1. Aldehydes and ketones DR AKM SHAFIQUL ISLAM
SCHOOL OF BIOPROCESS ENGINEERING
UNIVERSITY MALAYSIA PERLIS (UniMAP)

2. Carbonyl group
One of the most important functional groups in organic chemistry.
It is present in aldehydes and ketones

3. Carbonyl Compounds

4. Aldehydes
A compound in which the carbonyl group is connected to a hydrogen and an alkyl group or aromatic ring ( or to two hydrogens ).

5. Ketones
A compound in which the carbonyl group is connected to two alkyl groups or aromatic rings ( or one of each ).

6. IUPAC Nomenclature of Aldehydes
Find the longest continuous chain that includes the aldehyde group
Follow all the IUPAC naming rules for alkanes.
The carbonyl carbon is always at the end of the chain, so it is carbon number 1.
Replace the final -e ending of the alkane with -al.
Locate and name any other groups attached to the chain.
Aldehydes containing two aldehyde groups are called dials.

7. IUPAC Nomenclature of Aldehydes
The aldehyde group is abbreviated by CHO.
The IUPAC retains the common names benzaldehyde and cinnamaldehyde, as well formaldehyde and acetaldehyde.

8. IUPAC Nomenclature of Ketones
Because ketones have the general formula, the shortest ketone chain length is 3 carbons.
The carbonyl group cannot be at the end of the chain; it must be in the middle.

9. IUPAC Nomenclature of Ketones
Find the longest continuous chain that includes the carbonyl group
Follow all the IUPAC naming rules for alkanes.
The chain is numbered from the end closest to the carbonyl group.
Replace the final -e ending of the alkane with -one.
Locate and name any other groups attached to the chain.

10. Name the following ketones using IUPAC names and common names.
2-propanone
dimethyl ketone
acetone
2-butanone
ethyl methyl ketone
methyl ethyl ketone
MEK
5-chloro-4,4-dimethyl-2-hexanone 4 5 1 2 3 6
Copyright© 2005, Michael J. Wovkulich. All rights reserved.

11. Common names - ketones
name each alkyl group bonded to the carbonyl carbon as a separate word, followed by the word "ketone”

12. Natural Products

13. Physical Properties
What kind of intermolecular forces are possible between carbonyl groups?
Is H-bonding possible?
How do you think the boiling point of aldehydes and ketones compares to alkanes and alcohols?
Alkanes – very weak forces
Alcohols – H-bonds

14. Physical Properties
A C=O bond is polar, with oxygen bearing a partial negative charge and carbon bearing a partial positive charge
therefore, aldehydes and ketones are polar molecules

15. Dipole/Dipole Interactions
The electronegativity number (E.N.) of carbon is The E.N. of oxygen is 3.5.
As a result of unequal sharing, the carbonyl bond is polar covalent and the oxygen acquires a partial negative charge.
Dipole/dipole interactions aren’t as strong as hydrogen bonds, but they do cause aldehydes and ketones to boil at higher temperatures than alkanes. d+ d- d+ d-
dipole/dipole interaction d+ d-

16. Lack of Hydrogen Bonding
Because aldehydes and ketones lack a hydrogen on the oxygen, they cannot form hydrogen bonds between other aldehyde or ketone molecules.
Thus, their boiling points are lower than those of alcohols with similar molecular weights (which have extensive hydrogen bonding).
Aldehyde
Ketone

17. Solubility
Even though it cannot H-bond with other carbonyls, the carboxyl group can accept H-bonds from water
formaldehyde, acetaldehyde, and acetone are infinitely soluble in water
As the hydrocarbon portion of the molecule increases in size, solubility in water decreases
Larger ketones and aldehydes are soluble in organic solvents

18. Water Solubility
Aldehydes and ketones form strong hydrogen bonds with water:
As a result, low-molecular weight aldehydes and ketones show appreciable solubilities in water. Acetone and ethanal are soluble in water in all proportions.

19. Oxidation Aldehydes are oxidized to carboxylic acids
Change the –H to an –OH
Ketones are not oxidized further

20. Oxidation of Primary Alcohols
General equation:
oxidize
oxidize
RCH2OH
RCHO
RCOOH
Primary alcohol
Aldehyde
(in anhydrous media)
Carboxylic acid
(when water is present)
(O) +
H2O
(O)

21. Oxidation of Primary Alcohols
Examples:
(O)
(O)
CH3CH2OH
ethanol
ethanal
ethanoic acid
(O)
(O)
CH3(CH2)5CH2OH
1-heptanol
heptanal
heptanoic acid

22. Tests for Aldehydes
Tollens’ reagent and Benedict’s reagent are two common chemical reagents used to test for the presence of aldehydes.
Both are mild oxidizing solutions.

23. Tollens’ Reagent
Tollens’ reagent is a solution of aqueous silver nitrate (AgNO3) with aqueous ammonia (NH3).
All aldehydes give a positive Tollens’ test. In general, ketones don’t react with the Tollens’ reagent except a-hydroxy ketones.
NH3, H2O
+ Ag+(aq)
+ Ag(s)
heat
+1 oxidation state
0 oxidation state

24. Tollens’ Reagent (Silver Mirror Test)
If the rate of reaction is slow and the test tube or flask is clean, metallic silver deposits on the sides as a mirror.

25. Benedict’s Reagent
Benedict’s reagent is a solution containing blue, Cu2+ ions.
The copper is reduced from the +2 oxidation state to the +1 oxidation state. Red Cu2O is precipitated, giving a positive test.
+ Cu2+
+ Cu2O
+2 oxidation state
+1 oxidation state

26. with adjacent alcohol group with adjacent alcohol group
Benedict’s Reagent
Aldehydes and one type of easily oxidized ketone give a positive test result. The structural features necessary are:
Aldehyde
Aldehyde
with adjacent alcohol group
Ketone
with adjacent alcohol group
These features are found in a number of sugars.

27. Benedict’s Reagent
Benedict’s reagent is the key material in a test kit available from drugstores that permits individuals to monitor the glucose levels in their urine.

28. Nucleophilic Reaction
Reagents that attack the electron-rich d- end of the C=O bond are called electrophiles (literally, "lovers of electrons"). Electrophiles include ions (such as H+ and Fe3+) and neutral molecules (such as AlCl3 and BF3) that are Lewis acids, or electron-pair acceptors.
Reagents that attack the electron-poor d+ end of this bond are nucleophiles (literally, "lovers of nuclei"). Nucleophiles are Lewis bases (such as NH3 or the OH- ion).

29. Nucleophilic Addition
A strong nucleophile attacks the carbonyl carbon, forming an alkoxide ion that is then protonated.
A weak nucleophile will attack a carbonyl if it has been protonated, thus increasing its reactivity.
Aldehydes are more reactive than ketones.
=>

30. Reaction Themes, Nu attack at C
One of the most common reaction themes of a carbonyl group is addition of a nucleophile to form a tetrahedral carbonyl addition compound.

31. Reaction Themes, O attack at H
A second common theme is reaction with a proton or other Lewis acid to form a resonance-stabilized cation.
protonation increases the electron deficiency of the carbonyl carbon and makes it more reactive toward nucleophiles.

32. Addition of C Nucleophiles
Addition of carbon nucleophiles is one of the most important types of nucleophilic additions to a C=O group.
a new carbon-carbon bond is formed in the process.
we study addition of these carbon nucleophiles.

33. A. Grignard Reagents
Given the difference in electronegativity between carbon and magnesium ( ), the C-Mg bond is polar covalent, with C- and Mg+.
in its reactions, a Grignard reagent behaves as a carbanion.
Carbanion: an anion in which carbon has an unshared pair of electrons and bears a negative charge.
a carbanion is a good nucleophile and adds to the carbonyl group of aldehydes and ketones.

34. Grignard Reagents, 1o alcohols
addition of a Grignard reagent to formaldehyde followed by H3O+ gives a 1° alcohol.
these reactions require two steps.

35. Grignard Reagents, 2o alcohols
addition to any other aldehyde, RCHO, gives a 2° alcohol (two steps).

36. Grignard Reagents, 3o alcohols
addition to a ketone gives a 3° alcohol (two steps).

37. B. Organolithium Compounds
Organolithium compounds, RLi, give the same C=O addition reactions as RMgX but generally are more reactive and usually give higher yields.
Lithium is monovalent and does not insert between C and X like Mg.
Like the Grignard this requires two steps.

38. C. Salts of Terminal Alkynes
Addition of an alkyne anion followed by H3O+ gives an acetylenic alcohol.

39. Salts of Terminal Alkynes
Addition of water or hydroboration/oxidation of the product gives an enol which rearranges.

40. D. Addition of HCN
HCN adds to the C=O group of an aldehyde or ketone to give a cyanohydrin.
Cyanohydrin: a molecule containing an -OH group and a -CN group bonded to the same carbon. O O H C H 3 + H C N C H 3 - N H
2-Hydroxypropanenitrile
(Acetaldehyde cyanohydrin)

41. Addition of HCN Mechanism of cyanohydrin formation:
Step 1: nucleophilic addition of cyanide to the carbonyl carbon.
Step 2: proton transfer from HCN gives the cyanohydrin and regenerates cyanide ion.

42. Cyanohydrins The value of cyanohydrins:
1. acid-catalyzed dehydration of the alcohol gives an alkene.
2. catalytic reduction of the cyano group gives a 1° amine.

43. Cyanohydrins The value of cyanohydrins:
3. acid-catalyzed hydrolysis of the nitrile gives a carboxylic acid. O H
acid
catalyst O H C H 3 N C H 3 -
COOH H 2 O
2-Hydroxypropanenitrile
(Acetaldehyde cyanohydrin)
2-Hydroxypropanoic acid

44. Mechanism of Aldol Reactions
Aldol reactions, like all carbonyl condensations, occur by nucleophilic addition of the enolate ion of the donor molecule to the carbonyl group of the acceptor molecule
The addition intermediate is protonated to give an alcohol product

45. Conditions for Condensations
A small amount of base is used to generate a small amount of enolate in the presence of unreacted carbonyl compound
After the condensation, the basic catalyst is regenerated