TYPES OF CARBONYL COMPOUNDS�

General Name Name General Name

Name formula suffix formula suffix
O O
Aldehyde -al Ester -oate
C C R'
R H R O
O� O
Ketone C� -one Lactone C
R R' O
(cyclic ester)
O -oic
Carboxylic
acid� C H acid O
R O
Amide C R' -amide
Acid O
X=halogen -oyl R N
R"
halide C halide
R X O
Lactam�
C R'
Acid O O� -oic (cyclic amide) N
C
anhydride
anhydride R O
C
R
Detergents and "fatty acids" - amphiphilic molecules CO2H

CO2 omega-3-fatty
hydrophobic hydrophilic acid

H2O

H2O
H2O
Phospholipids - Fatty acid esters
of glycerol
grease
H2O OH glycerol
OH a triol
H2O
OH
H2O
MICELLE

O
O
O
O
O LIPID BILAYER
O P O
O NH3
Phosphatidylcholine
 O
Amides in Peptides and Proteins O
OH

NH2
a
OH OH OH OH
H2N H2N OH H2N H2N
H2N
O O O O
O
glycine alanine phenylalanine asparagine glutamic acid

Five of the 20 amino acid building blocks that go into all proteins
All a-amino acids

Proteins are polyamides

O O
H H
N N
N N
H H
O O

CO2H
Each protein is defined by a
specific primary sequence of
amino acids
 b -Lactam Antibiotics Other Penicillins
varied at this
position
H H
H2N S H H H
N S
N O
O
H N
HO2C O Penicillin G
H
6-Aminopenicillamic acid HO2C

b-lactam g-lactam d-lactam�

NH NH
NH
O
O O

a b O g a
H2N OH H2N H2N OH
OH d b
b O g a O

b-amino acid g-amino acid d-amino acid

SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES�
1. Oxidation of alcohols �
Cl- Na2Cr2O7 will over-oxidize to
O
N H CrO3
carboxylic acid
R1� OH� R1 H

R2 O O R2
Na2Cr2O 7� 1. R2MgBr

H 2SO4� H 2. pH7
R1 OH R1 R2 R1 R1 OH

2. From alkynes

O� O
2+
Hg , H2 O
R1 H 1. RBH2 R1
H2 SO 4 R1 H
R1 Me� 2. H2 O2, NaOH H
SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES�

3. Friedel-Crafts Acylation
O O

Cl R R
AlCl3

4. Ozonolysis
1. O3

2. Zn/H3O+ O O
H
 Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
1. Nucleophilic Addition:
Reactions with Aldehydes and Ketones (Chapter 19)

A.� O -O Nu HO Nu�
H3O+

R R'�

Nu

Example: Grignard Reaction� Section 19.8

O HO
CH3MgBr +

Example: Cyanohydrin Formation Section 19.7

O HO CN
HCN
H H
 Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
1. Nucleophilic Addition
A. Hydration and Acetal Formation
O H2O HO OH O OH
HO O O

H3O+
Section 19.6 Section 19.11

R H O O
+
H
OH OH R� H
Electrophilic at C
No longer electrophilic at C�

HO
OH OH OH
HO OH OH
R H H2O O
R H
HO R H

O O O Protected (masked)
aldehyde
R H R H
Acetals as Protecting Groups for Aldehydes�

M go
Br
O
H
X BrMg
O
H

+
H
OH OH

H H
Br Mgo
BrMg
O O O O

O
1.
electrophile
H
2. pH7

H
H
OH O H2O/H+ OH O O
 Overview of Reactions 4/27-5/9 - Reactions with carbonyls
1. Nucleophilic Addition
A.

CH3-Br BuLi
P P CH3
P CH2
O

triphenyl phosphine
Ph3P CH2

Wittig Reaction Ph3PO O

Ph = Phenyl

Section 19.12
 Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
1. Nucleophilic Addition

O Nu
B. -O Nu H3O+ H2O Nu

R R' R R'

Nu
Overview of Reactions 4/27-5/9 - Reactions with carbonyls
1. Nucleophilic Addition
B. continued
Example: Imine Formation
O H H2O H
O
NH2 H3O+
NH
H

H2N

H H
H2O H

N NH NH

Section 19.9
Sometimes called a Schiff base in biochemistry
 SUMMARY - Synthesis of Carboxylic Acids�
1. Oxidative cleavage of alkene
R' HO
KMnO4 HO
O O
R
R R'

2. Oxidation of 1 alcohols and aldehydes

O�

O�
R H Jones Oxidation�

OH R OH�
H

R H

3. Carboxylation of Grignard Reagents

O�
CO2�
RMgBr�
R OH�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
2. Nucleophilic Acyl Substitution:
Reactions with Carboxylic Acid derivatives (Chapter 21)
O -O Nu O

R Y Y R Nu
-
Y
Nu
Y = Leaving Group

O O OH
LiAlH4 LiAlH4
Ester hydride reduction
OR H H Chapter 17.5
RO-Li+

nucleophilic substitution nucleophilic addition

MeMgBr O MeMgBr OH
O Me Ester grignard reaction
Section 21.6
Me Me
OR RO-Li+�
nucleophilic substitution nucleophilic addition�
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
2. Nucleophilic Acyl Substitution
Carboxylic Acid Derivatives

Example:Acyl Halide Section 21.4 Example:Ester Section 21.6

O OH O Cl O OH O OEt

SOCl2 CH3CH2OH

HCl

O Cl O NR2

NHR2 Example:Amide
Section 21.7
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
3. Alpha Substitution: Enolate/Enol Chemistry

O O O

E+ = O
must have "a " H enolate electrophile
(pKa 10-20)
E
OH OH

enol

OH O
Br2
Alpha Halogenation Section 22.3
Br

Alpha Alkylation
O OLi O Section 22.8
LDA (base)
CH3I Li
N
H LDA =
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
4. Condensation Reactions: Enolate/Enol Chemistry

O O O O
base� R' OH

R R R'� R'' R'' R

H

Aldol Reaction Section 23.2-23.7

O OH O
base O

O
H� CH3 H3C C H
H CH2 H2
H3C H�

Claisen Condensation Section 23.8-23.9

O O O O
base
+ OEt -
O H3C C OEt
EtO CH3 EtO CH2 H2

H3C OEt
Key in fatty acid biosynthesis
Overview of Reactions 4/27-5/9 - Reactions with carbonyls�
4. Condensation Reactions: Enolate/Enol Chemistry
continued�
Michael Reaction Section 23.11�

O O O O O O
NaOEt

EtO Me EtO Me EtO Me

O
H H H H HOEt

Me O
H

Me

O O

EtO Me
H

H O
H
Me