TYPES OF CARBONYL COMPOUNDS - Chemistry IYC 2011 and

TYPES OF CARBONYL COMPOUNDS General Name Name formula suffix O -al Aldehyde C R H O Ketone C -one R R' O -oic C acid Carboxylic acid H...

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TYPES OF CARBONYL COMPOUNDS� General formula

Name

Name suffix -al

O

Aldehyde

C

R

Name

General formula O

Ester

H

R

C

O�

Ketone

C�

R

Acid anhydride

R'

O

Carboxylic acid� Acid halide

-one

R

C

O

O

-oyl halide

X=halogen

C

R

X

O R

C

O� O

C

Lactone (cyclic ester)

-oic acid

H

-oic anhydride R

Name suffix -oate

O O C

R'

O

O

Amide

R

Lactam� (cyclic amide)

C

N

-amide

R' R"

O C

N

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

O

O

LIPID BILAYER

O O P O O

NH3

Phosphatidylcholine

O

Amides in Peptides and Proteins

OH

O

NH2

a OH

H2N

OH

H2N

O

O

glycine

alanine

OH

H2N

OH

H2N

O

O

O

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

O

Each protein is defined by a specific primary sequence of amino acids

O

O

H N

N H

O

CO2H

b -Lactam Antibiotics H2N

H

H

Other Penicillins varied at this position

S

H H N

N

O

HO2C

H

O

g-lactam

NH

Penicillin G

H

d-lactam� NH

NH

O

O

b

N

HO2C

b-lactam

H2N

S

O

6-Aminopenicillamic acid

a

H

O

OH O

b-amino acid

a

H2N

H2N

g

g

O

b a

OH

g-amino acid

d

b

OH O

d-amino acid

SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 1. Oxidation of alcohols � ClN H CrO3 R1�

O

R2 R1

H

R1

OH�

Na2Cr2O7 will over-oxidize to carboxylic acid

O

O

Na2Cr2O 7� H 2SO4�

OH

R1

R1

R2

R2

1. R2MgBr 2. pH7

H

R1

OH

2. From alkynes O�

O

2+

R1

H

Hg , H2 O H2 SO 4

R1

Me�

R1

H

1. RBH2 2. H2 O2, NaOH

R1

H

SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 3. Friedel-Crafts Acylation O Cl

O R

R

AlCl3

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

H

O

O

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�

O

Section 19.8

HO

CH3MgBr +

Example: Cyanohydrin Formation O

Section 19.7

HO

CN

HCN H

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

O

O

HO

H3O+ Section 19.11

Section 19.6

O R

H

O

O

R�

H

+

OH OH

Electrophilic at C

H

No longer electrophilic at C�

OH R

HO

OH OH

H

HO

OH OH

R

H

HO

R

O

O

O

H

R

H

H2O

O

R

H

Protected (masked) aldehyde

O

Acetals as Protecting Groups for Aldehydes�

X

H Br O

OH OH

H

H

BrMg O

+

H Br

M go

O

Mgo

O

H BrMg

electrophile

O

O O

1.

H

2. pH7 H OH

O

H

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 Wittig Reaction

Section 19.12

Ph3PO

CH2

O

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

O NH2

H2O

H3O+

H

NH

H H2N

H

H N

H2O NH

Sometimes called a Schiff base in biochemistry

H

NH

Section 19.9

SUMMARY - Synthesis of Carboxylic Acids� 1.

Oxidative cleavage of alkene R'

HO

KMnO4

HO O

R

2.

R

O R'

Oxidation of 1 alcohols and aldehydes O� R

H OH

R

H R

3.

O�

Jones Oxidation�

OH�

H

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

O

Nu Y

Y

-

R

Nu

Y Nu Y = Leaving Group

O

LiAlH4 OR

O

RO-Li+

LiAlH4 H

O OR

Ester hydride reduction Chapter 17.5

H

nucleophilic substitution

MeMgBr

OH

nucleophilic addition

O

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

O

Example:Ester Section 21.6 O

Cl

OH

SOCl2

O

OEt

CH3CH2OH HCl

O

Cl

O

NHR2

NR2

Example:Amide Section 21.7

Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 3. Alpha Substitution: Enolate/Enol Chemistry O

O

O

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

E+ = electrophile

enolate

O E

OH

OH

enol

OH

Br2

O Br

O

H

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

O

O

base�

R'�

R

R

OH

R' R''

O

R''

R

H

Aldol Reaction O

Section 23.2-23.7

OH

O

base

O H�

CH3

H

H3C Claisen Condensation

O EtO

H

C H2

H�

Section 23.8-23.9

O

O

base CH3

H3C

CH2

O

EtO

+

O

CH2

H3C

O

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

O

EtO

Me

H

H

O

NaOEt

O

EtO

O

O Me

EtO

O

Me

H

H

HOEt

O

Me

H Me

O

O EtO

Me

H H

O H

Me