ALDEHYDES
KETONES
Organic Pharmacy
Aldehyde/ketone characteristics:
Carbonyl compounds
This group is largely involved in chemistry of
aldehydes and ketones.
Chemistry of both groups are closed but
influenced by the difference in structure.
Organic Pharmacy
Aldehyde/ketone characteristics:
R δ+ δ-
C O
R'
Organic Pharmacy
Aldehyde nomenclature:
H H H H
H C O CH3 C O CH3CH2CH2C O
CH3CH2 C O
Formaldehyde -
Acetaldehyde Propionaldehyde n butyraldehyde
Methanal
Ethanal Propanal Butanal
pentanal H CH 3
valeraldehyde
O CH 3CH CHCH 2CHC O
C
CH3CH 2CH 2CH2C O H
H benzaldehyde 2-methyl-4-hexenal
Organic Pharmacy
Aldehyde nomenclature:
CH3 H
C O
CH2 CH3
CH3
CH3 C CH CH C O
Br
CH3 Cl H CH2CH3
- - - - - - - -
5 bromo 4 ethyl 2 methyl benzaldehyde
3 chloro 2 4 4 trimethylhexanal
, ,
Organic Pharmacy
Aldehyde nomenclature:
O O O
Organic Pharmacy
Ketone nomenclature:
O
H2C CH2
O O
CH2
Organic Pharmacy
Aldehyde/ketone physical properties:
Testosterone Vanillin
Cortisone
Organic Pharmacy
ALDEHYDES
KETONES
REACTIONS
Organic Pharmacy
Aldehyde/ketone reactions:
NUCLEOPHILIC ADDITIONS:
Nucleophilic addition on the C of the
carbonyl.
C=O group provide a site for nucleophilic
addition and increase the acidity of the hydrogen
on the alpha carbon.
The oxygen is able to accommodate a
negative charge.
Organic Pharmacy
Aldehyde/ketone reactions:
REDUCTION
Catalytic reduction
Reduction by complex metal hydrides
Reduction to hydrocarbons: Clemmensen and
Wolff-Kishner reduction
OXIDATION
Aldehydes to carboxylic acids
Tollen’s reagent for aldehydes
Haloform reaction on methyl ketones
Organic Pharmacy
Aldehyde/ketone reactions: addition of water
1. acid as a catalyzer
2. formation of an oxygen cation (oxonium
ion) O+
3. release of H+ and of the instable product
Formation of
hydrates
which are
not stable
Organic Pharmacy
Aldehyde/ketone reactions: addition of alcohol
R2C=O + GNH2
GNH–(R2)C–O–H
R2C=NG + H2O
Organic Pharmacy
Aldehyde/ketone reactions: addition of ammonia
derivatives (1º amines)
REDUCTION / OXIDATION:
Reduction to alcohol by catalytic
hydrogenation or by using reducing agent
(LiAlH4, NaBH4) and reduction to
hydrocarbons by Clemmensen and Wolff-
Kishner reduction.
REDUCTION TO ALCOHOLS:
+
H2 Ni, Pt or Pd
C O C OH
LiAlH4 or NaBH4
+
then H
Organic Pharmacy
Aldehyde/ketone reactions:
REDUCTION TO HYDROCARBONS:
Clemmensen reduction: amalgamated Zinc in
acidic medium
OXIDATION:
Aldehydes:
Tollen’s reagent
Reaction of aldehydes with silver ion to release
acid and and free silver (silver mirror).
Organic Pharmacy
Aldehyde/ketone reactions:
X2
C C C C + HX
H+ or OH - O
H O X
alpha haloketone
Organic Pharmacy
Aldehyde/ketone reactions: halogenation of ketones
ALDOL REACTION:
Organic Pharmacy
Aldehyde/ketone reactions: aldol condensation
ALDOL REACTION:
nucleophile
Organic Pharmacy
Aldehyde/ketone reactions: aldol condensation
ALDOL REACTION:
Addition of the enolate (or enol=nucleophile)
on the carbonyl (or protonated carbonyl).
Important reaction because it can be used to
construct new C-C bonds.
Carbonyl compounds without alpha
hydrogen can not form enolate/enol form, then
they will not undergo aldol reaction.
Organic Pharmacy
Aldehyde/ketone reactions: aldol condensation
ALDOL REACTION:
Organic Pharmacy
Aldehyde/ketone reactions: aldol condensation
ALDOL REACTION:
Organic Pharmacy
Aldehyde/ketone reactions: aldol condensation
ALDEHYDES
KETONES
PREPARATION
Organic Pharmacy
Aldehydes preparation:
• Oxidation reactions:
oxidation of primary alcohols: aliphatic
aldehydes
oxidation of methylbenzene: aromatic
aldehydes
• Reduction reaction:
Reduction of acid/acyl chlorides (aliphatic
or aromatic)
Organic Pharmacy
Ketones preparation:
• Aliphatic ketones:
oxidation of secondary alcohols
reaction between an acid/acyl chloride with
an organocopper compounds
O
R C
Cl
Alcohol
R’
Primary: RCH2-OH Secondary: R-CH-OH
oxidation
Aldehydes Ketones
Organic Pharmacy
Aldehydes / ketones preparation:
Ketones
+ organocopper
compounds
Aldehydes Ketones
Organic Pharmacy
Aldehydes preparation:
BACK-UP
Organic Pharmacy
Aldehydes preparation:
alcohol
oxidation R-CH2OH
R-CHO
R-COOH R-COCl
Acid/Acyl chlorid
reduction
oxidation Ar-CH3
Ar-CHO
Ar-COOH Ar-COCl
Aromatic acid/acyl chlorid
reduction
Organic Pharmacy
Aldehydes preparation:
Ar-CH3 Ar-CHO
CrO3 Ar-CH(OAc)2 H2O
Acetic anhydre
Organic Pharmacy
Ketones preparation:
R-CH-R’
OH
R-C-R’
RCOOH RCOCl O
R2’-CuLi
Organic Pharmacy
Ketones preparation:
Ar-H
RCOCl / Ar’COCl, AlCl3
Ar-C-R’
Ar-Br Ar-Li Ar2-CuLi O
RCOCl / Ar’COCl
Ar-C-Ar’
Ar-COOH Ar-COCl O
R2’-CuLi / Ar2CuLi