第十一章 醛和酮

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11.3 Sources & Preparation 来源和制法
iii) Friedel-Crafts acylation of aromatic compounds 付克 酰基化
Electrophilic aromatic substitution 芳环亲电取代 Cannot be used in deactivated aromatic 芳环钝化不适用
3-己酮 3-Hexanone
4-甲基-2-戊酮 4-Methyl-2-pentanone
4-甲基环己酮 4-Methylcyclohexanone
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11.1.1 Nomenclature 命名
• 酮的普通命名法
The groups attached to the carbonyl group are named as
Over 2×109 lb/year of a variety of aldehydes and alcohols
is prepared in the USA by hydroformylation.
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11.3 Sources & Preparation 来源和制法
vi) Oxidation of alcohols 醇的氧化（最重要的方法）
1,3-二苯基-2-丙酮
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11.1.2 Structure 结构
• Geometry 几何构型
甲醛 Formaldehyde
乙醛 Acetaldehyde
丙酮 Acetone
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11.1.2 Structure 结构
• Electron distribution map 电子分布图
(a) 乙烯
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11.2.1 Physical Properties 物理性质
醇 醛或酮 醇 醛或酮 醚 烷烃
醚 烷烃
丁烷
丙醛
丙酮 1-丙醇
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Exercise 4
• Arrange the following compounds in order of increasing boiling point:按沸点升高的顺序排序
group 选择含羰基最长链为主链;
Number the chain starting with the end closest to the
ketone group 接近羰基的一端开始编号 命名取代基
Name the substitutes attached to the chain in the usual way.
Resonance (ppm) 9.0 -10.0
Interpretation -CH=O
~2.4
~2.0
-CHCH=O
-CHCH2CH=O
1H
NMR of acetaldehyde
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1H
NMR Spectrum
2-methylpropanal
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13C
NMR 碳核磁质谱
• 6个sp3杂化的C出现在 = 8～42ppm；
2-苯基丙二醛
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11.1.1 Nomenclature 命名
• Aromatic aldehydes 芳香醛
Containing an aldehyde group directly attached to a benzene
ring 醛基直接与苯环相连; 体命名
Named after the parent compound benzaldehyde以苯甲醛为母
2-pentanone 2-戊酮 2-methylpentane 2-甲基戌烷 2-pentanol 2-戊醇
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11.2.2 Spectroscopy Properties 光谱性质
• FI-IR 傅立叶红外光谱
Absorbance (cm-1) 1710 -1750 ~2720 ~2820 Interpretation C=O stretch C-H stretch of aldehydes
separate words followed by the word “ketone.” 羰基以外取代基独立命名，以“酮”结尾
乙基丙基酮
苯甲基乙基酮
二乙烯基酮
• 特殊酮的命名
苯乙酮
百度文库
二苯甲酮
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Exercise 1
• Give IUPAC Name of the following compounds 用系统 命名法命名下列化合物:
用于除酚类以外的活化苯环体系
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11.3 Sources & Preparation 来源和制法
• Formylation of phenols 酚类的甲酰基化
Vilsmeier-Haack Reaction 维勒斯梅尔反应
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11.3 Sources & Preparation 来源和制法
Carbonyl compounds are polar, containing a dipole along the
carbon-oxygen double bond 羰基化合物是有极性的，沿C=O双键 含有偶极;
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11.2.1 Physical Properties 物理性质
• Aldehydes and ketones do not form hydrogen bonds with themselves 羰基氧上无H原子，醛酮自身不形成氢键.
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11.3 Sources & Preparation 来源和制法
iv) Formylation of aromatic 芳环甲酰基化
Gatterman-Koch synthesis 加特曼-科特合成法
CO2 and HCl formed formyl chloride intermediate 形成甲酰氯 Only with activated benzene derivatives expect phenols 只适
The carbon and oxygen in the carbonyl group are
hybridized, with bond angles of 120°羰基中的碳和氧是sp2杂 化，键角120°
sp2-
In ketones, two carbon groups are attached to the carbonyl
-CHO中的C-H键在2820、2720 cm-1区域有非常特征的伸缩振动
吸收峰。
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Infrared Spectroscopy 红外光谱
2720 and 2820 cm-1(C- H) 1720 cm-1(C=O) butanal
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1H
NMR 核磁质谱
• -CH=O unit of aldehydes is the most easily recognized
>
Electron-releasing alkyl substituentes stabilize a carbonyl
group 给电子的烷基取代基可以稳定羰基
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11.2.1 Physical Properties 物理性质
• Polarity of the Carbonyl Group 羰基的极性
亲核加成反应
Oxidation & Reduction 氧化和还原反应 Reaction of -H -H的反应
11.5 Unsaturated Aldehydes & Ketones , -不饱和醛、酮
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11.1 Structrue & Nomenclature 结构和命名
• Carbonyl Group 羰基
11.1 Structure & Nomenclature 结构与命名 11.2 Physical & Spectroscopic Properties 物理和光谱性质 11.3 Sources & Preparation 来源和制法
11.4 Reactions 化学性质
Nucleophilic Additions
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11.3 Sources & Preparation 来源和制法
ii) Hydration of alkynes 炔烃的水化反应
By way of an enol intermediate formed by Markovnikov
addition of water to the triple bond 三键的马氏加成
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Exercise 2
• Convert each of the following functional class IUPAC names to a substitutive name 写出结构式并转成系统命 名
(a) Dibenzyl ketone 二苄基酮 (b) Ethyl isopropyl ketone 乙基异丙基酮 (c) Methyl 2,2-dimethylpropyl ketone 甲基(2,2-二甲基)丙基酮 (d) Allyl methyl ketone 甲基烯丙基酮
Sarret agent 沙瑞特试剂
Pyridinium dichromate (PDC) or pyridinium chlorochromate (PCC)
重铬酸吡啶或氯铬酸吡啶
Avoiding overoxidation to carboxylic acids 避免过度氧化
group 选择含羰基最长链为主链;
The carbonyl carbon is always numbered “1.” 羰基C为1 Name the substitutes attached to the chain in the usual way
命名取代基.
4, 4-二甲基戊醛
5-已烯醛
v) Hydroformylation 氢甲酰化 （工业方法）
Excess hydrogen brings about the hydrogenation of the
aldehyde and allows the process to be adapted to the preparation of primary alcohols.
醛基作为取代基，以“甲酰基”命之。
3-甲基苯甲醛 3-methylbenzaldehyde
4-甲酰基苯甲酸 4-formylbenzoic acid
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11.1.1 Nomenclature 命名
• Nomenclature of Ketones 酮的系统命名
Select the longest carbon chain containing the carbonyl
(b) 甲醛
Carbon is partially positive and oxygen is partially negative.
C原子带部分正电荷，O原子带部分负电荷
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11.1.2 Structure 结构
• Relative stability of carbonyl groups 羰基的相对稳定性
Chapter11 Aldehydes & Ketones 第十一章 醛和酮
Organic Chemistry II
By Meng Xiang-Fu Capital Normal University
生活中的醛和酮
醛 酮 让 生 活 更 美 好 ！
灵猫酮
柠檬醛
茉莉酮
2
Contents 本章重点内容
• C=O中sp2杂化的C在 = 210ppm;
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11.3 Sources & Preparation 来源和制法
I. Occurred naturally 天然生成
II. Made in lab from alkenes, alkynes, arenes, alcohols,etc 由烯烃、炔烃、芳烃、醇实验室合成
carbon, while in aldehydes at least one hydrogen is attached to the carbon.
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11.1.1 Nomenclature 命名
• Nomenclature of Aldehydes 醛的系统命名
Select the longest carbon chain containing the
i) Ozonolysis of alkenes 烯烃的臭氧化反应
Structural analysis 用于结构分析
Presence of zinc permits aldehyde to be isolated without
further oxidation Zn的存在阻止醛被进一步氧化