Physical Properties of Aldehydes & Ketones

SOLUBILITY
C1 C4: aldehydes & ketones contain oxygen atoms thus, they do form H-bonds
w/ water
higher molecular weight aldehydes & ketones are insoluble since water
molecules cannot solvate the large R groups
R-C-H
R-C-R
ll
ll
O----- H +-O-H
O-----H +-O-H
-

BOILING POINT
-OH C=O: 2 molecules of an aldehyde or ketone cannot form hydrogen bonds
w/ each other
R-C-H
O=C-R
ll
l
O
H
neither molecule contains O-H, N-H or F-H bond
C=O -O- R-H: aldehydes & ketones behave as dipoles that attract each other
thus, they boil at higher temperatures than the non polar alkanes or the less
polar ethers

Chemical Properties of Aldehydes & Ketones

MILD OXIDATION REACTIONS
Tollens Test

R-CHO + 2[Ag(NH3)2]
RA

OA

+ OH - R-COO- + 2Ag + 4 NH3 + 2H2O

Tollens reagent: AgNO3 & NH4OH

(+) VR: silver mirror or silver deposit
aldehydes are easily oxidized to the corresponding carboxylic acids or
carboxyate salts
ketones resist oxidation; they can only be oxidized by heating w/ very strong
oxidizing agents
Benedicts Test

R-CHO + 2Cu2+ + 5OH- R-COO - + Cu2O + 3H2O

RA

OA

Benedicts reagent: CuSO4 & NaOH

(+) VR: brick red ppt.
aldehydes are easy to oxidize & ketones are not

* compounds having an -OH group will also give a (+) VR in both Tollenss &
Benedicts tests

REDUCTION
aldehydes to 1o alcohols
[r]
H-CHO
CH3OH
ketones to 2o alcohols
[r]
CH3COCH3 CH3CHOHCH3
reduction/hydrogenation involves the addition of H to C=O
opposite of oxidation/dehydrogenation reaction
LiAlH4 & NaBH4 are the most common reducing agents in the laboratory but not
in the living system (NAD:H)
CH3-C-C-OH + NAD:H CH3CH- C -OH + NAD+
ll ll
l
ll
OO
OH O
pyruvic acid
lactic acid
ADDITION REACTIONS
Hemiacetal and Hemiketal Formations
R-CO-R + R-OH hemiketal
OR
R-C+ -R
ll
Oalcohol

RO- H+

ether

l
R- C- R
l
OH

CH3CH2COCH3 + CH3CH2CH2OH hemiketal

OCH2CH2CH3
CH3CH2C+ -CH3 + CH3CH2CH2O- H+
ll
O-

l
CH3CH2C-CH3
l
OH

1 mole of an alcohol added to a ketone yields a hemiketal

hemiketal - has both ether & alcohol groups
- unstable compounds (but carbohydrates are
considered stable
hemiketals)
Acetal and Ketal Formations

R-CO-R + 2 moles R-OH ketal

OR
l
R-C-R
+ RO- H+
l
OH
hemiketal

OR

ether
l

R-C -

CH3
l
OR

ether

ketal

CH3CH2COCH3 + 2 moles CH3CH2CH2OH ketal

OCH2CH2CH3
OCH2CH2CH3
l
l
-
+
CH3CH2C-CH3 + CH3CH2CH2O H CH3CH2C-CH3
l
l
OH
OCH2CH2CH3
hemiketal
ketal
addition of a 2nd mole of alcohol involves the removal of H2O & the formation of
a more stable ketal compound
ketal has 2 ether groups
HYDROLYSIS
(CH3)2-C - OCH2CH3
l
OCH2CH3

CH3 C CH3
ll
O
ketone

and

CH3CH2OH
alcohol