirteen Carboxylic Acids Derivatives2. The Reduction Reaction of Carboxylic Acids DerivativesLiAlH4 / H3O+ROH3. Chemistry of amides4. Spectroscopy of Carboxylic Acid DerivativesChapter Thirteen Carboxylic Acids Deriv

19、ativesExample Formula Infrared absorption (cm-1)Acetyl chloride CH3COCl 1810Acetyl anhydride (CH3CO) 2O 1820Ethyl acetate CH3COO CH2CH3 1735Acetamide CH3CONH2 1690Acetic acid CH3COOH 1710Acetone CH3COCH3 1715Chapter Thirteen Carboxylic Acids Derivatives1HNMR (ppm)Chapter Fourteen - Keto EstersFinal

20、ReviewChapter Fourteen - Keto Esters1. Claisen condensation reaction酯分子中-氫的酸性-碳負離子的生成-酮酸酯堿親核取代烷氧基離去Mechanism ?Two step: (1)EtONa/EtOH, (2) H+The mixed Claisen CondensationThe Dieckmann CyclizationMixed Claisen-like reactions-diketones 2. The Acetoacetic Ester(乙酰乙酸乙酯) SynthesisChapter Fourteen - Keto

21、 EstersThese three carbons from acetoacetic esterThis R group from alkyl halide1) NaH / RCOCl; 2) H3O+, heat1) EtONa / RX; 2) EtONa / RX ; 3) H3O+, heat（為引入烷基）（為引入?；┓磻獥l件寫完整！合成甲基酮在哪里拆分？3. The Malonic Ester (丙二酸酯) SynthesisChapter Fourteen - Keto Esters取代乙酸，在哪里拆分？To prepare1) EtONa / RX; 2) EtONa /

22、RX ; 3) H3O+, heat（為引入烷基）The Knoevenagel ReactionThe Perkin ReactionThe Michael ReactionThe Robinson annulation (環(huán)化)- Michael reaction + intramolecular Aldol reaction. Chapter Fourteen - Keto Esters含有活性氫的化合物，在EtONa/EtOH條件下容易失去活性H，產生C-離子中間體，是親核的質點，會和另外分子的醛酮發(fā)生親核加成，和羧酸的衍生物（酯）發(fā)生親核取代或和，不飽和化合物發(fā)生加成。這里考點比較多

23、，大家關注！Final ReviewChapter Fifteen Nitro Compounds and Amines1. Aromatic Nitro CompoundsH2 / Ni ?a) Electrophilic substitution reaction : b) Nucleophilic substitution reaction : Chapter Fifteen Nitro Compounds and Amines2. Synthesis of AminesChapter Fifteen Nitro Compounds and Aminesa. Reduction reac

24、tion :(b) Gabriel amine synthesisChapter Fifteen Nitro Compounds and Amines(c). Reductive Amination of Aldehydes and Ketones(d). Hofmann Rearrangement3. Chemical Properties of Amines(1) . Basicity of AminesThe density of the lone pair electron B A D CTo purify and separate aminesComparing the relati

25、ve basicity:會完成反應Chapter Fifteen Nitro Compounds and Aminesa). 分離，提純-b). 鑒定和氨基的保護-c). 降低氨基的定位活性，一般只在對位引入取代基(2). Acylation (?；? of AminesAmino group NH2-AcylationAmido group RCONH-(3). Sulfonamides (磺酰胺) formationHinsberg Test: To distinguish primary , secondary and tertiary amines 試劑： PhSO2Cl + NaOH不同胺的現(xiàn)象？(4). Electrophilic Aromatic Substitution ReactionChapter Fifteen Nitro Compounds and Aminesa). 胺基容易被氧