附件2 粒大浮 教 案 2003~~2004学年第Ⅰ学期 院(系、所、部)化学与环境学院有机化学研究所 教研室有机化学 课程名称有机化学(双语教学 授课对象化学教育 授课教师杨定乔 职称职务教授 教材名称 Organic Chemistry 2003年09月01日
附件 2 教 案 2003~~ 2004 学年 第 I 学期 院（系、所、部）化学与环境学院有机化学研究所 教 研 室 有机化学 课 程 名 称 有机化学(双语教学) 授 课 对 象 化学教育 授 课 教 师 杨定乔 职 称 职 务 教授 教 材 名 称 Organic Chemistry 2003 年 09 月 01 日
有机化学(双语教学)课程教案 授课题目(教学章节或主题):第十章.醇,酚,醚授课类型|理论课 (Alcohols, Phenols, Ethers) 授课时间第15周第47-54节 教学目标或要求:了解醇,酚,醚的分类,命名及同分异构现象。了解醇的化学性质 酚的化学性质,醚的化学性质。重点掌握醇,酚,醚的化学性质。 教学内容(包括基本内容、重点、难点) 醇,酚,醚 基本内容包括了解醇,酚,醚的分类,命名及同分异构现象。本章的重点是醇、酚、醚的重要反应 及其应用。重要反应有亲核取代反应、消除反应、重排反应等。历程主要是指SN1和SN2历程, Alcohols ethers: nomenclature Simple alcohols are named as derivatives of the parent alkane, using the suffix -ol, using the following simple rules Select the longest continuous carbon chain, conta ining the hydroxyl group, and derive the parent name by replacing the -e ending with -oL 2. Num ber the carbon chain, beginning at the end nearest to the hydroxyl group 3. Num ber the substituents and write the name, listing substituents alpha betically Some examples
有机化学（双语教学） 课程教案 授课题目（教学章节或主题）：第十章．醇，酚，醚 (Alcohols,Phenols,Ethers) 授课类型 理论课 授课时间 第 15周第 47-54节 教学目标或要求：了解醇，酚，醚的分类，命名及同分异构现象。了解醇的化学性质， 酚的化学性质，醚的化学性质。重点掌握醇，酚，醚的化学性质。 教学内容（包括基本内容、重点、难点）： 醇，酚，醚 基本内容包括了解醇，酚，醚的分类，命名及同分异构现象。本章的重点是醇、酚、醚的重要反应 及其应用。重要反应有亲核取代反应、消除反应、重排反应等。历程主要是指 SN1 和 SN2 历程， Alcohols & Ethers: Nomenclature Simple alcohols are named as derivatives of the parent alkane, using the suffix -ol, using the following simple rules: 1. Select the longest continuous carbon chain, containing the hydroxyl group, and derive the parent name by replacing the -e ending with -ol. 2. Number the carbon chain, beginning at the end nearest to the hydroxyl group. 3. Number the substituents and write the name, listing substituents alphabetically. Some Examples:
<2-13-ccloheranediol HO 4 4dimethyicycloheranol Alcohols are also known by a wide variety of common names, some of which are given below: H3C Isopropy alcohol NButyl alcohol c-methyl-2-propanon (123-propanetniol CH2OH Allylalcohol Benzyl alcohol Simple ethers are named either by identifying the two organic residues and adding the word ether, or, if other functionality is present, the ether residue is named as an alkoxy substituent, as shown below ethyl methyl ether 4-bromo-l-methoxybu Some example:
Alcohols are also known by a wide variety of common names, some of which are given below: Simple ethers are named either by identifying the two organic residues and adding the word ether, or, if other functionality is present, the ether residue is named as an alkoxy substituent, as shown below: Some Examples:
e-methyl-1-proporypropane chloro 1(2-chloroproporyh2-methyipropane Reactions of alcohols Conversion to Alkyl Chlorides by Reaction with HCl: Tertiary alcohols, or alcohols which can lose the hydroxyl group to form a stable carbocation, can undergo an S,I substitution reaction with hcl gas dissolved in ether to give the corresponding alkyl chloride. Again, the reaction is limited to alcohols that can from stable carbocations ether.0°c CH Conversion to Alkyl Bromides by Reaction with PBr. Primary and secondary alcohols react with PBr, to form an intermediate phosphite ester which undergoes S,2 attack by bromide anion to yield the alkyl bromide with inversion of configuration(the stereochemical inversion is simply a result of the displacement)
Reactions of Alcohols Conversion to Alkyl Chlorides by Reaction with HCl: Tertiary alcohols, or alcohols which can lose the hydroxyl group to form a stable carbocation, can undergo an SN1 substitution reaction with HCl gas dissolved in ether to give the corresponding alkyl chloride. Again, the reaction is limited to alcohols that can from stable carbocations. Conversion to Alkyl Bromides by Reaction with PBr3: Primary and secondary alcohols react with PBr3 to form an intermediate phosphite ester which undergoes SN2 attack by bromide anion to yield the alkyl bromide with inversion of configuration (the stereochemical inversion is simply a result of the SN2 displacement)
R ether.35°c PB -Br Displac B CH3CH CH3CH2 a phosphite ester Conversion to Alkyl Chlorides by Reaction with SoCl, Primary and secondary alcohols react with SoCl, in polar solvents (i. e, pyridine) to form an intermediate sulfite ester which undergoes S2 attack by chloride anion to yield the alkyl chloride with inversion of configuration(the stereochemical inversion is simply a result of the S,2 displacement). If the reaction is performed in a non-polar solvent such as benzene, an unusual S, i mechanism occurs involving frontside attack, and yielding retention of stereochemistry. This reaction is unusual, but is often useful if you desire to control the stereochemical course of a synthesis sOCI2 pendine Non-Polar CI/NN2Displacement SNi Displacement with Inversion with Retention a sulfite ester a sulfite este Dehydration of Tertiary Alcohols: Tertiary alcohols, or alcohols which can lose the hydroxyl group to form a stable carbocation, can undergo an acid-catalyzed El elimination reaction to form the corresponding alkene. Again, the reaction is limited to alcohols that can from stable carbocations
Conversion to Alkyl Chlorides by Reaction with SOCl2: Primary and secondary alcohols react with SOCl2 in polar solvents (i.e., pyridine) to form an intermediate sulfite ester which undergoes SN2 attack by chloride anion to yield the alkyl chloride with inversion of configuration (the stereochemical inversion is simply a result of the SN2 displacement). If the reaction is performed in a non-polar solvent such as benzene, an unusual SNi mechanism occurs involving frontside attack, and yielding retention of stereochemistry. This reaction is unusual, but is often useful if you desire to control the stereochemical course of a synthesis. Dehydration of Tertiary Alcohols: Tertiary alcohols, or alcohols which can lose the hydroxyl group to form a stable carbocation, can undergo an acid-catalyzed E1 elimination reaction to form the corresponding alkene. Again, the reaction is limited to alcohols that can from stable carbocations
Ho、gh H2SO4, THF Dehydration of Secondary and Tertiary Alcohols with PoCl, Secondary and tertiary alcohols react with pocl, to form a dichlorophosphate ester, which undergos an E2 elimination reaction to form the corresponding alkene. Since an E2 elimination is occurring, the hydrogen abstracted must be anti-and coplanar with the oxygen on the leaving group(antarafacial) pande a dichlorophosphate ester Oxidation of Alcohols with Pyridinium Chlorochromate: Primary and secondary lcohols are smoothly oxidized by pyridinium chlorochromate( PCc) in CH,Cl,to form aldehydes and ketones, respectively. The PCC oxidation of primary alcohols to give aldehydes is a very useful reaction, since aldehydes are difficult to prepare and are easily over-oxidized to the carboxylic acid. -CHOH PCC PCC: pyridinium chlorochromate )NHCro
Dehydration of Secondary and Tertiary Alcohols with POCl3: Secondary and tertiary alcohols react with POCl3 to form a dichlorophosphate ester, which undergos an E2 elimination reaction to form the corresponding alkene. Since an E2 elimination is occurring, the hydrogen abstracted must be anti- and coplanar with the oxygen on the leaving group (antarafacial). Oxidation of Alcohols with Pyridinium Chlorochromate: Primary and secondary alcohols are smoothly oxidized by pyridinium chlorochromate (PCC) in CH2Cl2 to form aldehydes and ketones, respectively. The PCC oxidation of primary alcohols to give aldehydes is a very useful reaction, since aldehydes are difficult to prepare and are easily over-oxidized to the carboxylic acid
Oxidation of Alcohols with" Jones Reagent": Primary and secondary alcohols are oxidized by CrO,/H,SO, (Jones Reagent) to form carboxylic acids and ketones respectively; sodium dichromate in acetic acid (Na,Cr0, can also be used CrO3, H2So4 (Jones Reagent) CH COOHIH2O 2° alcohols CH2 CCH.OH Conversion to Silyl Ethers: Alcohols react with chlorotrimethylsilane to form trimethylsilyl ethers which are stable to many reactions which occur in aprotic medium, but can be readily cleaved by reaction with aqueous acid, regenerating the alcohol. This reaction is often utilized to protect an alcohol during a synthesis, such as that shown below (in the synthesis shown, the grignard reagent would react with the acidic proton on the alcohol, destroying the reagent) H HTH2O Chlorotrimethylsilane HO CH3)3 1(CH3)3 1 Mg, ether Ethers, Synthesis& Reactions Synthesis by Sm2 Displacement Reactions: Unhindered primary and secondary alkyl halides react with simple (unhindered)alkoxides by an S,2 mechanism yielding
Oxidation of Alcohols with "Jones Reagent": Primary and secondary alcohols are oxidized by CrO3/H2SO4 (Jones Reagent) to form carboxylic acids and ketones, respectively; sodium dichromate in acetic acid (Na2Cr2O7) can also be used. Conversion to Silyl Ethers: Alcohols react with chlorotrimethylsilane to form trimethylsilyl ethers which are stable to many reactions which occur in aprotic medium, but can be readily cleaved by reaction with aqueous acid, regenerating the alcohol. This reaction is often utilized to "protect" an alcohol during a synthesis, such as that shown below (in the synthesis shown, the Grignard reagent would react with the acidic proton on the alcohol, destroying the reagent). Ethers, Synthesis & Reactions Synthesis by SN2 Displacement Reactions: Unhindered primary and secondary alkyl halides react with simple (unhindered) alkoxides by an SN2 mechanism yielding
ethers (the Williamson Ether Synthesis CH3-o HOCH. H-C≡-CH2OTo3 H-C≡c-CH2-O Synthesis Oxymercuration of Alkenes in the Presence of Alcohols: Oxymercuration of alkenes is a stepwise reaction involving a bridged mercurinium ion intermediate. In unsymmetrical alkenes, the alkene carbon which would form the most stable carbocation will bear more of the positive charge and, in alcohols will be attacked by alkoxide anion or the alcohol) to give the additio intermediate; rearrangements do not occur, but the orientation follows Markovnikov's Rule. In a second step, BH- is used to remove the mercury and ive the final product 1. Hg(OAC)2, CH3OH 评x Hg+ OAC tertiary carbon bears more of the positive charge 2, NaBH4 OCH Formation of epoxides by Oxidation of Alkenes: Alkenes undergo partial oxidation with peracids to form epoxides. a stable and useful reagent for this reaction is the magnesium salt of monoperoxyphthalate(MMPP)
ethers (the Williamson Ether Synthesis). Synthesis Oxymercuration of Alkenes in the Presence of Alcohols: Oxymercuration of alkenes is a stepwise reaction involving a bridged mercurinium ion intermediate. In unsymmetrical alkenes, the alkene carbon which would form the most stable carbocation will bear more of the positive charge and, in alcohols, will be attacked by alkoxide anion (or the alcohol) to give the addition intermediate; rearrangements do not occur, but the orientation follows Markovnikov's Rule. In a second step, BH4 - is used to remove the mercury and give the final product. Formation of Epoxides by Oxidation of Alkenes: Alkenes undergo partial oxidation with peracids to form epoxides. A stable and useful reagent for this reaction is the magnesium salt of monoperoxyphthalate (MMPP)
R→-0oH a Ae/UR OH Magnesium Monoperoxyphthalate Formation of Epoxides by an Internal S,2 Reaction in halohydrins: Halohydrins (prepared by the addition of HoX to an alkene)undergo an internal S, 2 reaction in the presence of strong base(Naoh) to give epoxides. HOBr (NB SHH2ONDMSO) 下 Reactions of phenols Phenols, like simple alcohols, will form an anion which will undergo an S,2 reaction with alkyl halides (or alkyl groups with "good leaving groups")to give ethers. They will also react with activated carbony l compounds to undergo acyl transfer reactions; thus ary l esters are readily formed by the reaction of phenols with acid halides or acid anhydrides. As with aryl amines, the ring of phenols is electron-rich and will rapidly react with Br to give a tri-substituted product
Formation of Epoxides by an Internal SN2 Reaction in Halohydrins: Halohydrins (prepared by the addition of HOX to an alkene) undergo an internal SN2 reaction in the presence of strong base (NaOH) to give epoxides. Reactions of Phenols Phenols, like simple alcohols, will form an anion which will undergo an SN2 reaction with alkyl halides (or alkyl groups with "good leaving groups") to give ethers. They will also react with activated carbonyl compounds to undergo acyl transfer reactions; thus aryl esters are readily formed by the reaction of phenols with acid halides or acid anhydrides. As with aryl amines, the ring of phenols is electron-rich and will rapidly react with Br2 to give a tri-substituted product
Kolbe-Schmitt car boration The last reaction shown above is a specific and unusual reaction of phenols, that is the direct reaction with Co, to give carboxylation at the ortho postion. This reaction is called the Kolbe-Schmitt carboxylation, and is important since the product is salicylic acid, which is widely used in pharmaceuticals. Another reaction which is highly specific for phenols is oxidation with Fremys salt: potassium nitrosodisulfonate to give the para-quinone as product. (KSOs)2NO Fremys salt: potassium nitrosodisulfonate Reactions Cleavage of Ethers with HI: Ethers undergo cleavage in the presence of aqueous hi to give the corresponding alkyl iodide. Attack will be at the least hindered carbon and El reactions, with carbocation intermediates, are common with ethers with groups which can form stable carbocations
The last reaction shown above is a specific and unusual reaction of phenols, that is the direct reaction with CO2 to give carboxylation at the ortho-postion. This reaction is called the Kolbe-Schmitt carboxylation, and is important since the product is salicylic acid, which is widely used in pharmaceuticals. Another reaction which is highly specific for phenols is oxidation with Fremy's salt: potassium nitrosodisulfonate, to give the para-quinone as product. Reactions Cleavage of Ethers with HI: Ethers undergo cleavage in the presence of aqueous HI to give the corresponding alkyl iodide. Attack will be at the least hindered carbon and E1 reactions, with carbocation intermediates, are common with ethers with groups which can form stable carbocations
