ALDEHYDES AND KETONES

Ald h d
Aldehyde STRUCTURE

C R = H, alkyl, aryl
R H

Ketone

O
R and
d R' = alkyl
lk l or aryll
C R and R' cannot be hydrogen!
R R'
NOMENCLATURE
IUPAC Nomenclature of Ketones

• Ch
Choose th
the llongestt continuous
ti carbon
b chain
h i th
thatt
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

g Nomenclature
program!
 EXAMPLES
O

C CH 2
CH 3 CH 2 CH 3
2-Pentanone O

CH3 C CH2
CH2 CH CH3

CH2
CH3
4-Ethyl-3-hexanone
 O

CH CH3

CH3

3-Isopropylcyclopentanone
 KETONES
Common or Trivial
Common, Trivial, Names
• Name each group attached to the carbonyl
group as an alkyl group

• Combine into a name, according to the pattern:

alkyl
lk l alkyl’
lk l’ ketone
k t

NOTE
NOTE: This is not all one word!
Example of Common Names
O

C CH 2
CH 3 CH 2 CH 3

Methyl propyl ketone O

CH3 C CH3
CH2 CH2

Diethyl ketone
 SPECIAL CASES
O O
C C
CH3 CH3
diphenyl ketone
di th l ketone
dimethyl k t
benzophenone
acetone
A common laboratory O
solvent and cleaning
agent
g C CH3

methyl phenyl ketone

KNOW
THESE
acetophenone
IUPAC Nomenclature of Aldehydes

• Choose the longest continuous carbon chain that

contains
t i the
th carbonyl
b l carbon
b

• 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
aldehyde group is
CH2 CH2 O always carbon 1
H3C CH2 C
H
pentanal
Cl
CH3 3 CH 1
O
4 CH 2 C
CH3 H

2 chloro 3 methylbutanal
2-chloro-3-methylbutanal
Common Names of the Aldehydes
O O O

C C C
H H CH3 H H3C CH2 H
Formaldehyde Acetaldehyde Propionaldehyde
1 2 3
O O

C C
H3C CH2 C H H3C CH2 CH2 C H
Butyraldehyde Valeraldehyde
4 5
O

C
H3C CH2 CH2 CH2 CH2 H RECOGNIZE
Caproaldehyde THESE
6
 SPECIAL CASES
O

C
H H O
formaldehyde C H

O
benzaldehyde
C
H CH3
KNOW
THESE
acetaldehyde
Forming Common Names of Aldehydes
USE OF GREEK LETTERS O

C C C C C C C H
ω ……. ε δ γ β α −−

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

CHO CHO

Cl
α-chlorocaproaldehyde
chlorocaproaldehyde
( α-chlorohexanal )
Cl
ω-chlorocaproaldehyde
chlorocaproaldehyde
( ω-chlorohexanal )
REACTIVITY OF THE C=O GROUP

NUCLEOPHILIC ADDITION
 GENERALIZED CHEMISTRY

THE CARBONYL GROUP

nucleophilic
att oxygen
electrophiles H+ or E+
add here
.. δ- .. -
O: :O :
δ+
C C
+
nucleophiles
attack here
Nu:
electrophilic
at carbon
NUCLEOPHILIC ADDITION TO C=O
MECHANISMS
IN ACID AND IN BASE
Nucleophilic Addition to Carbonyl
Basic or Neutral Solution
.. _
.. :O:
O: an
+
-:Nu slow
C
alkoxide
C ion
Nu
.. _ ..
:O: :O H
fast
C + H2O C

Nu or on adding acid Nu

Good nucleophiles
and
d strong
t b
bases BASIC SOLUTION
(usually charged)
Nucleophilic Addition to Carbonyl
Acid Catalyzed
+ more reactive to
.. :O H
O: fast addition than the un-
+
+ H C protonated precursor
C

..
.. + :O H
O H slow
+ C
C :Nu

Nu
(+)

Acid catalysis speeds the rate of

addition of ACIDIC SOLUTION
weakk nucleophiles
l hil and d stronger acid
weak bases (usually uncharged). pH 5-6 protonates the
nucleophile
CYANOHYDRINS
Addition of Cyanide
y :C N:
Buffered to pH 6-8 .. _
:O : :O :
_
R C R + CN R C R

CN
.. _ ..
:O : :O H

R C R + H2O R C R

CN CN
a cyanohydrin

In acid solution there would be littleACN -,

cyanohydrin
and HCN (g) would be a problem (poison).
 CYANIDE ION BONDS TO HEMOGLOBIN
..
CYANIDE IS
N Cyanide bonds
IS A POISON C (irreversibly) to the
.. site (Fe II) where
CH3 oxygen usually bonds.

H3C
N N You die
Y di off
Fe suffocation -
N N lack of oxygen.
H3C CH3

CH2CH2COOH
CH2CH2COOH

HCN is a gas that you can easily breathe into your lungs.
ORGANOMETALLICS
 Synthesis of Alcohols
Addition of Organometallic Reagents
.. _ +
:O : :O: M
ether
R M + R C R
C
(R-MgBr) R R
R
(R-Li)
:R - H2O workup
k
+ step
H
These reagents cannot
..
exist in acid solution :O H

R C R + M (OH)x

alcohol
l h l
R
 Summary of Reactions of
Organometallics with
Carbonyl Compounds
All review
• Organometallics with ketones yield t you
to
tertiary alcohols
• Organometallics with aldehydes yield
secondary alcohols
• Organometallics with formaldehyde yield
primary alcohols.
• Organometallics with carbon dioxide yield
carboxylic acids.
etc.
HYDRATES
 Addition of Water
O O H
+
H
C + H2O R C R'
R R'
O H
aldehyde or ketone
favored a hydrate

hydrates are unstable

most hydrates revert to an aldehyde and cannot be isolated
or ketone as soon as they form in most cases
O H
O
R C R' + H2O
C
R R'
O H
 ACID CATALYSIS
RECALL
H
+
O H
H ..
.. + ..
:O :O H :O H

Acid catalysis enhances the reactivity

of the carbonyl group - nucleophilic :Nu
N
addition proceeds more easily. weak nucleophiles
can react

Water is a weak nucleophile.

WATER ADDS TO THE CARBONYL GROUP OF
ALDEHYDES AND KETONES TO FORM HYDRATES
H catalyzed by a
+ trace of acid
O H
.. H .. .. ..
+ H H H
:O :O :O :O
C C
O+ :O a hydrate
.. H .. H .. H
O H
.. .. H
H O H
H
.. +
O H
H ..

for most compounds the equilibrium MICROREVERSIBILITY:

favors the starting
g materials In a reaction where all steps
p are
and you cannot isolate the hydrate reversible, the steps in the reverse
reaction are the same as those in
the forward reaction, reversed!
ISOTOPE EXCHANGE REVEALS THE PRESENCE
OF THE HYDRATE

O O18 an excess off H2O18

18 H+ shifts the equilibrium
+ H2O
R R R R to the right
excess

O H
+H2O18 -H2O
R C R
18 O
H exchange shows the
presence of a symmetric
intermediate
 SOME STABLE HYDRATES
these also indicate that hydrates
y are possible
p

δ−
Cl O Cl OH
Cl C Cl C OH
δ− δ+Cl H
Cl H
chloral chloral hydrate
δ−

120o expected
60o required OH
109o expected
O 60o required
sp2 sp3 OH
cyclopropanone
l cyclopropanone
l
hydrate
SOME ADDITIONAL STABLE HYDRATES

O O O OH
H C C H C C OH
glyoxal H
H

O O O OH
Ph C C Ph C C OH
H
H
phenylglyoxal
ACETALS AND
HEMIACETALS
 ACID CATALYSIS
RECALL
H
+
O H
H ..
.. + ..
:O :O H :O H

Acid catalysis enhances the reactivity

of the carbonyl group - nucleophilic :Nu
N
addition proceeds more easily. weak nucleophiles
can react

Alcohols are weak nucleophiles.

 Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD

addition of one mole

O O H
H+
hemiketal
R C R' + ROH R C R'
O R
addition of second mole

O H O R
H+
R C R' + ROH R C R' + H O
O R O R H
an aketal

The equilibria normally favor the aldehyde or ketone starting

material, but we will show how they can be made.
ACETALS AND HEMIACETALS
R R OH ROH R OR
ROH
C O C C
OR OR
H aldehyde H H

hemiacetal acetal

R R OH ROH R OR
ROH
C O C C
OR OR
R ketone R R
(h ik t l)*
(hemiketal)* (k t l)*
(ketal)*
*older term *older term
 ..
R OH + H 2S O4 R O H Like a
+ hydronium
y
H ion
R
H O
+
.. .. H + ..
:O :O H :O H

R C R R C R R C R
.. O+
O H .. R
H .. R ..
ACID CATALYZED :
FORMATION OF A
first R O
addition H
HEMIACETAL
.. H
Normally the starting :O H
material is favored -
but a second molecule R C R + R O+
of alcohol can react .. H
if in excess (next slide) : ..
O
hemiacetal R
FORMATION OF THE ACETAL ( from the hemiacetal )
remove
R
H O
+ H ..
.. H O H
H
.. second
.. H .. : ..
O
addition
:O H + O H R
R C R R C R R C R
R C R +
:O
.. :O
..
SN1 :O + :O
R R R R
hemiacetal
Resonance
stabilized
.. .. .. carbocation
H
:O R R O: O R
+ H H +
R O
: R C R R C R
H :O :O
.. R .. R
acetal
STABILITY OF ACETALS AND HEMIACETALS

Most hemiacetals are not stable, except for those of sugars

(see later).
later)

Acetals are not stable in aqueous acid, but they are stable to
aqueous base.
base

OR H2SO4 ROH
AQUEOUS
ACID
C C O +
H2O
OR
ROH

AQUEOUS OR NaOH
BASE C no reaction
OR H2O
ADDITION OF WATER AND ALCOHOLS
WATER O H2O HO OH
C hydrate
y

ALCOHOLS
O ROH
R-O-H ROH
R-O-H
HO OR RO OR
C
H2O
hemiacetal acetal

O acetals are
RO OR H+
+2 ROH stable to base
H2O
but not to
H2O aqueous acid
no reaction
NaOH
REAKSI OKSIDASI
 OKSIDASI ALDEHID DAN KETON

• Keton tidak mudah dioksidasi

• Aldehid sangat mudah dioksidasi
dioksidasi, menjadi
asam karboksilat

Zat pengoksidasi : KMnO4, H, H2O

Reaksi Reduksi
 Reaksi Reduksi
• Reduksi aldehid menghasilkan alkohol primer
• Reduksi keton menghasilkan alkohol sekunder
• Zat pereduksi:
H2 kkatalis
H2, li
Zn/Hg, HCl
Reaksi Adisi-eliminasi
 Reaksi Adisi-eliminasi
• Aldehid + Amina Primer Imina
• Aldehid + Amina sekunder Enamina
• Aldehid + Amina tersier hidrazon
 Ramalkan produk hemiasetal atau
hemiasetal siklik dari:

11. 5-hidroksi-2-heksanon
5 hidroksi 2 heksanon dengan air
2. 1,3,4,5,6-pentahidroksi-2-heksanon
dengan air
3. propanal dengan metanol
4. Aseton dengan 1,2,3-propanatriol
Ramalkan apa produk reaksi sikloheksanon
dengan :

1. CH3NH2
2. (CH3)2NH