1、Chapter 10,Alcohols and phenols 第十章 醇與酚,Organic Chemistry A (1) By Prof. Li Yan-Mei Tsinghua University,醇（Alcohol）,酚（Phenol）,Content,Part I Alcohols 10.1 Structure, isomerization, classification and nomenclature 10.2 Physical and spectroscopic properties 10.3 Monobasic/Monohydroxyl alcohol 10.4 Poly

2、basic alcohol 10.5 Preparation of alcohol 10.6 Sources and usages,Part II Phenol/Hydroxybenzene 10.7 Structure and nomenclature 10.8 Physical and spectroscopic properties 10.9 Chemical reactions 10.10 Preparations 10.11 Sources and usages,Part I Alcohols 第一部分 醇,10.1.1 Structure 10.1.2 Isomerization

3、10.1.3 Classification 10.1.4 Nomenclature,10.1 Structure, isomerization, classification and nomenclature,sp3 hybridization, 2D,Very close to water Many alcohols completely miscible with water,10.1.1 Structure 結(jié)構(gòu),10.1.2 Isomerization 異構(gòu),位置異構(gòu),碳架異構(gòu),官能團(tuán)異構(gòu),10.1.3 Classification 分類(lèi), C4,C5 C11, C12,根據(jù)羥基數(shù)目：

4、,一元醇 二元醇 三元醇,根據(jù)所連的碳原子不同：,一級(jí)醇（伯醇） 二級(jí)醇（仲醇） 三級(jí)醇（叔醇）,根據(jù)所含碳原子數(shù)目：,低級(jí)醇 中級(jí)醇 高級(jí)醇,10.1.4 Nomenclature 命名,Inter molecular hydrogen bond,Boiling point,Melting point,Simple alcohols completely miscible with water 與水形成氫鍵 低級(jí)醇一般與水任意混溶,10.2 Physical and spectroscopic properties,10.2.1 Physical properties,分子間氫鍵導(dǎo)致熔點(diǎn)、沸

5、點(diǎn)較高,Simple alcohols may form co-crystals with inorganic salts. 低級(jí)醇與一些無(wú)機(jī)鹽（如：MgCl2、CaCl2、CuSO4等）形成結(jié)晶狀的分子化合物 結(jié)晶醇（醇化物）,MgCl2, CuSO4 ,MgCl2 6 CH3OH,CaCl2 4 C2H5OH,CaCl2 4 CH3OH,用途：除去有機(jī)溶劑中少量的醇 將醇與其它有機(jī)物分開(kāi) 危害：不可用MgCl2、CaCl2、CuSO4等來(lái)干燥低級(jí)醇,10.2.1 Spectrometry,IR,(O-H),35503450cm-1,(O-H),34003200cm-1,in inter m

6、olecular hydrogen bonding systems,(-OH),36003500cm-1,in intra molecular hydrogen bonding systems,(-OH),32003500cm-1,multi molecule cluster,(-OH),34003200cm-1,(O-H),3710cm-1,(O-H),3300cm-1,(O-H),36003450cm-1,IR of OH bond in water molecule,Solid, ice,Crystallized water,Liquid water,NMR,0.5 - 5.5, 3.7

7、,15 - 19,活潑氫,10.3.1 Acidity and basicity 10.3.2 Esterifying 10.3.3 Nucleophilic substitution 10.3.4 Dehydration and elimination,10.3 Monobasic/Monohydroxyl alcohol,Lone pair electrons Basicity Nucleophile,Acidity Ionization Reacting with alkali metals,Labile beta-hydrogen Elimination Oxidation Dehyd

8、ration,Brief introduction,OH is not a good leaving group. Proton is often required to change the bad leaving group OH into a good leaving group OH2+,好的離去基團(tuán),10.3.1 Acidity and basicity 酸、堿性,Stronger acidity,Weaker acidity,(1) Relative acidity 酸性順序,(A) Acidity 酸性,原因：溶劑化效應(yīng)的影響,More solvation leads to mo

9、re stable positive ion.,溶劑化效應(yīng)的影響：,Stronger acidity,Weaker acidity,Inductive effect,Electron cloud pulled,誘導(dǎo)效應(yīng)的影響：,Na,(2) Reaction with metals 與金屬的反應(yīng),K,Ca,Mg,Al,Rb,Sr,Ba,Cs,Reaction rate,RCH2OH R2CHOH R3COH,Applications,Deal with such metals with alcohol, reducing reaction rate, avoiding explosion. A

10、lcoholic metals are good nucleophiles. 醇金屬可作為好的親核試劑。,(B) Basicity 堿性,Boron trifluoride,好的離去基團(tuán),好的離去基團(tuán),10.3.2 Esterification 酯化反應(yīng),Organic acid,Inorganic acid,某酸某酯,硝酸某酯,亞硝酸某酯,硫酸氫某酯,Acyl chloride,Anhydride,Mechanism 機(jī)理,10.3.3 Nucleophilic substitution 親核取代反應(yīng),Nucleophilic reagent 親核試劑,HX, PX3, SOCl2 .,常見(jiàn)

11、產(chǎn)物：RX（RCl）,(A). Reactions with HX 與HX的反應(yīng),Reactivity,Mechanism：H+及ZnCl2的作用 - 形成好的離去基團(tuán),SN1 or SN2 ?,Generally, 1o ROH follows SN2 mechanism, while 2o and 3o ROH follows SN1 mechanism, which is often coupled with an anion rearrangement.,易發(fā)生重排,Mechanism-neighboring group participation 鄰基參與,Lucas reagent

12、: Lucas試劑,Reactivity 反應(yīng)性,Reaction occurs immediately 立刻反應(yīng),Reaction occurs after 25 min 片刻(2-5分鐘)后反應(yīng),Reaction occurs when heated 加熱才反應(yīng),C6以下一元醇 溶于HCl,不溶于HCl 變渾,由于鑒別10、20、30醇,(B). Reactions with PXn,Reaction,Mechanism,RCl is often prepared with PCl5 and the corresponding alcohol, while RI with P, iodin

13、e, and the corresponding alcohol.,不重排,(C) Reactions with SOCl2,No rearrangement!,不重排,10.3.4 Dehydration and elimination 脫水與消除,(A) Intermolecular 分子間脫水,Example,A side reaction of alcohol dehydration to form ethene. You have performed this experiment at high school.,Mechanism,本質(zhì)：親核取代反應(yīng),(B) Intramolecu

14、lar dehydration,Example,This reaction follows an E1 elimination mechanism.,Mechanism,Reactivity,Product,Follows Zaitzevs rule E form,本質(zhì)：消去反應(yīng),Rearrangement occurs when a more stable anion is formed.,注意：,Competition between intermolecular and intramolecular reaction often exists. Under high temperatur

15、e, elimination is favored, otherwise intramolecular dehydration.,10.3.5 Oxidation 氧化反應(yīng),O: Na2Cr2O7, HNO3, KMnO4,一般地：,Sarrett reagent：,CrO3 + pyridine,特殊情況：,實(shí)驗(yàn)室常用方法：,Jones reagent：,CrO3 + diluted H2SO4,橙色透明,藍(lán)綠色 不透明,鑒別！,pyridinium chlorochromate: 氯鉻酸吡啶鹽（PCC）,When air is pumped in, water vapor is gener

16、ated.,工業(yè)上常用方法：脫氫,還原性氣氛，易將產(chǎn)物又還原為醇,10.4.1 Reactions similar to monobasic alcohol 10.4.2 Reactions different from monobasic alcohol,10.4 Polybasic alcohol 多元醇,10.4.1 Reactions similar to monobasic alcohol 與一元醇類(lèi)似的性質(zhì),Acid-base reaction Esterifying Nucleophilic substitution Dehydration and elimination Hyd

17、rogenation (Oxidation) Dehydrogenation,10.4.2 Reactions different from monobasic alcohol 多元醇的特殊性質(zhì),(A). Reaction with Cu(OH)2,Identification of 1,2-diol, or some substance with similar substructure. 用于鑒別1,2-二醇或具有鄰二羥基的多元醇,Soluble, blue 藍(lán)色 可溶,(B). Reaction with periodic acid 與高碘酸的反應(yīng),Reaction,This react

18、ion is usually used to identify structures.,Mechanism,環(huán)狀酯中間體,氧化值：7,氧化值：5,注意：環(huán)狀酯中間體，要求兩個(gè)羥基處于順式,均難發(fā)生反應(yīng),Application,反應(yīng)定量進(jìn)行，由消耗的高碘酸的量可測(cè)定鄰二醇的量 推斷結(jié)構(gòu)：,(C). Pinacol rearrangement 嚬哪醇重排,Pinacol 嚬哪醇,Pinacolone 嚬哪酮,鄰二醇在酸作用下的重排,較不穩(wěn)定的碳正離子（碳外層6個(gè)電子）,較穩(wěn)定的 鹽（碳外層8個(gè)電子）,甲基遷移,Which carbocation is favored ? 生成哪個(gè)碳正離子？,主產(chǎn)物

19、,次產(chǎn)物,Which group shifts ? 哪個(gè)基團(tuán)遷移？,遷移能力： R-ph ph NO2-ph R CH3 H 即：提供電子、穩(wěn)定正電荷能 力較強(qiáng)的基團(tuán)優(yōu)先遷移,Shifting group and leaving group 遷移的立體化學(xué)要求,遷移基團(tuán)與離去基團(tuán)處于反式位置時(shí)較易遷移,(D). Polymerization and cyclization 聚合與成環(huán),聚乙二醇,10.5 Preparation of alcohol (learn on your own) 10.6 Sources and usages (learn on your own),Part II P

20、henols 第一部分 酚,10.7 Structure and nomenclature 結(jié)構(gòu)和命名,Phenol 酚,Alcohol 醇,Electron-donating conjugation, = 1.6 D,強(qiáng)給電子基團(tuán),Nomenclature 命名,采用芳烴命名原則。,10.8 Physical and spectroscopic properties,10.8.1 Physical properties,苯酚在冷水中微溶，加熱時(shí)可無(wú)限溶解 分子間氫鍵 純的酚無(wú)色，但易被空氣中的氧氣氧化而呈略紅或褐色 毒性,10.8.1 spectroscopic data,IR,(O-H),(C-O),3610cm-1,1200cm-1,NMR,4 - 12 ppm,Mass spectrometry,10.9.1 Electrophilic reactions 10.9.2 Other properties,10.9 Chemical reactions,10.9.1 Electrophilic reactions,鄰對(duì)位活化基,反應(yīng)條件溫和 反應(yīng)速度快 產(chǎn)物鄰、對(duì)位為主 容易發(fā)生多取代,白色 極靈敏（10ppm即可顯色） 可用于鑒別苯酚,控制條件才可獲得一鹵代產(chǎn)物,10.9.2 Other pr