Chapter 18 CO

Ketones and Aldehydes Chapter 18
酮和醛 Lecture
© 2017 Pearson Education, Ltd.
© 2014 Pearson Education, Inc.

18-1 Carbonyl Compounds

Structure of the Carbonyl Group

18-2 Structure of the Carbonyl Group 羰基的結構
• Carbon is sp2 hybridized.

碳是sp2混成
• The C═O bond is shorter, stronger, and more polar than the
C═C bond in alkenes.
C = O鍵比烯烴中的C = C鍵更短，更強和更有極性。

Resonance 共振
• The first resonance is better because all atoms complete the octet and
there are no charges.
⼀個共振是更好的，因為所有的原⼦符合八嵎體，沒有帶價數
• The carbonyl carbon has a partial positive and will react as an
electrophile.
羰基碳具有部分正電荷並將作為親電⼦試劑反應。

Dipole Moments
偶極矩

18-3 Nomenclature of Ketons and Aldehydes
酮和醛的命名
• Number the chain so that the carbonyl carbon has the lowest
number.
給鏈條編號，使羰基碳數⽬最少。
• Replace the alkane -e with -one.
⽤-one替換烷烴-e

Cyclic Ketone Nomenclature
環酮命名法
• For cyclic ketones, the carbonyl carbon is assigned the number 1.

對於環狀酮，羰基碳被指定為1。
• When the compound has a carbonyl and a double bond, the
carbonyl takes precedence.
• 當化合物具有羰基和雙鍵時，羰基優先。

Aldehydes Nomenclature 醛命名法
• The aldehyde carbon is number 1.

醛碳是1號。
• IUPAC: Replace -e with -al.
IUPAC：⽤-al替換-e。
• If the aldehyde group is attached to a ring, the suffix -
carbaldehyde is used.
如果醛基連接到環上，則使⽤後綴 - 甲醛。
Carbonyl as Substituent 羰基作為取代基
• On a molecule with a higher-priority functional group, a
ketone is an oxo and an aldehyde is a formyl group.
在具有更⾼優先級官能團的分⼦上，酮是氧基，醛是甲
醯基。
• Aldehydes have a higher priority than ketones.
醛比酮更優先

Common Names for Ketones
酮的通⽤名稱
• Named as alkyl attachments to —C═O
命名為-C = O的烷基附著物
• Use Greek letters instead of numbers.
• 使⽤希臘字⺟⽽不是數字。

Common Names of Acids and Aldehydes

Historical Common Names 歷史通⽤名稱
Problem 1, 38
18-4 Physical Properties of Ketones and Aldehydes
Boiling Points
• Ketones and aldehydes are more polar, so they have a higher

boiling point than comparable alkanes or ethers.
酮類和醛類具有更⾼的極性，因此它們的沸點⾼於同類
烷烴或醚類。
• They cannot hydrogen-bond to each other, so their boiling
point is lower than the comparable alcohol.
它們不能相互氫鍵，所以它們的沸點比可比的醇低。

Solubility of Ketones and Aldehydes 酮和醛的溶解度
• Good solvent for alcohols
良好的醇溶劑
• Lone pair of electrons on oxygen of carbonyl can accept a
hydrogen bond from O—H or N—H.
羰基氧上的孤對電⼦可以接受來⾃O-H或N-H的氫鍵。
• Acetone and acetaldehyde are miscible in water.
丙酮和⼄醛可溶於⽔。

Formaldehyde
• Gas at room temperature

氣體在室溫下
• Formalin is a 40% aqueous solution.
福爾⾺林是⼀種40％的⽔溶液。
• Trioxane is a cyclic trimer of formaldehyde.
三惡烷是甲醛的環狀三聚體。
• When trioxane is heated, it generates formaldehyde.
當三惡烷加熱時，會產⽣甲醛。
18-6 Industrial Importance of Ketones and Aldehydes
• Acetone and methyl ethyl ketone are common industrial

solvents.
丙酮和甲基⼄基酮是常⾒的⼯業溶劑。
• Formaldehyde is used in polymers like Bakelite and
many other polymeric products.
甲醛⽤於聚合物如Bakelite®和許多其他聚合物產品。
• Also used as flavorings and additives for food
也⽤作食品的調味劑和添加劑

18-7 Review of Syntheses of Ketones and Aldehydes
Grignards As a Source for Ketones and Aldehydes
• A Grignard reagent can be used to make an alcohol, and

then the alcohol can be easily oxidized.
Grignard試劑可以⽤來製造酒精，然後酒精可以很容
易地被氧化。

Oxidation of Primary Alcohols to Aldehydes
• Pyridinium chlorochromate (PCC) is selectively used to

oxidize primary alcohols to aldehydes.
氯鉻酸吡啶（PCC）被選擇性地⽤於將伯醇氧化成醛。
• The Swern oxidation could also be used.
Swern氧化也可以使⽤。

Ozonolysis of Alkenes
• The double bond is oxidatively cleaved by ozone,

followed by reduction.
雙鍵被臭氧氧化分解，然後還原。
• Ketones and aldehydes can be isolated as products under
these conditions.
酮和醛可以在這些條件下作為產物分離。

Hydration of Alkynes
• The initial product of Markovnikov hydration is an enol, which

quickly tautomerizes to its keto form.
Markovnikov⽔合的初始產物是⼀種烯醇，它迅速互變為其酮形
式
• Internal alkynes can be hydrated, but mixtures of ketones often result.
內部炔烴可以被⽔合，但通常會產⽣酮的混合物。
Hydroboration–Oxidation of Alkynes
• Hydroboration–oxidation of an alkyne gives anti-Markovnikov

addition of water across the triple bond.
炔烴的硼氫化 - 氧化反應給三鍵上的anti-Markovnikov加⽔。

Solved Problem 1
Show how you would synthesize each compound from starting materials containing no more than six
carbon atoms.
說明如何從含有不超過6個碳原⼦的原料合成每種化合物。
(a) (b)
Solution
(a) This compound is a ketone with 12 carbon atoms. The carbon skeleton might be assembled from
two six-carbon fragments using a Grignard reaction, which gives an alcohol that is easily oxidized
to the target compound.
這種化合物是⼀個有12個碳原⼦的酮。碳骨架可能是由兩個六碳片段組裝⽽成，使⽤
Grignard reaction可以使醇容易氧化成⽬標化合物。

Solved Problem 1 (Continued)
(a) This compound is an aldehyde with eight carbon atoms. An aldehyde might come from
oxidation of an alcohol (possibly a Grignard product) or hydroboration of an alkyne. If we use a
Grignard, the restriction to six-carbon starting materials means we need to add two carbons to a
methylcyclopentyl fragment, ending in a primary alcohol. Grignard addition to an epoxide does
this.
這種化合物是八個碳原⼦的醛。醛可能來⾃醇（可能是格利雅產品）的氧化或炔烴的硼氫
化。
如果我們使⽤格⽒試劑，對六碳原料的限制意味著我們需要在甲基環戊基片段中添加兩個碳
原⼦，最後是⼀個伯醇。 Grignard除了環氧化物做到這⼀點。

Solved Problem 1 (Continued)
Solution (Continued)
Alternatively, we could construct the carbon skeleton using acetylene as the two-carbon fragment.
The resulting terminal alkyne undergoes hydroboration to the correct aldehyde
或者，我們可以⽤⼄炔作為⼆碳片段構建碳骨架。所得到的末端炔烴經歷硼氫化反應成為正
確的醛.
Problem 6, 64
18-8 Synthesis of Ketones from Carboxylic Acids
• Organolithiums will attack the lithium salts of carboxylate

anions to give dianions.
有機鋰將會攻擊羧酸根陰離⼦的鋰鹽以產⽣⼆價陰離⼦
• Protonation of the dianion forms the hydrate of a ketone,
which quickly loses water to give the ketone.
⼆價陰離⼦的質⼦化形成酮的⽔合物，其迅速失去⽔分
⽽得到酮。

18-9 Synthesis of Ketones from Nitriles
• A Grignard or organolithium reagent can attack the carbon

of the nitrile.
Grignard試劑或有機鋰試劑可以攻擊腈的碳。
• The imine is then hydrolyzed to form a ketone.
然後將亞胺⽔解形成酮

Reduction of Nitriles to Aldehydes
• Aluminum hydrides can reduce nitriles to aldehydes.

氫化鋁可以將腈還原成醛
• Diisobutylaluminum hydride, abbreviated (i-Bu)2AlH or DIBAL-H, is
commonly used for the reduction of nitriles.
氫化⼆異丁基鋁（縮寫為（i-Bu）2AlH或DIBAL-H）通常⽤於還
原腈 Problem 7, 8
18-10 Synthesis of Aldehydes and Ketones from Acid
Chlorides and Esters
• Aldehydes are easily oxidized to acids.

醛很容易被氧化成酸。
• The hydride anion adds to the carbonyl carbon; the alkoxide

is protonated to form an alcohol.
氫陰離⼦加成羰基碳; 醇鹽被質⼦化形成醇。
Acids to Acid Chlorides
Aldehydes from Acid Chlorides
• Lithium aluminum tri(t-butoxy)hydride is a milder

reducing agent that reacts faster with acid chlorides than
with aldehydes.
三（叔丁氧基）氫化鋰鋁是⼀種溫和的還原劑，與酰
氯的反應速度比醛快。
Lithium Dialkyl Cuprate Reagents
• A lithium dialkylcuprate will transfer one of its alkyl

groups to the acid chloride.
⼆烷基銅酸鋰將其烷基之⼀轉移到酰氯中。
• Grignards and organolithiums cannot do this reaction.
Grignards和有機鋰不能做這個反應。

Reaction with a Grignard Reagent
• A strong nucleophile attacks the carbonyl carbon, forming an alkoxide ion that is
then protonated.
強烈的親核試劑攻擊羰基碳，形成⼀個醇鹽離⼦，然後被質⼦化。

Problem 10, 11, 12
18-12 Hydration of Ketones and Aldehydes
• In an aqueous solution, a ketone or an aldehyde is in equilibrium with

its hydrate, a geminal diol.
在⽔溶液中，酮或醛與其⽔合物（⼀種偕⼆醇）處於平衡狀態。
• With ketones, the equilibrium favors the unhydrated keto form
(carbonyl).
⽤酮，平衡有利於未⽔合的酮形式（羰基）。

Acid-Catalyzed Hydration of Carbonyls
• Hydration occurs through the nucleophilic addition mechanism,

with water (in acid) or hydroxide (in base) serving as the
nucleophile.
通過親核加成機理髮⽣⽔合作⽤，⽤⽔（在酸中）或氫氧化
物（在鹼中）作為親核試劑。

Base-Catalyzed Hydration of Carbonyls

18-13 Formation of Cyanohydrins
• The mechanism is a base-catalyzed nucleophilic addition: attack by

cyanide ion on the carbonyl group, followed by protonation of the
intermediate.
其機理是鹼催化的親核加成：氰化物離⼦對羰基的攻擊，隨後質
⼦
化中間體。
• HCN is highly toxic.
HCN是劇毒的

Cyanohydrin Reactions
Problem 13, 14, 16, 67, 68

18-14 Formation of Imines
• Ammonia or a primary amine reacts with a ketone or an aldehyde to

form an imine.
氨或伯胺與酮或醛反應形成亞胺。
• Imines are nitrogen analogues of ketones and aldehydes with a C═N
bond in place of the carbonyl group.
亞胺是酮和具有C = N鍵代替羰基的醛的氮類似物。
• Optimum pH is around 4.5.
最適pH約為4.5。

Acid-catalyzed addition of the amine to the carbonyl
compound group
將胺催化加成到羰基化合物基團上
Acid-catalyzed dehydration
酸催化脫⽔

Imine Reactions

18-15 Condensations with Hydroxylamine and Hydrazines

Other Condensations with Amines
Problem 22, 23, 39, 69, 70

18-16 Formation of Acetals

Mechanism for Hemiacetal Formation
• Must be acid-catalyzed
必須是酸催化的
• Adding H+ to carbonyl makes it more reactive with the
weak nucleophile, ROH.
向羰基添加H +使其與弱親核試劑ROH更具反應性。

Acetal Formation

Hydrolysis of Acetals
• Acetals can be hydrolyzed by addition of

dilute acid.
縮醛可以通過加入稀酸⽔解。
• The excess of water drives the equilibrium toward the
formation of the ketone or aldehyde.
過量的⽔驅使平衡形成酮或醛。

Cyclic Acetals
• Addition of a diol produces a cyclic acetal.

加入⼆醇產⽣環狀縮醛。
• The reaction is reversible.
反應是可逆的
• This reaction is used in synthesis to protect carbonyls from
reaction.
該反應⽤於合成以保護羰基免於反應。
Problem 26, 49, 40, 41, 52
Problem 40

18-17 Use of Acetals as Protecting Groups
Problem 29
18-18 The Wittig Reaction
• The Wittig reaction converts the carbonyl group into a new

C═C double bond where no bond existed before.
Wittig反應將羰基轉化為新的C = C雙鍵，其中之前不存
在鍵
• A phosphorus ylide is used as the nucleophile in the
reaction.
磷葉立德被⽤作反應中的親核試劑。

Preparation of Phosphorus Ylides
• Prepared from triphenylphosphine and an unhindered alkyl

halide
由三苯基膦和無阻的烷基滷製備
• Butyllithium then abstracts a hydrogen from the carbon
attached to phosphorus.
丁基鋰然後從與磷相連的碳中提取氫。
Mechanism of the Wittig Reaction
Betaine formation
Oxaphosphetane formation
Oxaphosphetane形成

Mechanism for Wittig
• The oxaphosphetane will collapse, forming a carbonyl

(ketone or aldehyde) and a molecule of triphenyl phosphine
oxide.
• oxaphosphetane將崩潰，形成羰基（酮或醛）和三苯基
氧化膦分⼦

Problem 33, 47, 50, 59
Problem 50

18-19 Oxidation of Aldehydes
Aldehydes are easily oxidized to carboxylic acids.

The Tollens Test
• The Tollens test involves

adding a solution of silver–
ammonia complex (the
Tollens reagent) to the
unknown compound.
• Tollens試驗涉及將銀 - 氨
絡合物（Tollens試劑）的
溶液加入到未知的化合物
中
如果存在醛，則其氧化將銀離⼦
• If an aldehyde is present, its 還原成⾦屬銀
oxidation reduces silver ion
to metallic silver.
© 2017 Pearson Education, Ltd. Problem 34

Catalytic Hydrogenation
• Widely used in industry

廣泛⽤於⼯業
• Raney nickel is finely divided Ni powder saturated with
hydrogen gas.
阮內鎳是⽤氫氣充分分散的鎳粉末。
• It will attack the alkene first, then the carbonyl.
它會⾸先攻擊烯烴，然後是羰基。
Deoxygenation of Ketones
and Aldehydes
• The Clemmensen reduction or the Wolff–Kishner

reduction can be used to deoxygenate ketones and
aldehydes.
Clemmensen還原或Wolff-Kishner還原可⽤於脫氧酮
和醛。
Clemmensen Reduction

Wolff–Kishner Reduction
• Form hydrazone, then heat with strong base like KOH or

potassium tert-butoxide.
形成腙，然後⽤強鹼如KOH或叔丁醇鉀加熱。
• Use a high-boiling solvent: ethylene glycol, diethylene glycol, or
DMSO.
使⽤⾼沸點溶劑：⼄⼆醇，⼆⽢醇或DMSO。
• A molecule of nitrogen is lost in the last steps of the reaction.
在反應的最後幾步中失去了⼀個氮分⼦。

Wolff–Kishner Mechanism
Problem 36, 51
Problem 48, 53, 54, 55, 56, 61, 51, 52, 39
Problem 48

Problem 51
Problem 52

Problem 39

Problem 47

Problem 66

Chapter 18 CO

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 18 CO

Uploaded by

Copyright:

Available Formats

Ketones and Aldehydes Chapter 18

© 2014 Pearson Education, Inc.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• Carbon is sp2 hybridized.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• For cyclic ketones, the carbonyl carbon is assigned the number 1.

© 2017 Pearson Education, Ltd.

• The aldehyde carbon is number 1.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• Ketones and aldehydes are more polar, so they have a higher

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• Gas at room temperature

• Acetone and methyl ethyl ketone are common industrial

© 2017 Pearson Education, Ltd.

• A Grignard reagent can be used to make an alcohol, and

© 2017 Pearson Education, Ltd.

• Pyridinium chlorochromate (PCC) is selectively used to

© 2017 Pearson Education, Ltd.

• The double bond is oxidatively cleaved by ozone,

© 2017 Pearson Education, Ltd.

• The initial product of Markovnikov hydration is an enol, which

• Hydroboration–oxidation of an alkyne gives anti-Markovnikov

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• Organolithiums will attack the lithium salts of carboxylate

© 2017 Pearson Education, Ltd.

• A Grignard or organolithium reagent can attack the carbon

© 2017 Pearson Education, Ltd.

• Aluminum hydrides can reduce nitriles to aldehydes.

• Aldehydes are easily oxidized to acids.

• The hydride anion adds to the carbonyl carbon; the alkoxide

Aldehydes from Acid Chlorides

• Lithium aluminum tri(t-butoxy)hydride is a milder

• A lithium dialkylcuprate will transfer one of its alkyl

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• In an aqueous solution, a ketone or an aldehyde is in equilibrium with

© 2017 Pearson Education, Ltd.

• Hydration occurs through the nucleophilic addition mechanism,

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• The mechanism is a base-catalyzed nucleophilic addition: attack by

© 2017 Pearson Education, Ltd.

Problem 13, 14, 16, 67, 68

• Ammonia or a primary amine reacts with a ketone or an aldehyde to

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

Problem 22, 23, 39, 69, 70

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

© 2017 Pearson Education, Ltd.

• Acetals can be hydrolyzed by addition of

© 2017 Pearson Education, Ltd.

• Addition of a diol produces a cyclic acetal.