Chapter 9.
Aldehydes and Ketones
Aldehydes and ketones both have functional group --- carbonyl group
C O
In aldehydes --- the carbon of the carbonyl group attaches to at least one H atom.
(-CHO), R-CHO Ar-CHO
In ketones --- the carbonyl carbon attaches two carbon atoms.
O O O
C O
R C R Ar C Ar R C Ar
9.1 Nomenclature of Aldehydes and Ketones
IUPAC system uses the characteristic ending –al for aldehydes.
O O
H C H CH3CH2CH2CH2CH2C H
methanal hexanal
(2) For substituted aldehydes, the numbering starts with the aldehyde carbon. The
aldehyde group also has priority over a C=C or –OH in numbering and suffix.
O
8 7 6 5 4 3 2 1
CH3CH2CH C CH2 CH CH2 C H
CH3 OH
1 3-hydroxy-5-methyl-5-octenal
(3) Cyclic aldehyde name = cycloalkane name + suffix –carbaldehyde.
For aromatic aldehydes, common names are used.
O CHO
C H
Br
cyclohexanecarbaldehyde o-bromo-benzaldehyde
(4) IUPAC system uses the ending –one for ketones. The chain is numbered in
order to give the lowest possible number for the carbonyl carbon.
O
O O O
CH3CH2CH2CCH3 CH3CH2CCH2CH3 CH3C C C CH3
2-pentanone 3-pentanone 3-pentyn-2-one
3-methylcyclohexanone
The common name for ketones = the names of alkyl or aryl groups + kenone.
O O
C CH2CH3 C
ethyl phenyl ketone dicyclopentyl ketone
2
9.2 Common Aldehydes and Ketones (read on your own)
9.3 Synthesis of Aldehydes and Ketones
(1) Oxidation Reaction
PCC
using primary alcohol aldehyde
using secondary alcohol ketone (Jones reagent and PCC both work)
PCC Jones' reagent
CH2OH CHO OH O
(2) Friedel-Crafts Acylation --- making aromatic ketones
catalyst
O O
AlCl3
CH3CH2 C Cl C CH2CH3
(3) Hydration of terminal alkynes --- making methyl ketones
O
H2O
CH3CH2C CH CH3CH2CCH3
H+, Hg2+
catalyst
9.4
3
Aldehydes and Ketones in Nature (read on your own)
9.5 The Carbonyl Group
>C=O --- 1 bond and 1 bond, three atoms attached to the carbonyl carbon are
in the same plane with bond angles of 120º.
o
120
C O C O
C O
C O C O
sp2 The C=O bond is highly polarized.
a proton may
Chemical properties: a nucleophile C O
can attack here react here
Physical properties: (1) boiling point: alcohol > carbonyl compound > hydrocarbons
(with comparable MW)
C O C O C O dipole-dipole interactions
O C O C O C
H
C O H O
(2) low MW carbonyl compound --- soluble in water
forming hydrogen bonds with water molecules hydrogen bond
4
9.6 Chemical Reactions of Carbonyl compounds
1. Nucleophilic Addition to Carbonyl Groups (9.6 – 9.11 section in the book)
Nu H2O Nu
Nu: C O C O C O H
sp2 sp3 sp3
Acid can catalyze the addition:
Nu: Nu
C O H+ C OH C OH C OH
The carbonyl compound reactivity: aldehydes > ketones
(1) Steric effect:
size of H < size of R (more strain for the addition of ketone with nucleophiles)
(2) Electronic effect:
R group --- electron-donating to neutralize the partial positive charge on the
carbon atom of the C=O. This decreases the reactivity of carbonyl
compounds towards to nucleophiles.
aldehydes --- one R group ketones --- 2 R groups
5
(5) Addition of Nitrogen Nucleophiles
RNH2 or Ar NH2 C NR or C NAr (imine)
(primary amine)
NH2OH C NOH (oxime)
(hydroxylamine)
NH2NH2 C NNH2 (hydrazone)
(hydrazine)
C O H2O
H2NNH C NNH
(phenylhydrazine) (phenylhydrazone)
O O
NH2NHCNH2 C NNHCNH2
(semicarbazide) (semicarbazone)
CHO H2NNH CH NNH
(phenylhydrazine) (phenylhydrazone)
6
9.7 Reduction of Carbonyl compounds (9.12 in textbook)
reducing agents --- metal hydrides: lithium aluminum hydride (LiAlH4)
sodium borohydride (NaBH4)
Aldehydes can be reduced to primary alcohols.
1. LiAlH4
CHO CH2OH
2. H+, H2O
Ketones can be reduced to secondary alcohols.
O OH
1. NaBH 4
CH3CH2CCH2CH3 CH3CH2CCH2CH3
2. H+, H2O
H
C=C and C=O bonds coexisting in the molecule, NaBH4 can reduce C=O bond
without affecting C=C bond. O H OH
C 1. NaBH 4 C
CH3 CH3
2. H+, H2O
1. NaBH 4
CH CHCHO CH CHCH2OH
2. H+, H2O
7
9.8 Oxidation of Carbonyl compounds (9.13)
Normally aldehydes can be easily oxidized to carboxylic acids. But at normal
conditions, ketones can not be oxidized.
Oxidizing reagents:
(1) Jones’ reagent (CrO3, H+) O O
CrO3, H+
C H C OH
(2) Ag2O --- selectively oxidize -CHO no effect on C=C
CrO3, H+
CH CHCHO CH CHCOOH
(3) Tollen’s reagent (silver-ammonia complex ion) --- Tollen’s silver mirror test
O O
C H 2Ag(NH3)2+ 3OH C O 2Ag 4NH3 2H2O
O
C CH3 2Ag(NH3)2+ 3OH no reaction (no silver mirror)
Tollen’s
8 silver mirror test is a lab test to distinguish aldehydes from ketones.