Aldehydes and Ketones.

Nucleophilic Addition to the Carbonyl Group

O R C H
R

O C R

An aldehyde
CHO

A ketone
O CH3 CCH3 H CH3

OH

OH

OH

OH

CH2OH

Progresterone

Ribose

IUPAC Nomenclature of Aldehydes O O

H
5-hexenal 4,4-dimethylpentanal

2-phenylpropanedial HCCHCH (keep the -e ending before -dial)

1) Base the name on the chain that contains the carbonyl group and replace the -e ending of the hydrocarbon by -al.

IUPAC Nomenclature of Aldehydes

2. The aldehyde functional group has priority over -X, -OH, -OR, double and triple bonds. Name OH as hydroxy substituent Name OR as alkoxy substituent

Substitutive IUPAC Nomenclature of Ketones

O CH3CH2CCH2CH2CH3 3-hexanone O CH3CHCH2CCH3 CH3 4-methyl-2-pentanone

1) Base the name on the chain that contains the H3C O carbonyl group and replace e by -one. Number the chain 4-methylcyclohexanone in the direction that gives the lowest number to the carbonyl carbon.

Trivial name for common aldehydes and ketones are widely used. Aldehydes are named after the parent carboxylic acids with oic acid or ic acid ending changed to aldehyde. (Table) Propanone is usually called acetone, while the other simple ketones are sometimes named by a functional-group name. The alkyl or aryl groups attached to the carbonyl group are named, then the word ketone is added.
O O O

CH3CCH3 IUPAC: trivial: propanone acetone

CH3CCH2CH3 butanone methyl ethyl ketone

(CH3)2CHCCH2(CH3)3 2,2,4-trimethyl-3-pentanone isopropyl tert-butyl ketone

Trivial names for some carboxylic acids and aldehydes Carboxylic acid
O HCOH O CH3COH O CH3CH2COH O CH3CH2CH2COH O COH benzoic acid butyric acid propionic acid acetic acid formic acid

Aldehydes
O HCH O CH3CH O CH3CH2CH O CH3CH2CH2CH O CH benzaldehyde butyraldehyde propionaldehyde acetaldehyde formaldehyde

Other positions in a molecule in relation to the carbonyl group may be referred to be Greek letters

Preparation of aldehyde

1. Oxidation of primary alcohols

CH3CH2OH + CrO3.2 N CH3CHO

Etanol

Kromat piridin oksida

Etanal

2. Reduction of acid derivates

RCOOH

SOCl2

RCOCl

H2/Pt

RCHO
COCH3

(H3C)2HC

CH3 + CH3COCl

AlCl 3

(H3C)2HC

CH3

Isopropil toluena

Asetil klorida

5-isopropil-2-metil asetofenon

3. From terminus of alkyne (hydroboration)

R C CH + Sia2BH R CH CH BSia2 H 2O 2 OH-/H2O RCH2CHO

disiamilboran Vinyl boran

Preparation of Ketone 1. Friedel-Craft Acylation

ArH

RCOCl

AlCl3

ArCOR

2. Oxidation of secondary alcohol

O CH3CH(OH)CH3 H2CrO4, H+ H3C C CH3

3. From Alkyne
R C C R H3O+, Hg 2+ H2O RCOCHR RCOCH2R

Hidration

(1) (BH3)2 (2) H2O2, OH-

RC(OH)=CHR

RCOCH2R

Hidroboration

Aldehydes and ketones have higher boiling than alkenes, but lower boiling points than alcohols.
boiling point 6C O 49C More polar than alkenes, but cannot form intermolecular hydrogen bonds to other carbonyl groups

OH

97C

Resonance Description of Carbonyl Group

O
C

O C +

nucleophiles attack carbon; electrophiles attack oxygen

Acid Catalyst Makes Carbon More Electrophilic

Step 1:
C O

H + H O + H H

+ OH

+C

OH

Nucleophilic
Addition to Carbonyl Groups

Basic Reaction

Nu:

Nu

Ketones are Less Reactive Than Aldehydes

1. Steric Reasons 2. R Groups are more electron donating than H

Grignard reagents act as nucleophiles toward the carbonyl group

R

+ C

diethyl ether

C + MgX O H3O+

MgX O

two-step sequence gives an alcohol as the isolated product

C
OH

Examples
H MgCl + H C O

2) H3O

CH2OH

H3C
CH3(CH2)4CH2MgBr + C O

2) H3O+

H
CH3(CH2)4CH2CHCH3 OH

Example

CH3 C CH2CH3

There are two other possibilities.

OH

Can you see them?

CH3MgX

O
C CH2CH3

Hydration of Aldehydes and Ketones

H2O

HO

Substituent Effects on Hydration Equilibria

OH + H2O R'
compared to H R

C
R

C
OH

R'

electronic:

alkyl groups stabilize reactants

steric:

alkyl groups crowd product

Mechanism of Hydration (acid)

Step 1: Acid Catalyst H C O

H + O
H

+ + C OH

H H

Step 2: Nucleophilic attack

H
O

+ OH

H
O +

OH

Mechanism of Hydration (acid) Step 3: Regeneration of catalyst H +O H +

O

H H O

H OH

O +

OH

One Alcohol Will React with a Ketone to Form a Hemiketal; Two Will Form a Ketal R C R' R-OH / H+ H O

R + R-OH

R"O

C R'

a hemiketal.

R"O

C R'

R"O

C R'

OR

+ H2O

A ketal

Example

O
CH + 2CH3CH2OH HCl CH(OCH2CH3)2 + H2O

Benzaldehyde diethyl acetal (66%)

Mechanism; Step 1: Protonate O of Carbonyl group H C

O

O + R

H O

Step 2: Nucleophilic atom (O) attacks electrophilic C. R

O

C O

O C +

O H

Step 3: H is abstracted to form hemiketal/hemiacetal R R O C O O C O H H + H H + O O R H R H Step 4: Hemiacteal/hemiketal is protonated to form A good leaving group (H2O) H H R R H O + + H O O C O O C O + H H R R

Hemiacetal/hemiketal-to-acetal/ketal Stage
Step 5: Leaving group (H2O) leaves and forms carbocation R
O

O+

O C+

Carbocation is stabilized by delocalization of unshared electron pair of oxygen

R O

C+

+ O

Hemiacetal/hemiketal-to-acetal/ketal Stage
Step 6: Second nucleophile (ROH) attacks carbocation

R O + O C O H H Step 7: Alcohol abstracts acidic H to form acetal/ketal.

O C+

R C O+ H

R
H

O C O

H + O

R
H

Hemiacetal/hemiketal-to-acetal/ketal Stage
Step 7: Alcohol abstracts acidic H to form acetal/ketal. R
O

R C O+ H

R
H

O C O

H + O

R
H

Hydrolysis of Acetals

OR"
R

O
R' + H2O C + R' 2R"OH

OR" mechanism:

reverse of acetal formation; hemiacetal is intermediate application:

aldehydes and ketones can be "protected" as acetals.

Reduction Reactions
Reducing Agents; LiAlH4 , NaBH4

Examples

O CH3 CH2 C CH2 CH3 + LiAlH4

+ 2) H 3O

OH CH3 CH2 CH CH2 CH3

Reduction of Aldehydes and ketones 1. Hydrogenation

2. Metal Hydrides

Wolff-Kishner reduction
O CCH3 H+ NH2NH2 NNH2 CCH3 KOH CH2CH3

Clemmensen reduction
O CCH3 Zn/Hg HCl CH2CH3

Oxidation of Aldehydes

O RCH H2O

OH RCH OH

RCOH

in aqueous solution

Example

O O

K2Cr2O7 H2SO4 H2O OH O

CH

COH
(75%)

via

CH OH