1、9.1 IUPAC Nomenclature of Alcohols, Ethers and Phenols9.1.1 Naming Alcohols9.1.2 Naming Phenols9.1.3 Naming Ethers 9.2 Preparation of alcohols,Ethers andPhenols 9.2.1 Preparation of alcohols A. Preparation of alcohols by reduction of carbonyl compounds(1) Hydrogenation of aldehydes andketones by cat
2、alysis of metals (2) Reduction of carbonyl compounds by metal hydridesB. Preparation of diols,Chapter 9 Alcohols, Ethers and phenols,9.2.2 Preparation of EthersA. Ethers by intermolecular dehydration of alcoholsB. Williamson Synthesis of Ethers9.2.3 Preparation of phenolsA. Laboratory synthesisB. In
3、dustrial synthesis 9.3 Reactions of Alcohols The sites of reactions of a Alcohol9.3.1 Acidity and Basicity of Alcohols9.3.2 Conversion of alcohols to ethers9.3.3 Oxidation of alcoholsA. Oxidation of primary alcoholsB. Oxidation of secondary alcoholsC. Oxidation of vicinal diols,9.4 Reactions of phen
4、ols 9.4.1 Acidity of Phenols 9.4.2 Electrophilic aromatic substitutions 9.4.3 Acylation of phenolsFries rearrangement 9.4.4 Kolbe-Schmitt reaction 9.4.5 Preparation of aryl ethers 9.4.6 Cleavage of aryl ethers by hydrogenhalides 9.4.7 Claisen rearrangement of allyl aryl ethers 9.4.8 Oxidation of phe
5、nols: Quinones,9.5 Reactions of Ethers9.5.1 Acid-catalyzed cleavage of ethers 9.5.2 Preparation of epoxidesA.Epoxidation of alkenes by reactionwith peroxy acidsB. Conversion of vicinal halodrins to epoxides9.5.3 Reactions of EpoxidesA. Base-catalyzed ring opening B. Acid-catalyzed ring opening,Carbo
6、xylic Carboxylic acidacid derivatives羧酸 羧酸衍生物,Compounds with O-containingfunctional groups,Alcohol Ether Phenol Aldehyde Ketone醇 醚 酚 醛 酮,The interplay of these compounds is fundamental to organic chemistry and biochemistry,Alcohol Ether Phenol Aldehyde Ketone醇 醚 酚 醛 酮,Compounds that have hydroxylgro
7、up bonded to a saturated,sp3-C atomAlcohols.,Compounds that have hydroxyl group bonded to a aromatic ringPhenols.,Compounds that have a oxygen atom bonded to two carbon atom Ethers,Class of Alcohols:,Class of Ethers:,Ethers,Epoxides,9.1 IUPAC Nomenclature of Alcohols, Ethers and Phenols,P252,8.1,9.1
8、.1 Naming Alcohols,Common name:,Alkyl + alcohol,Substitutive name:,Number: begin at the end nearer the hydroxyl group.,Benzyl alcohol (苄醇),Phenyl methanol (苯甲醇),Allyl alcohol (烯丙醇),2-Propen-1-ol (2-丙烯-1-醇),tert-Butylalcohol (叔丁醇),2-Metyl-2-propanol (2-甲基-2-丙醇),ClCH2CH2CH2OH,Glycerol(甘油) 1,2,3-Propan
9、etriol,3-Chloro-1-propanol (3-氯-1-丙醇),9.1.2 Naming Phenols,Phenol is the base name:,o-, m-, p-: substitutent,4-Methylphenol p-Methylphenol p-Cresol（甲酚）,1-Naphthol - Naphthol （1-萘酚）,2-Naphthol - Naphthol （2-萘酚）,9.1.3 Naming of Ethers,CH3CH2OCH3,Ethyl methyl ether (甲乙醚),P253,tert-Butyl phenyl ether (苯
10、叔丁基醚),Diethyl ether (乙醚),Anisole Methyl phenyl ether (茴香醚) (苯甲醚),Tetrahydrofuran(THF)(四氢呋喃),Functional class IUPAC names,Substitutive IUPAC,2-Methoxypentane (2-甲氧基戊烷),Alkoxy (烷氧基),1-Ethoxy-4-methylbenzene (4-甲基-1-乙氧基苯),Cyclic ethers:,Transformation of the several functional groups to alcohols:,A. Pr
11、eparation of Alcohols by Reduction of Carbonyl Compounds,9.2 Preparation of alcohols, Ethers andPhenols,9.2.1 Preparation of Alcohols,P258,8.4,(1) Hydrogenation of aldehydes and ketones by Catalysis of metals,Aldehydes Primary alcohols,Ketones Secondary alcohols,(2) Reduction of carbonyl compounds b
12、y metal hydrides,Metal hydrides:,P259, 8.5,Reaction of NaBH4 with aldehydes and ketones,An aqueous oralcoholic solution,Reaction of LiAlH4 with Aldehydes and Ketones,Reaction of LiAlH4 with carboxylic acids and esters,Characteristics of reactions:,Selective reduction:NaBH4 does not reduce C=C, and C
13、OOH, COOR。LiAlH4 does not reduce C=C,Methyl 2-pentenoate 2-Penten-1-ol(91%),LiAlH4 reacts violently with water.,Solvents:,Vicinal diols,B. Preparation of diols,KMnO4 / OH(cold),OsO4 Osmium tetraoxide (四氧化锇),tert-butyl hydroperoxide (叔丁基氢过氧化物),Alkaline (碱性),Hydroxylation,Syn-addition,9.2.2 Preparatio
14、n of Ethers,A. Ethers by intermolecular dehydration of alcohols,Substrate: Primary alcohols Acid-catalyzed Products: symmetric ethers,B. The Williamson Synthesis of Ethers,Sodium alkoxide,Alkyl halide and derivatives,Mixed ethers,P261, 8.6,The reaction characteristic: SN2 reaction 2. The best substr
15、ate is primary alkyl halide,Alexander W. Williamson (1824-1904),Alexander W. Williamson was Born in London, England, and received his Ph.D. at the University of Giessen in 1846.His ability to work in laboratory was hampered by a childhood injury that caused the loss of an arm. From 1849,utill 1887,
16、he was professor of Chemistry at University College, London.,Bonding in organic compounds at that time was thought to be of either the water type, as in alcohols, ROH, or of the radical type, as in ethers which would be given the formula RO. But Williamson, by his ether synthesis, showed that mixed
17、ethers, with two different alkyl groups, could be prepared. Ethers thus has to have the water-type formula ROR, and oxygen had the equivalent weight of 8 but the atomic weight of 16. By this type of argument he established and rationalised the structures of many of the families of simple organic com
18、pounds. Thus, in 1850 he predicted the existence of acetic anhydride, which was prepared in 1851.We still have some examples of his early apparatus, and his copper pelicans, in which he prepared ether, areshown at right. When you realise the scale on which these reactions were carried out, and the f
19、act that the pelican was heated over a charcoal brazier,it is remarkable that we do not seem to have records of catastrophic accidents taking place. Later on Williamson, again with people such as Liebig, was responsible for the introduction of much of the glassware which we are familiar with today,
20、except that it was usually fitted together with corks rather than ground glass joints. Standard joints, blown in a mould, as we know them today did not come into use until the middle of the last (20th) century. Towards the end of his period as Head of Department, Williamson became very much involved
21、 in College and University politics, and his research suffered. This was the period when the other London colleges - Kings,Birkbeck, Queen Mary, what is now Imperial College, and so on were combined into a federal university, and presumably Williamson felt the need to fight the University College co
22、rner.,碱熔法,9.2.3 Preparation of phenols,A. Laboratory synthesis,From aniline:,(80%),B. Industrial synthesis,(1) Reaction of benzenesulfonic acid with NaOH,Toluene p-Toluenesulfonic p-methylphenolacid (72%),(2) Hydrolysis of chlorobenzene,3. From cumene（枯烯）,Friedel-Crafts alkylation,Cumene hydroperxid
23、e (氢过氧化枯烯),卤苯水解,Cumene is oxidized to cumene hydroperoxide,9.3. Reactions of Alcohols,异丙苯法,Weak acidity,Protona- tion,Nu:,Oxidation,The sites of reactions of a Alcohol:,Elimination,9.3.1 Acidity and Basicity of Alcohols,Like water, alcohols are both weakly basic and weakly acidic.,As a weak base:,An
24、 alcohol An oxonium ion,As a weak acid:,Acid (base) conjugate conjugate base acid,An alcohol An Alkoxide Hydroniumion(烷氧负离子) ion(水合离子),P256,8.3,P257, Table 8.1,In any proton-transfer process:,Relative acidity:,Relative basicity:,9.3.2 Conversion of Alcohols to Ethers,P263.8.7,Dehydration,NaH, NaNH2,
25、Characteristics of the reaction: Condensation(缩合反应) 2. Only for primary alcohols 3. The temperature of condensation is lower than elimination. 4. SN2 mechanism,A. Oxidation of primary alcohols,PCC reagent issoluble in CH2Cl2,P 263,9.3.3 Oxidation of alcohols,B. Oxidation of secondary alcohols,PCC do
26、esnt attack C=C bond,Chromic acid H2CrO4,C. Oxidation of vicinal diols,Vicinal diols react with HIO4, the C-C bond is broken to form carbonylcompounds,AgNO3 is added to identify the vicinal diols,Ch.P225,(3),9.4 Reactions of phenols,Acidity,Acylation,Aromatic Electrophilic substitution,Formation of
27、aryl ethers,The sites of reactions,9.4.1 Acidity of Phenols,TABLE 1 The acidity constants of phenols,P256,8.3,Substituted phenols:,Substuents on the positiono- or p-,Electron delocalization in phenoxide ion:,9.4.2 Electrophilic aromatic substitutions,A hydroxyl group is a very powerful activating su
28、bstituent:,Bromination:,Sulfonation:,Rate control,Equilibrium control,P266; Ch.P322,(2),9.4.3 Acylation of phenols,Acylating agents: acyl halides and carboxylic acid anhydrides,Fries rearrangement:,Phenol benzoate,p-hydroxylbenzopheone （对-羟基二苯酮）(64%),(9%),Phenolic Esters （酚酯）,Conversion of aryl este
29、rs to aryl ketones.,Ch.P319(丙),9.4.4 Kolbe-Schmitt reaction:,Carboxylaltion of phenols,Sodium phenoxide,CO2,Heated under pressure,Acidified,Salicylic acid,Salicylic acid （水杨酸）(79%),Aspirin （阿斯匹林） （乙酰水杨酸）,9.4.5 Preparation of aryl ethers,Williamson Method,A Phenoxide anion,A alkyl halide,Alkylation o
30、f hydroxyl oxygen a phenol,Why?,Me2SO4methylating agent,9.4.6 Cleavage of aryl ethers by hydrogen halides,The bond of OR was broken!,The bond of CO in phenols has partial doublebond character,9.4.7 Claisen rearrangement of allyl aryl ethers,Heating allyl aryl ether,Intramolecular reaction,The produc
31、t is o-allylphenol,Transition state,Claisen was professor in Aachen in 1890, Kiel in 1897 and Berlin in 1904. Several syntheses especially condensationreactions between aldehydes, ketones, and esters (1881-1890) are connected with Claisens name. He also carried out research on tautomerism andrearran
32、gement reactions(Umlagerungsreaktionen),19th Century Claisen, Ludwig Born: Kln (Germany), 1851 Died: Godesberg near Bonn (Germany), 1930,http:/www.chemsoc.org/networks/enc/FECS/ Claisen.htm,9.4.8 Oxidation of phenols: Quinones (醌）,P266,Vitamin K,9.5.1 Acid-catalyzed cleavage of ethers,Mechanism of t
33、he reaction:,9.5 Reactions of Ethers,P267,8.9,A. Epoxidation of alkenes by reaction withperoxy acids (过氧酸),B. Conversion of vicinal halohydrins (-卤代醇) to epoxides,9.5.2 Preparation of epoxides,Intramolecular Williamson ether synthesis:,1. Anti-addition, 2. Inversion of configuration,A. Base-catalyze
34、d ring opening,To the unsymmetric epoxide, in base- catalyzed ring-opening, attack by nucleophile occurs at less substituted carbon atom.,B. Acid-catalyzed ring opening,9.5.3 Reactions of epoxides,In the acid-catalyzed ring opening, thenucleophile attacks primarily at the more substituted carbon atom.,SN2 reaction,With inversion of configuration,Anti- hydroxylation,Problems to Chapter 9,P276 8.24 (c), (d) 8.25 (b), (c) 8.28 8.31(a),(b) 8.33(a), (c), (e) 8.35(a),(d) 8.36(b), (e) 8.37(b) 8.38(b), (c),8.40 8.41 8.43 8.46 8.48 8.51 8.53 8.54(b) 8.55,
