ALDEHYDES AND KETONES

Aldehyde
O C R H

STRUCTURE

R = H, alkyl, aryl

Ketone

O C R R' R and R' = alkyl or aryl R and R' cannot be hydrogen!

NOMENCLATURE

IUPAC Nomenclature of Ketones

Choose the longest continuous carbon chain that 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 Nomenclature program!

EXAMPLES
O C CH 3 CH 2
2-Pentanone

CH 2 CH 3
O CH3 CH2 C CH CH2 CH3
4-Ethyl-3-hexanone

CH2 CH3

CH CH3

CH3

3-Isopropylcyclopentanone

KETONES

Common, or Trivial, Names

Name each group attached to the carbonyl group as an alkyl group
Combine into a name, according to the pattern:

alkyl alkyl ketone

NOTE: This is not all one word!

Example of Common Names

O C CH 3 CH 2 CH 2 CH 3
O CH3 CH2 C CH2 CH3

Methyl propyl ketone

Diethyl ketone

SPECIAL CASES
O C CH3
acetone
A common laboratory solvent and cleaning agent

O C
CH3
diphenyl ketone
benzophenone

dimethyl ketone

O C CH3
methyl phenyl ketone
acetophenone

KNOW THESE

IUPAC Nomenclature of Aldehydes

Choose the longest continuous carbon chain that contains the carbonyl carbon 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
H3C CH2 CH2 CH2
pentanal

C H

aldehyde group is always carbon 1

Cl
4

CH3

CH
2

CH CH3

C H

2-chloro-3-methylbutanal

Common Names of the Aldehydes

O C H H CH3 Formaldehyde 1 O C H3C CH2 C Butyraldehyde 4 O C H3C CH2 CH2 CH2 CH2 Caproaldehyde 6 H H H3C CH2 CH2 C Valeraldehyde 5 O C H H3C CH2 Acetaldehyde 2 O C H Propionaldehyde 3 O C H

RECOGNIZE THESE

O C H

SPECIAL CASES
H

O C H

formaldehyde

O C H CH3

benzaldehyde

acetaldehyde

KNOW THESE

Forming Common Names of Aldehydes

USE OF GREEK LETTERS

O H

C C C C C C C .

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

CHO Cl
-chlorocaproaldehyde ( -chlorohexanal )

CHO Cl
-chlorocaproaldehyde ( -chlorohexanal )

REACTIVITY OF THE C=O GROUP

NUCLEOPHILIC ADDITION

GENERALIZED CHEMISTRY

THE CARBONYL GROUP

nucleophilic at oxygen electrophiles add here H+ or E+

.. O:

.. :O :

C
+
Nu:

nucleophiles attack here electrophilic at carbon

NUCLEOPHILIC ADDITION TO C=O

MECHANISMS IN ACID AND IN BASE

Nucleophilic Addition to Carbonyl Basic or Neutral Solution

.. O: + C .. _ : O:

-:Nu

slow C Nu

an alkoxide ion

.. _ : O: fast C Nu + H2O

.. :O H C Nu

or on adding acid Good nucleophiles and strong bases (usually charged)

BASIC SOLUTION

Nucleophilic Addition to Carbonyl Acid Catalyzed

.. O: C + + H + :O fast C H

more reactive to addition than the unprotonated precursor

.. + O H + C :Nu

.. :O slow C Nu

(+)

Acid catalysis speeds the rate of addition of weak nucleophiles and weak bases (usually uncharged).

ACIDIC SOLUTION pH 5-6

stronger acid protonates the nucleophile

CYANOHYDRINS

Addition of Cyanide
Buffered to pH 6-8
:O : _ R C .. _ :O : R C CN R + H2O R R + CN R C CN .. :O C CN

:C N:

.. _ :O : R

H R

a cyanohydrin

In acid solution there would be little CN-, A cyanohydrin and HCN (g) would be a problem (poison).

CYANIDE ION BONDS TO HEMOGLOBIN .. N CYANIDE IS Cyanide bonds IS A POISON (irreversibly) to the C ..
CH3 H3C

site (Fe II) where oxygen usually bonds.

N Fe N

N N CH3 CH2CH2COOH

You die of suffocation lack of oxygen.

H3C

CH2CH2COOH

HCN is a gas that you can easily breathe into your lungs.

ORGANOMETALLICS

Synthesis of Alcohols

Addition of Organometallic Reagents

:O : R M + R C R .. _ + :O: M
ether

C R

(R-MgBr)

(R-Li)
These reagents cannot exist in acid solution

:R .. :O R C R

H2O + H H R

workup step

M (OH)x

alcohol

Summary of Reactions of Organometallics with Carbonyl Compounds

Organometallics with ketones yield tertiary alcohols Organometallics with aldehydes yield secondary alcohols Organometallics with formaldehyde yield primary alcohols. Organometallics with carbon dioxide yield carboxylic acids. All review to you

etc.

HYDRATES

Addition of Water
O C R R'
aldehyde or ketone favored

+ H
+ H2O R

O H C O H a hydrate
hydrates are unstable and cannot be isolated in most cases

R'

most hydrates revert to an aldehyde or ketone as soon as they form

O H R C O H R' R O C + R' H2O

ACID CATALYSIS
RECALL

H O H H .. .. + :O :O H
+

.. :O H
+

Acid catalysis enhances the reactivity of the carbonyl group - nucleophilic addition proceeds more easily.

:Nu
weak nucleophiles can react

Water is a weak nucleophile.

WATER ADDS TO THE CARBONYL GROUP OF ALDEHYDES AND KETONES TO FORM HYDRATES
H O H
+

:O

..

..

catalyzed by a trace of acid + H :O

:O
C

..

:O
C

..

.. O ..

O+ H .. H H

:O ..
H H
+

a hydrate

.. O ..

O H

..

for most compounds the equilibrium favors the starting materials and you cannot isolate the hydrate

MICROREVERSIBILITY: In a reaction where all steps are 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 R R O18
H+ an excess of H2O18 shifts the equilibrium to the right

+ H2O

18

excess

+H2O18

O H R C R
18 O

-H2O

exchange shows the presence of a symmetric intermediate

SOME STABLE HYDRATES

these also indicate that hydrates are possible

Cl

O Cl H

Cl C Cl H

OH OH

Cl

+Cl

chloral

chloral hydrate

120o expected 60o required

OH
sp3 OH

O
sp2 cyclopropanone

109o expected 60o required

cyclopropanone hydrate

SOME ADDITIONAL STABLE HYDRATES

O H C C
glyoxal

O H H

OH

C C OH H O OH

O Ph C C

O Ph H

phenylglyoxal

C C OH H

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 addition proceeds more easily.

:Nu
weak nucleophiles can react

Alcohols are weak nucleophiles.

Addition of Alcohols
TWO MOLES OF ALCOHOL WILL ADD

addition of one mole

O R C R' + ROH
addition of second mole

H+

O H R C R' O R
hemiketal

O H R C R' O R + ROH

H+

O R R C R' + H O O R
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 C O
ROH

R C H

OH ROH OR

R C H

OR OR

H aldehyde

hemiacetal

acetal

R C O R
ketone

ROH

R C R

OH ROH OR

R C R

OR OR

(hemiketal)*
*older term

(ketal)*
*older term

..
R OH

+ H 2S O4
R

O H

Like a hydronium ion

:O
R C R

..

H O

+
H

..

:O H
R C R

:O
O+

..

R C R H

ACID CATALYZED FORMATION OF A HEMIACETAL

Normally the starting material is favored but a second molecule of alcohol can react if in excess (next slide)

.. O ..

..

first addition

: R O H :O :O .. ..
H
H

..

R C R
hemiacetal

+ R O+

..

FORMATION OF THE ACETAL ( from the hemiacetal )

remove

R H O

..

+
H

:O H
R C R

..

O H + R C R

..

.. O ..

:O ..
R C R
SN1

second addition

R C R

:O ..
hemiacetal

:O .. ..

:O +

:O

: R O H

:O R
R C R

: R O H
acetal

..

O R

..

Resonance stabilized carbocation

R C R

:O ..

:O ..

STABILITY OF ACETALS AND HEMIACETALS

Most hemiacetals are not stable, except for those of sugars (see later). Acetals are not stable in aqueous acid, but they are stable to aqueous base.

AQUEOUS ACID

OR H2SO4 OR
H2O

ROH C O + ROH

AQUEOUS BASE

OR NaOH C OR H2O

no reaction

ADDITION OF WATER AND ALCOHOLS

WATER

O C

H2O

HO

OH
hydrate

ALCOHOLS
O C

R-O-H
HO OR

R-O-H
RO OR

H2O
hemiacetal acetal

RO

OR

H+ H2O H2O

O +2 ROH
no reaction

acetals are stable to base but not to aqueous acid

NaOH

REAKSI OKSIDASI

OKSIDASI ALDEHID DAN KETON

Keton tidak mudah dioksidasi Aldehid sangat mudah 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, katalis Zn/Hg, HCl

Reaksi Adisi-eliminasi

Reaksi Adisi-eliminasi
Aldehid + Amina Primer Aldehid + Amina sekunder Aldehid + Amina tersier Imina Enamina hidrazon

Ramalkan produk hemiasetal atau hemiasetal siklik dari:

1. 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