TYPES OF CARBONYL COMPOUNDS

General
formula

Name

Name
suffix
-al

Aldehyde

Name

General
formula
O

Ester

Ketone

Acid
anhydride

R'

Carboxylic
acid
Acid
halide

-one

-oyl
halide

X=halogen

O
R

O
O

Lactone
(cyclic ester)

-oic
acid

-oic
anhydride
R

Name
suffix
-oate

O
O
C

R'

Amide

Lactam
(cyclic amide)

-amide

R'
R"

O
C

R'

Detergents and "fatty acids" - amphiphilic molecules

CO2

hydrophobic

hydrophilic

CO2H

omega-3-fatty
acid

H2O
H2O

H2O

Phospholipids - Fatty acid esters

of glycerol

grease
OH

H2O
H2O

OH

glycerol
a triol

OH
H2O

MICELLE
O
O

LIPID BILAYER

O
O P O
O

NH3

Phosphatidylcholine

Amides in Peptides and Proteins

OH

NH2

a
OH

H2N

OH

H2N

glycine

alanine

OH

H2N

OH

H2N

phenylalanine

OH

H2N

glutamic acid

asparagine

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

Proteins are polyamides

H
N

N
H

Each protein is defined by a

specific primary sequence of
amino acids

H
N

N
H

CO2H

b -Lactam Antibiotics
H2N

Other Penicillins
varied at this
position

H H
N

HO2C

g-lactam

NH

Penicillin G

d-lactam
NH

NH

HO2C

b-lactam

H2N

6-Aminopenicillamic acid

OH
O

b-amino acid

H2N

H2N

b
a

OH

g-amino acid

OH
O

d-amino acid

SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES

1. Oxidation of alcohols
ClN H CrO3
R1

R2
R1

R1

OH

Na2Cr2O7 will over-oxidize to

carboxylic acid

Na2Cr2O 7
H 2SO4

OH

R1

R1

R2

R2

1. R2MgBr
2. pH7

R1

OH

2. From alkynes
O

2+

R1

Hg , H2 O
H2 SO 4

R1

Me

R1

1. RBH2
2. H2 O2, NaOH

R1

SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES

3. Friedel-Crafts Acylation
O
Cl

O
R

AlCl3

4. Ozonolysis
1. O3
2. Zn/H3O+

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

1. Nucleophilic Addition:
Reactions with Aldehydes and Ketones (Chapter 19)
O

A.
R

-O

Nu

H3O+

HO

R'
Nu

Example: Grignard Reaction

Section 19.8

HO

CH3MgBr +

Example: Cyanohydrin Formation

O

Section 19.7

HO

CN

HCN
H

Nu

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

1. Nucleophilic Addition
A. Hydration and Acetal Formation
O

H2O

HO

OH

OH

HO

H3O+
Section 19.11

Section 19.6

O
R

OH OH

Electrophilic at C

No longer electrophilic at C

OH
R

HO

OH OH

HO

OH OH

HO

H2O

Protected (masked)
aldehyde

Acetals as Protecting Groups for Aldehydes

H
Br
O

OH OH

BrMg
O

H
Br

M go

Mgo

H
BrMg

electrophile

O
O

1.

2. pH7
H
OH

H2O/H+

OH

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

1. Nucleophilic Addition
A.

CH3-Br

BuLi
P

CH3

CH2

triphenyl phosphine

Ph3P
Wittig Reaction

Section 19.12

Ph3PO

CH2

Ph = Phenyl

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

1. Nucleophilic Addition
O

B.
R

-O

Nu

H3O+

H2O

Nu

Nu
R

R'
Nu

R'

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

1. Nucleophilic Addition
B. continued
Example: Imine Formation
H

O
NH2

H2O

H3O+

NH

H
H2N

H
N

H2O
NH

Sometimes called a Schiff base in biochemistry

NH

Section 19.9

SUMMARY - Synthesis of Carboxylic Acids

1.

Oxidative cleavage of alkene

R'

HO

KMnO4

HO
O

2.

O
R'

Oxidation of 1 alcohols and aldehydes

O
R

H
OH

H
R

3.

Jones Oxidation

OH

Carboxylation of Grignard Reagents

O
RMgBr

CO2
R

OH

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

2. Nucleophilic Acyl Substitution:
Reactions with Carboxylic Acid derivatives (Chapter 21)
O
R

-O

Nu
Y

Nu

Y
Nu
Y = Leaving Group

LiAlH4
OR

RO-Li+

LiAlH4
H

O
OR

Ester hydride reduction

Chapter 17.5

nucleophilic substitution

MeMgBr

OH

nucleophilic addition

RO-Li+

nucleophilic substitution

MeMgBr
Me

OH
Me
Me

nucleophilic addition

Ester grignard reaction

Section 21.6

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

2. Nucleophilic Acyl Substitution
Carboxylic Acid Derivatives

Example:Acyl Halide Section 21.4

O

OH

Example:Ester Section 21.6

O

Cl

OH

SOCl2

OEt

CH3CH2OH
HCl

Cl

NHR2

NR2

Example:Amide
Section 21.7

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

3. Alpha Substitution: Enolate/Enol Chemistry
O

H
must have "a " H
(pKa 10-20)

E+ =
electrophile

enolate

O
E

OH

OH

enol

OH

Br2

O
Br

LDA (base)

Alpha Halogenation Section 22.3

OLi

Alpha Alkylation
Section 22.8

O
CH3I
LDA =

Li
N

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

4. Condensation Reactions: Enolate/Enol Chemistry
O

base

R'

OH

R'
R''

R''

Aldol Reaction
O

Section 23.2-23.7

OH

base

O
H

CH3

H3C
Claisen Condensation

O
EtO

C
H2

Section 23.8-23.9

base
CH3

H3C

CH2

EtO

CH2

H3C

H3C
OEt

C
H2

OEt -

OEt

Key in fatty acid biosynthesis

Overview of Reactions 4/27-5/9 - Reactions with carbonyls

4. Condensation Reactions: Enolate/Enol Chemistry
continued
Section 23.11

Michael Reaction
O

EtO

Me

NaOEt

EtO

O
Me

EtO

Me

HOEt

Me

H
Me

O
EtO

Me

H
H

O
H

Me