ALDEHYDES AND KETONES

Aldehyde
O C R H

STRUCTURE

R = H, alkyl, aryl

Ketone

O C R R' R and R' = alkyl or aryl R and R' cannot be hydrogen!

NOMENCLATURE

IUPAC Nomenclature of Ketones

Choose the longest continuous carbon chain that contains the carbonyl carbon
Number from the end of the chain closest to the carbonyl carbon Ketone ending is -one

Do the ketones section of Organic Nomenclature program!

EXAMPLES
O C CH 3 CH 2
2-Pentanone

CH 2 CH 3
O CH3 CH2 C CH CH2 CH3
4-Ethyl-3-hexanone

CH2 CH3

CH CH3

CH3

3-Isopropylcyclopentanone

KETONES

Common, or Trivial, Names

Name each group attached to the carbonyl group as an alkyl group
Combine into a name, according to the pattern:

alkyl alkyl ketone

NOTE: This is not all one word!

Example of Common Names

O C CH 3 CH 2 CH 2 CH 3
O CH3 CH2 C CH2 CH3

Methyl propyl ketone

Diethyl ketone

SPECIAL CASES
O C CH3
acetone
A common laboratory solvent and cleaning agent

O C
CH3
diphenyl ketone
benzophenone

dimethyl ketone

O C CH3
methyl phenyl ketone
acetophenone

KNOW THESE

IUPAC Nomenclature of Aldehydes

Choose the longest continuous carbon chain that contains the carbonyl carbon Number from the end of the chain closest to the carbonyl carbon (carbon #1!) Aldehyde ending is -al

Do the aldehydes section of Organic Nomenclature program.

EXAMPLES
H3C CH2 CH2 CH2
pentanal

C H

aldehyde group is always carbon 1

Cl
4

CH3

CH
2

CH CH3

C H

2-chloro-3-methylbutanal

Common Names of the Aldehydes

O C H H CH3 Formaldehyde 1 O C H3C CH2 C Butyraldehyde 4 O C H3C CH2 CH2 CH2 CH2 Caproaldehyde 6 H H H3C CH2 CH2 C Valeraldehyde 5 O C H H3C CH2 Acetaldehyde 2 O C H Propionaldehyde 3 O C H

RECOGNIZE THESE

O C H

SPECIAL CASES
H

O C H

formaldehyde

O C H CH3

benzaldehyde

acetaldehyde

KNOW THESE

Forming Common Names of Aldehydes

USE OF GREEK LETTERS

O H

C C C C C C C .

is always the end of the chain, no matter how long

CHO Cl
-chlorocaproaldehyde ( -chlorohexanal )

CHO Cl
-chlorocaproaldehyde ( -chlorohexanal )

Molecular Geometry
Carbonyl group = Planar Triangle

Common Aldehydes
Carbonyl group = Planar Triangle

Common Ketones
Carbonyl group = Planar Triangle

Polar Property
Carbonyl group = Planar Triangle

Boiling Points
Carbonyl group = Planar Triangle

Solubility in Water
Carbonyl group = Planar Triangle

Physical Properties
Carbonyl group = Planar Triangle

Preparing Aldehyde
1. Oxidation of primary alcohol and oxidative cleavage of alkenes
o Primary alcohol can be oxidized to give aldehydes. The reaction is often carried out using piridinium chlorochromate (PCC) in dichloromethane solvent at room temperature

2. Alkenes with at least one vinylic hydrogen undergo oxodative cleavage when treated with ozone to yield aldehydes.
If the ozonolysis reaction is carried out on a cyclic alkene, a dicarbonyl compound

3. Carboxylic acid derivatives can be partially reduced to yield aldehydes

DIBAH : diisobutylaluminium hydride

Preparing Ketones
1. Secondary alcohol are oxidized by a variety of reagent to give ketones

2. Ozonolysis of alkenes yield ketones if one of the unsaturated carbon atom is disubtitused

3. Aryl ketones are prepared by FriedelCrafts acylation of an aromatic ring with an acid chloride in the presence of AlCl3 catalyst

REACTIVITY OF THE C=O GROUP

NUCLEOPHILIC ADDITION

GENERALIZED CHEMISTRY

THE CARBONYL GROUP

nucleophilic at oxygen electrophiles add here H+ or E+

.. O:

.. :O :

C
+
Nu:

nucleophiles attack here electrophilic at carbon

CYANOHYDRINS

Addition of Cyanide
Buffered to pH 6-8
:O : _ R C .. _ :O : R C CN R + H2O R R + CN R C CN .. :O C CN

:C N:

.. _ :O : R

H R

a cyanohydrin

In acid solution there would be little CN-, A cyanohydrin and HCN (g) would be a problem (poison).

CYANIDE ION BONDS TO HEMOGLOBIN .. N CYANIDE IS Cyanide bonds IS A POISON (irreversibly) to the C ..
CH3 H3C

site (Fe II) where oxygen usually bonds.

N Fe N

N N CH3 CH2CH2COOH

You die of suffocation lack of oxygen.

H3C

CH2CH2COOH

HCN is a gas that you can easily breathe into your lungs.

ORGANOMETALLICS

Synthesis of Alcohols

Addition of Organometallic Reagents

:O : R M + R C R .. _ + :O: M
ether

C R

(R-MgBr)

(R-Li)
These reagents cannot exist in acid solution

:R .. :O R C R

H2O + H H R

workup step

M (OH)x

alcohol

Summary of Reactions of Organometallics with Carbonyl Compounds

Organometallics with ketones yield tertiary alcohols Organometallics with aldehydes yield secondary alcohols Organometallics with formaldehyde yield primary alcohols. Organometallics with carbon dioxide yield carboxylic acids. All review to you

etc.

SOME STABLE HYDRATES

these also indicate that hydrates are possible

Cl

O Cl H

Cl C Cl H

OH OH

Cl

+Cl

chloral

chloral hydrate

120o expected 60o required

OH
sp3 OH

O
sp2 cyclopropanone

109o expected 60o required

cyclopropanone hydrate

Oxidation of Aldehydes and Ketones

 Aldehydes are readily oxidized to yield carboxylic acid Ketones are generally inert toward oxidation The difference is a consequence of structure : Aldehydes have a CHO proton that can be abstracted during oxidation, but ketones do not

 Many oxidizing agents, including KMnO4 and hot HNO3 convert aldehydes into carboxylic acids CrO3 in aqueous acid is a more common choice in the laboratory. The oxidation occurs rapidly at room temperature and results in good yields

 In the such cases, the laboratory oxidation of an aldehyde can be carried out using a solution of silver oxide, Ag2O, in aqueous ammonia, that so-called Tollens reagent

 Aldehyde oxidation occur through intermediate 1,1-diols, or hydrates which are formed by reversible nucleophilic addition of water to carbonyl groups

 Ketones are inert to the most oxidizing agents but undergo a slow cleavage reaction when treated with hot alkaline KMnO4. The CC bond next to the carbonyl group is broken, and carboxylic acid are produced