1. (ALKANALS & ALKANONES)
ALDEHYDES & KETONES
(ALKANALS & ALKANONES)

2. alkane
alcohol
reduction
reduction
aldehyde
ketone
addition
product
nucleophilic
addition
oxidation
carboxylic acid

3. Aldehydes and Ketones Some common classes of carbonyl compounds
Aldehydes and ketones are characterized by the the carbonyl functional group (C=O).
Some common classes of carbonyl compounds

4. Carbonyl Structure
Carbon is sp2 hybridized. C=O bond is shorter, stronger, and more polar than C=C bond in alkenes.

5. Naming Aldehydes and Ketones
Aldehydes are named by replacing the terminal -e of the corresponding alkane name with –al
The parent chain must contain the CHO group
The CHO carbon is numbered possible minimum number.

6. Naming Ketones Replace the terminal -e of the alkane name with –one
Parent chain is the longest one that contains the ketone group
Numbering begins at the end nearer the carbonyl carbon

7. Solubility Good solvent for alcohols.
Lone pair of electrons on oxygen of carbonyl can accept a hydrogen bond from O-H or N-H.
Acetone and acetaldehyde are miscible in water.

8. Preparation of Aldehydes & ketones
1] Oxidation of 1& 2 alcohol :
C2H5OH [O] CH3CHO [O] CH3COOH
CH3CHOHCH [O] CH3COCH3
isopropanol

9. Physical Properties Boiling Points
More polar, so boiling point higher than corresponding alkane or ether.
Absence of H-bond, so boiling point lower than corresponding alcohol.

10. 2- Dehydrogenation
A- 10 Alcohol gives aldehydes: CH3CH2OH Cu/ 350 oC CH3CHO + H2 B- Secondary Alcohol gives Ketones: OH O CH3CHCH3 Cu/350oC CH3CCH3 + H2

11. 3] Ozonolysis of alkenes:

12. 4- Hydration of Alkynes

13. 5- Hydrolysis of gem-dihalides by the action of base:
A) If dihalogen are terminal:
CH3CHCl2 H2O/NaOH CH3CH(OH)2 H2O CH3CHO acetaldehyde
B) If dihalogen aren’t terminal:
CH3CCl2CH3 H2O/NaOH CH3COCH3 acetone

14. 6-From Acid Chlorides: Rosenmund reduction
R-CO-Cl H2/Pd R-CHO +HCl
CH3COCl H2/Pd CH3CHO + HCl

15. Chemical Reactions

16. 1] Reactions with Grignard reagent:

17. Nucleophilic addition to carbonyl:

18. Addition of Alcohol
In presence of dry HCl aldehydes and ketones react with two equivalent of alcohols to form acetals and ketals

19. Acetal Formation
Acetals are geminal diethers- structurally related to hydrates,
which are geminal diols.
hydrate
(gem-diol)
acetal
(gem-diether)
aldehyde
hemi-acetal
ketal
(gem-diether)
ketone
hemi-ketal

20. 4-Reduction of Aldehydes/Ketones
Hydrogenation

21. B- Condensation reaction:
1- Hydroxylamine:
-C=O + NH2OH C=NOH + H2O (oxime)
CH3COCH3 + NH2OH CH3-C=NOH
CH3
2- Hydrazine:
-C=O + H2N-NH C=N-NH2 + H2O (hydrazone)
CH3CHO +H2N-NH CH3CH=N.NH2+H2O

22. 3-Aldol Condensation
Aldol Condensation - Under the influence of dilute base or dilute acid two molecules of an aldehyde or a ketone may combine to form b- hydroxaldehyde or b-hydroxyketone. This reaction is called aldol condensation.

23. The Aldol Condensation+ ol
base
an aldol
(b-hydroxyaldehyde)
H3O+
- H2O
aldols easily lose
water to form a
double bond
a,b-unsaturated aldehyde

24. Aldol Condensation -- Mechanism
fast
enolate ion
slow
forms new
C-C bond
fast

25. C- Substitution reaction:1-
1-Haloform reaction:
CH3COCH3 3I Cl3COCH3 NaOH CHI3 + CH3CO2Na
2- Cannizzaro’s reaction:
2CH2O + NaOH CH3OH + HCOONa

26. Cannizzaro’s reaction

27. Tollens Test
Add ammonia solution to AgNO3 solution until precipitate dissolves.
Aldehyde reaction forms a silver mirror.

28. Identification of aldehydes
Tollen’s test
Fehling’s test
Schiff’s test
Schiff's Test for aldehydes. Use 2 mL Schiff's reagent + 3 drops unknown. Positive test showing a magenta color after ten minutes.

29. Carboxylic Acids O A carboxylic acid
Contains a carboxyl group, which is a carbonyl group (C=O) attached to a hydroxyl group (—OH).
Has the carboxyl group on carbon 1.
carbonyl group O 
CH3 — C—OH hydroxyl group or CH3COOH
carboxyl group

30. IUPAC Names The IUPAC names of carboxylic acids
Replace the -e in the alkane name with -oic acid.
CH4 methane HCOOH methanoic acid
CH3—CH3 ethane CH3—COOH ethanoic acid
Number substituents from the carboxyl carbon 1.
CH O
| ║
CH3—CH—CH2—C—OH
3-methylbutanoic acid

31. Carboxylic acid Nomenclature : R-COOH Ar-COOH
Aliphatic (carboxylic cid) aromatic (benzoic acid)
Nomenclature :
1) replace ane by ic acid
Common
IUPAC
Formula
No. C
Formic acid
Acetic acid
Prpionic acid
Butyric acid
valeric acid
Methanoic acid
Ethanoic acid
Prpanoic acid
Butanoic acid
Pentanoc acid
HCOOH
CH3COOH
CH3CH2COOH
CH3(CH2)2COOH
CH3(CH2)3COOH 1 2 3 4 5

32. 2) Longest continuous chain
CH3CH2CHCH2CH2COOH Methyl hexanoic acid
CH3
    
C-C-C-C-C-COOH
CH3CH2CHCH2CH2COOH γ-Methyl hexenoic acid
CH3
commmone: -- Dimethyl butyric acid
IUPAC: ,3-Dimethyl butanoic a
CH3-CHBr-CHCl-CO2H 3-Bromo-2-chlorobutnoic acid

33. Common Carboxylic Acids
Methanoic acid (formic acid) O ║
H─C─OH
ethanoic acid (acetic acid)
CH3─C─OH

34. Physical properties:
1] They form hydrogen
2] comp. 1-7 soli in H2O .
3] mor than 7 carbon less soli. (bec. R increased)
4] Aromatic acids insoluble. In H2O
5] BP. Acid > Alcohol

35. Polarity of Carboxylic Acids
Are strongly polar.
Have two polar groups:
hydroxyl (−OH) and carbonyl (C=O). δ- O
║δ+ δ δ+
CH3CO H

36. Boiling Points of Carboxylic Acids
The boiling points of carboxylic acids
Are higher than alcohols, ketones, and aldehydes of similar mass.
Are high because they form dimers in which hydrogen bonds form between the polar groups in the two carboxyl groups.
O H—O
|| |
CH3—C C—CH3
| ||
O—H O
A dimer of acetic acid

37. Solubility in Water Carboxylic acids
Form hydrogen bonds with many water molecules.
With 1-4 carbon atoms are very soluble in water.
Water molecules 37

38. Preparation of carboxylic acid
1] Oxidation
a) 1 alcohols & Aldehydes

39. Preparation of Carboxylic Acids
Carboxylic acids can be prepared by oxidizing primary alcohols or aldehydes.
The oxidation of ethanol produces ethanoic acid (acetic acid).
OH O O
| [O] || [O] ||
CH3—CH CH3—C—H CH3—C—OH
ethanol ethanal ethanoic acid
(ethyl alcohol) (acetaldehyde) (acetic acid)

40. 2] Carbonation of Grignard reagent:

41. Chemical Reaction

42. Reactions of acids 1)Salt formation:
it react with strong base & we can use Ca or K
It reacts with weak base
Sodium bicarb. Can be used to distinguish between carboxylic acid and phenols

43. nucleophilic substitution
2) Formation of Ester:
nucleophilic substitution H+ +
+ H2O
carboxylic acid
alcohol
ester
condensation reaction
reverse =
hydrolysis H+
ester
+ H2O
carboxylic acid +
alcohol

44. 2) Formation of Ester:
3) Formation of acid chloride:
4) Formation of acid anhydride:
2RCOOH + P2O (RCO)2O + H2O
2CH3COOH + P2O (CH3CO)2O + H2O

45. 5- Reduction:
RCO2H LiAlH4; then H+  RCH2OH 1o alcohol
6- Decarboxylation:( Soda lime)
CH3COOH + NaOH/CaO CH4 + Na2CO3 Alkane

46. ketone
aldehyde
RCOOH
ROH
ROR
alkene
Alcohols are central to organic syntheses RX RH
alkyne