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Aldehydes and Ketones I.

OXIDATION,
REDUCTION AND SYNTHESIS

SUBTOPIC
1.
2.
3.

Naming aldehyde and ketone (or sketch the hydrocarbon given its
IUPAC name).
Physical properties of aldehyde and ketone (boiling point, solubility)
Reaction of aldehyde and ketone.
reduction of aldehyde and ketone using catalytic reduction
hydride reducing reagents: NaBH4, LiAlH4
complete removal of carbonyl group; Clemmensen and Wolf-Kishner Reduction

4.

Preparation of aldehydes and ketones


reduction of acid chlorides and esters
using Rosenmund Reduction
DIBAL-H
oxidation of alcohols by using oxidation of 1o and 2o alcohols

Jones, Sarret and PCC Reagents

5.

Describe the Tollens Test for aldehyde and ketone


Chapter 2

The Carbonyl Group


The carbonyl group consists of
one s bond formed by the overlap of sp2 hybrid orbitals,

and
one p bond formed by the overlap of parallel 2p orbitals

Structure of Aldehydes
The functional group of an aldehyde is a carbonyl

group bonded to a H atom


in methanal, it is bonded to two H atoms

in all other aldehydes it is bonded to one H and one

carbon atom

H
C

H
Methanal
(formaldehyde)

H3 C
Ethanal
(acetaldehyde)

Structure of Ketones
The functional group of a ketone is a carbonyl

group bonded to two carbon atoms


O
CH 3 -C-CH
Propanone
(Acetone)

O
3

Cyclohexanone

NOMENCLATURE
ALDEHYDE AND KETONE
1. Name by the IUPAC system on aldehyde and ketone
structure (or sketch the hydrocarbon given its IUPAC
name).
PAGE : 730-731

Chapter 2

Nomenclature-Aldehydes
IUPAC names: select as the parent alkane the

longest chain of carbon atoms that contains the


carbonyl group
because the carbonyl group of the aldehyde must be on

carbon 1, there is no need to give it a number


Aldehydes are named by replacing the -e of the corresponding parent
alkane with -al

For unsaturated aldehydes, show the presence of

the C=C by changing the infix -an- to -en the location of the suffix determines the numbering

pattern

Nomenclature-Aldehydes
O
CH3CH

O
CH3CH2CH

CH3

CH3CHCH2CH2CHCH
CH2CH3

ethanal

propanal

2-ethyl-5-methylhexanal

Nomenclature-Aldehdyes
For cyclic molecules in which the -CHO group is

attached to the ring, the name is derived by


adding the suffix -carbaldehyde to the name of
the ring
O
C

2-cyclopentenecarbaldehyde

Nomenclature-Ketones
IUPAC names:
select as the parent alkane the longest chain that contains the

carbonyl group,
indicate its presence by changing the suffix -e to -one, and
number to give C=O the smaller number

O
CH3CH2CCH2CH2CH2
3-hexanone

O
CH3CH

CHCH2CCH3

4-hexen-2-one

CH3CH2CCH2CCH3
2,4-hexanedione

Sometimes, acyl groups must be named as substituents. The three most common
acyl groups are shown below

Chapter 2

11

2. Relate molecular structure to physical properties


such as boiling point, solubility

Chapter 2

12

PHYSICAL PROPERTIES OF ALDEHYDES AND


KETONES

BOILING POINTS

- Polarization of the carbonyl group creates


dipole-dipole attractions between the molecules
of ketones and aldehydes.
- this attractions resulting in higher boiling points
for ketones and aldehydes than for hydrocarbons
and ethers of similar molecular weights.
- did not have O-H and N-H bonds can not form
hydrogen bonds with each other.
- boiling points of ketones and aldehydes are
lower than alcohols of similar molecular weight.

Boiling points of alkane, ether, aldehyde,


ketone and alcohol of similar molecular
weight.
O
CH3CH2CH2CH3
butane
bp 0oC

CH3 O CH2CH3 CH3CH2 C H

O
CH3 C CH3

CH3CH2CH2-OH
1-propanol

methoxyethane

propanal

acetone

bp 8oC

bp 49oC

bp 56 C

bp 97oC

bp alkane < bp ether < bp ketone, bp aldehyde < bp alcohol

bp ketone, bp aldehyde > bp alkyl halides

WATER SOLUBILITIES
- ketones and aldehydes have lone pairs of electrons
and can act as hydogen bond acceptors with other
compounds having O-H or N-H bonds.
- for example, the OH hydrogen of water or an alcohol
can form a hydrogen bond with unshared electrons on
a carbonyl oxygen atom.
R

+ -

C O

C O
R'

+ -

hydrogen bonding

H
O

hydrogen bonding

R
O
-

Because of the hydrogen bonding, ketones and

aldehydes are good solvents for polar hydroxylic


substances such as alcohols.
Ketones and aldehydes are soluble in water.

- ketones and aldehydes with up to 4 carbon atoms are


fairly soluble in water.
- the solubility of ketones and aldehydes in water
decreases with the increasing length of the carbon
chain.

3. Predict the product form by reduction of aldehyde


and ketone using catalytic reduction, hydride
reducing reagents: NaBH4, LiAlH4 and complete
removal of carbonyl group; Clemmensen and WolfKishner Reduction

Chapter 2

17

Mechanism of Reduction

The mechanism involves:

Addition of nucleophilic hydride ion, H-, to the


positively polarized electrophilic carbon of C=O to
form an alkoxide ion intermediate

Protonation of the alkoxide ion intermediate

18

Reduction
Aldehydes can be reduced to 1 alcohols and ketones

to 2 alcohols. In addition, the C=O group can be


reduced to a -CH2- group

Aldehydes
O

Can be
Reduced to

Ketones

Can be
Reduced to
OH

RCH 2 OH

RCH

RCHR'

RCR'
RCH 3

RCH 2 R'

1. CATALYTIC REDUCTION (PAGE : 552)

Reduction of a carbonyl compound in general

gives an alcohol
Note that organic reduction reactions add the equivalent

of H2 to a molecule

Chapter 2

20

Aldehydes are reduced to give primary


alcohols
Ketones are reduced to give secondary
alcohols

Chapter 2

21

Catalytic reductions are generally carried out from 25 to 100C

and from 1 to 5 atm H2

OH
+

H2

Pt
25o C, 2 atm

Cyclohexanone

Cyclohexanol

A carbon-carbon double bond may also be reduced under these

conditions
O
H

CH
C

H3 C
H
trans-2-Butenal
(Crotonaldehyde)

2 H2
Ni

CH 3 CH 2 CH 2 CH 2 OH
1-Butanol

- be careful choice of experimental conditions, it is often


possible to selectively reduce a carbon-carbon double in the
presence of an aldehyde or ketone

2. Metal Hydride Reduction


The most common laboratory reagents for the

reduction of aldehydes and ketones are NaBH4 and


LiAlH4
both reagents are sources of hydride ion, H:-, a very

powerful nucleophile

H
H
S odium
borohydride

Li + H-Al-H
H
Lithium aluminum
hydride (LAH)

Na H-B-H

H
H

Hydride ion

2A. HYDRIDE REDUCING AGENT : i) Sodium


Borohydride (NaBH4) (PAGE : 553)

NaBH4 is not sensitive to moisture and it does not reduce other


common functional groups
It adds the equivalent of H-

Chapter 2

24

NaBH4 Reduction
The key step in metal hydride reduction is transfer of

a hydride ion to the C=O group to form a tetrahedral


carbonyl addition compound
H

+
Na H-B-H + R-C-R'

O BH 3 Na

R-C-R'
H
from the hydride
reducing agent

H2 O
OH
R-C-R'
H

from
water

COMPARISON BETWEEN CATALYTIC REDUCTION AND


METAL HYDRIDE REDUCTION
Metal hydride reducing agents do not normally

reduce carbon-carbon double bonds, and selective


reduction of C=O or C=C is often possible

O
RCH=CHCR'

1 . NaBH 4
2. H 2O

O
RCH=CHCR'

+ H2

Rh

OH
RCH=CHCHR'

O
RCH 2 CH 2 CR'

2. HYDRIDE REDUCING AGENT : ii) Lithium Aluminum


Hydride (LiAlH4) (PAGE : 553)

LiAlH4 is more powerful, less specific, and very reactive with


water

Like NaBH4, it adds the equivalent of H-

Chapter 2

27

Unlike NaBH4, LiAlH4 reacts violently with water,

methanol, and other protic solvents. Reductions


using it are carried out in diethyl ether or
tetrahydrofuran (THF)
O
ether
4 RCR + LiAlH 4
-

(R 2 CHO) 4 Al Li
A tetraalky aluminate

H2 O

OH
4 RCHR + aluminum salts

3. REMOVAL OF CARBONYL GROUP :


Deoxygenation
Reduction of C=O to CH2
Two methods:
Clemmensen reduction if molecule is stable in hot acid.
Wolff-Kishner reduction if molecule is stable in very strong

base.

Chapter 2

29

i. Clemmensen Reduction (PAGE :


690-691)
Refluxing

an aldehyde or ketone with amalgamated zinc in


concentrated HCl converts the carbonyl group to a methylene group

O
C

CH2CH3

Zn(Hg)

CH2CH2CH3

HCl, H2O
O
CH2

Zn(Hg)
H

CH2

CH3

HCl, H2O
Chapter 2

30

ii. Wolff-Kishner Reduction


In the original procedure, the aldehyde or ketone and hydrazine

are refluxed with KOH in a high-boiling solvent. The same


reaction can be brought about using hydrazine and potassium
tert-butoxide in DMSO

O
CCH 3 + H2 NNH 2
Hydrazine

KOH
diethylene glycol
(reflux)
CH 2 CH 3 + N2
Chapter 2

+ H2 O
31

Wolff-Kishner Reduction
O
R

N
R

NH2

OH
N

H2O
R

N H

N
R

N H
R

H2O
H
R
R

H2O
H

H2O N N R
R

N
H
R

N H

R H

OH

PREPARATION OF ALDEHYDE
4. Predict the product of aldehydes and ketones from
reduction of acid chlorides and esters using
Rosenmund Reduction and DIBAL-H

5. Predict the product of aldehyde and ketone through


oxidation of alcohols by using oxidation of 1o and 2o
alcohols, Jones, Sarret and PCC Reagents

Chapter 2

33

1) Oxidation of primary alcohol (1)

-Can be using two reagents;


i)

PCC in CH2Cl2(PAGE 733)


CH2OH

PCC
CH2Cl2

Collins/Sarrret reagents (CrO3 in pyridine)


- Primary Alcohols are oxidized to aldehydes.
ii)

CHO

PCC Reagents
- Pyridinium chlorochromate is a reddish orange solid reagent
used to oxidize primary alcohols to aldehydes and secondary
alcohols to ketones.
- A reagent which stops the oxidation at the aldehyde stage is
pyridinium chlorochromate (PCC)
-PCC is made from chromium trioxide under acidic conditions
-It is used in organic solvents such as methylene chloride (CH2Cl2

- Pyridinium chlorochromate, or PCC, will not fully oxidize a


primary alcohol to the carboxylic acid as does the Jones reagent.
- A disadvantage to using PCC is its toxicity

Chapter 2

35

2) Reduction of acid chlorides and esters


Using Diisobutylaluminium hydride (DIBAL-H) (DIBAH)
(PAGE : 735)
Reduction to an aldehyde can be accomplished by using a
more reactive carboxylic acid derivatives such as an acyl
chloride, ester or nitrile and a less reactive hydride source
The use of a sterically hindered and therefore less

reactive aluminum hydride reagent is important


Acid chlorides react with Diisobutylaluminium hydride

(DIBAL-H) at low temperature to give aldehydes

i) Reduction of an ester
O
CH3(CH2)10COCH3

1. DIBAH, toluene, -78 C


2. H3O+

O
CH3(CH2)10CH

H
DIBAH =

(CH3)2CHCH2 Al

CH2CH(CH3)2

ii) Reduction of an acid chloride

: O:

: O:
R

..
Cl
.. :

R
1 DIBAH
+
2 H3O

aldehyde

acid
chloride

Dry ice (solid


CO2) sublimes
at 78C.

: O:
R

..
Cl
.. :

-78C
1equiv.

: O:
R

: O:

ester
R

..
OR
..

1 DIBAH
+
2 H3O

Chapter 2

aldehyde
Only 1 equivalent of
very cold DIBAL-H
is used to avoid
further reduction of
the aldehyde to an
alcohol.

38

Reduction of an ester to an aldehyde can be accomplished at low


temperature using DIBAL-H
As the carbonyl re-forms, an alkoxide leaving group departs

Chapter 2

39

3) ROSENMUND REDUCTION
Chemical reaction that reduces an acid halide to
an aldehyde using hydrogen gas over palladium-oncarbon poisoned with barium sulfate.

PREPARATION OF KETONE

Chapter 2

41

1) Oxidation of secondary alcohols (2) (PAGE 738,557)

Can be using;
i) PCC in CH2CI2
(CH3)3C

OH

PCC
CH2Cl2

(CH3)3C

ii) Jones reagent (CrO3 with diluted H2SO4 in acetone)

Secondary alcohols are oxidized to give ketones. (PAGE


: 558)

iii) Collins/Sarrret reagents (CrO3 in pyridine)


- Secondary Alcohols are oxidized to ketones.

Chemistry 243 - Lecture 25 and 26

43

2) Acid Chlorides + Lithium Dialkyl Copper (Gilman Reagent):

O
CH3 (CH2)4 C

+
Cl

hexanoyl chloride

(CH3)2 Cu- Li+


dimethyl copper lithium
Gilman reagent

O
CH3 (CH2)4 C

2-heptanone

CH3

- 78C
ether

6. Describe the Tollens Test for aldehyde and ketone

Chapter 2

45

5. Tollens Test (PAGE : 761)


For identifying aldehydes and ketones.
It is a mixture of aqueous silver nitrate and ammonia.
In this reaction aldehyde is oxidised to carboxylate ion and

argentum is deposited onthe wall of the test tube as silver


mirror.
Tollens (works for aliphatic aldehydes, aromatic aldehyde
reacts slowly, ketones NO reactions)
O
O
_ H2O
_
+
2 Ag + R C O +
R C H + 2 Ag(NH3)2 + 3 OH

+
NH3)2

_
+

3 OH

O
H2O

2 Ag + R C O
Chapter 2

_
+

4 NH3 +

2 H2O
46

4 N

Tollen's test
Ag2O
H

OH

Ag (silver mirror ppt)

O
propanoic acid

propanal
ketone

no reaction

Fehling's test
H3C

O
ethanal
ketone

2CuO

H3C

OH
+

Cu2O (red ppt)

Chapter
2
no reaction

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