Organic Reactions –

Aldehydes, Ketones and

the Carbonyl Group
Aldehydes and Ketones

• Oxidation of alcohols using a range of reagents

- Most are chromium(VI) compounds ( CrO 3 ).

• Different types of alcohols yield different pro ducts

- Primary alcohols can lead to aldehydes and carboxylic acids.

- Secondary alcohols lead to ketones. OH O O

oxidation oxidation
- Tertiary alcohols do not oxidise. H
H A A H A OH
1o alcohol aldehyde carboxylic acid
Ketones
Preparation of Aldehydes and Ketones

OH O
K2Cr2O7
H3C H3C
H H
H H2SO4

1-pentanol pentanal not isolated

H3C
OH

pentanoic acid
Preparation of Aldehydes and Ketones

Using pyridinium chlorochromate ( PCC)

+
OH N CrO3Cl- O
H
H3C H3C
H H
H
1-pentanol PCC pentanal
 Preparation of Aldehydes and Ketones

Secondary alcohols can be oxidised by PCC, Jones Reagent (CrO 3 ) or

K 2 Cr 2 O 7 to yield the corresponding ketone.

H3C CH3 H3C CH3

CrO3
O
OH
H2SO4
H2O
R-2,2-dimethylcyclopentanol 2,2-dimethylcyclopentanone
 Ozonolysis

Aldehydes and ketones can also be prepared by the reaction of alkenes with ozone, followed
by a mild reduction using dimethyl sulfide. This reaction is called ozonolysis

R R '' R R ''
1. O3
O + O + (CH3)2S=O

R ' H
2. (CH3)2S R ' H

alkene ketone aldehyde dimethylsulfoxide

R
R R
1. O3
2 O + (CH3)2S=O
2. (CH3)2S R
R R
alkene ketone dimethylsulfoxide
Exercise

1.
CH3
H
1. O3
2. (CH3)2S
H3C CH3

H3C
2. 1. O3
2. (CH3)2S
H3C H
 Reactions of Aldehydes and Ketones

H
General reaction for reduction: + : OH
H O
ketone
: O: δ -
: O– : H
δ+
R R' R' Nu R'
Nu
R R

As an example: Nu:- H an alcohol

+
– H O OH
O
:
O H
+ MgBr H CH3
H CH3 2o alcohol
H CH3
H3C
H3C

CH3CH2- +MgBr ethyl magnesium

Grignard reagent
 Reduction reactions

• Aldehydes and ketones can be reduced to form alcohols, e.g., catalytic

hydrogenation H .. H
O:
Pt
OH
H3C + H2 H3C
H
aldehyde 1o alcohol
O OH
H
Pt
+ H2

ketone 2o alcohol
 Exercises O
H2
1. H CH3
Pd/C or Pt
Provide the structure of CH3

the reaction products 2. H3C

CH3 H2

from the following O Pd/C or Pt

equations. O
H2
3.
Pd/C or Pt

O H2

4. H Pd/C or Pt
Organic Reactions –
Carboxylic Acids
Characteristics of Carboxylic Acids

▪ Have hydroxyl group bonded to carbonyl group

▪ Tart tasting

▪ Carboxylic acids are weak acids

▪ Intermolecular forces - hydrogen bonding, including with itself to form dimers

Carboxylic Acids
Reactions of Carboxylic Acids

• Previously saw that oxidation of alcohols forms aldehydes and further

oxidation forms carboxylic acid

• Reduction of carboxylic acid forms the alcohol

O LiAlH4 H
strong reducing
R OH agent R OH
carboxylic acid 1o alcohol
Carboxylic Acids – Reactions with Bases
HCl(aq) + NaOH(aq) Na+Cl-(aq) + H2O(l)

..
water O .. –
salt ..
O
OH
..
O
Na+

+ NaOH(aq) +H O
2
sodium hydroxide water

benzoic acid sodium benzoate

..O.. .. ..O..
+ CH3CH2NH2
.. ethylamine ..– +
H3C .OH
. H3C .O. NH3CH2CH3
acetic acid/ethanoic acid
ethylammonium acetate
(vinegar)
Acidity of Carboxylic Acids
O O O
F Cl H
OH OH OH
F Cl H
F Cl H
Trifluoroacetic Trichloroacetic Acetic acid
acid acid

Electron-withdrawing substituents adjacent to the COOH

group induces the formation of carboxylate conjugate base,
weakening the O-H bond, making it a stronger acid.
The stronger the electron-withdrawing ability, the weaker the
O-H bond, the stronger the acid
EXERCISE

Provide the structure of the reaction products for the following reactions:
O
1.
KOH
HO CH3

propanoic acid
2. O OH

KOH

cyclopentanoic acid
Esterification reactions

• Esters form when carboxylic acids and alcohols react

O O
H+
R C OH + R' OH R C O R' + H2O
carboxylic acid alcohol ester

• Esters have a sweet aroma (perfumes, fruits, etc)

 Ester Hydrolysis

Hydrolysis of esters using a base is called saponification (used

in soap making process)
O O
– +
H2O Na
H3C
O
CH3
+ NaOH H3C
O
+ CH3OH
methyl propionate sodium propionate methanol
Acid Chlorides

• Acid chlorides form when carboxylic acids react with thionyl chloride
O O
+ SOCl2
+
SO2 + HCl
H3C OH H3C Cl

carboxylic acid acid chloride

• Example:
O
+ SOCl2
H3C OH

butanoic acid
EXERCISES

Provide the structures of the reaction products from the following

equations:
O
H3C
i) CH3 +
HO OH
propanoic acid ethanol
O
ii) dilute NaOH
O F
H2O

3-fluoropropyl cyclopentanecarboxylate
 EXERCISE

Provide the appropriate starting reagents or compounds used to form

the products in the following equations:

iii) O
? + ? + SO2 + HCl
CH3
Cl
Organic Reactions –
Amines and Amides
Lecture 10
 Amines

General formula: ..
N
R"
R R'
• Amines are organic derivatives of ammonia
• Can be aliphatic, aromatic or heterocyclic
• Can be 1 o, 2 o, 3 o or even 4 o (quaternary ammonium salts)
• Because of the lone pair of electrons on the nitrogen, amines like
ammonia act as bases
 Aliphatic Amines

CH3
H .. ..
H3C N : H3C N CH3 H3C N H3C N
+
CH3
CH3
H H
-
H3C H3C
F
.. .. ..
CH3CH2NH2 CH3CH2NH CH3CH2N CH3CH2N+F-

ethylamine diethylamine triethylamine tetraethylammonium

fluoride
1o amine 2o amine 3o amine 4o ammonium salt
Heterocyclic and Aromatic Amines

.. ..
NH
NH N
.. ..NH
piperidine pyrrolidine pyridine pyrrole
aliphatic aliphatic aromatic aromatic
amine amine amine amine
o
2 amine o
2 amine
o
3 amine 2o amine
Examples of Nitrogen Containing Compounds

.. CH3
CH3

:N
NH2
H3C OH
.. ..
NH N
OH
CH3 O
codeine
..
N
OCH3 3o amine
heterocyclic
aniline coniine nicotine amine

1o amine 2o amine 3o amine HO H ..

HO NH
CH3
aromatic heterocyclic heterocyclic &
amine amine aromatic amine HO adrenaline
2o amine
aliphatic
amine
Reactivity of Amines

• Amines react with acids to form ammonium salts

R R
-
N: + .. N
+
H + Cl
: .. :
H
H
H+:Cl
.. :-
H
H

primary amine alkyl ammonium salt

• Amines react with alkyl halides to form ammonium salts

R R
.. : X : -
N: + R" ..X:
+
N + ..
R' R' R"
H H

secondary amine trialkyl ammonium salt

Example

H
.. N
+
Cl-
CH3CH2CH2Cl + H2NCH3 H3C
H
CH3 dialkyl ammonium
salt
alkyl halide alkyl amine
aq NaHCO3

..
HCl + NH
H3C CH3

dialkyl amine
N-methyl propanamine
Amides

• Are derivatives of carboxylic acids

• Can be 1 o, 2 o or 3 o
O O O
H CH3 CH3
H3C NH H3C NH H3C N
CH3

1o o
2 3o
 Formation of Amides

• Amides form when amines react with “activated” carboxylic acids

O
O
+ H2NCH2CH3 H3C NH CH3 + HCl
H3C Cl

acetyl chloride ethanamine N-ethyl acetamide

acid chloride 1o amine amide

SOCl2
O H
O H
O + :N CH3 H3C
N + HCl
H3C Cl H
H3C OH CH3
Exercise

Describe a synthesis for procaine, a local anaesthetic, from the suggested

starting material. You may choose any reagents and conditions you like that
will bring about the transformation needed.
CH3
O
O
N CH3
NH CH3 O
O

H2N
O 2N procaine
 EXERCISE

Capsaicin, shown below, is the compound responsible for the sensation felt when
chillis are eaten. It is often used as a tool in neurobiological research and has
application as a topical analgesic. (a) Draw the structure of the carboxylic acid
and amine that lead to capsaicin. (b) What is the general name given to this
reaction? O
H3CO
CH3
NH

CH3
HO
capsaicin