ALDEHYDES KETONES

Calledcarbonyl compounds
becausetheycontainthe carbonyl
group
11
c
Aldehydes ketones
0 o
1 pterminalhydrogen 1
R C i ti R C R
whereRicanbe H where Reanentbe H
O 0
it 11
1st H c H methanal 1st Ctb C CH propanone
or acetone
ketone
or dimethyl
2nd CHz C H ethanol would be
0 written as CH3COCHs
O
3rd CH3CH2 C H propanal 2nd i
0 CHS C CH2CH
butanone
4th cHzCHzCHz C H butanal
0
Example 3rd
written as CH3CH2CHO for CHS 2C CHzCHzCH3
propanol f
Positional
i 3 n s
pent 2 one
Isomers
o or Z pentanone
Ii
CHzCHz C cHzCH3
Precedence is i 2 3 u s
naming
Acids
i Carboxylic pent 3 one
2 Nitriles or 3 pentanone
3 Aldehydes
4 Ketones
5 Alcohols

Examples i O l
S y 3 2 li l
CHIH z CH CHEE's l aldehydegetsprecedence

III Alcohol
substituent
3 hydroxypentanal
 OH 0 O O
I 11 11 11
CHs CHz CH C CH CHz C CH2 C H
3 hydroxy
pent 2 one 3 oxobutanal
note whenaldehydes and ketones
are substituents theyarecalled
oxo and are a number
given
0 O onthechain
Il l
H C LCH2 z C OH 0 O
s ns z
l
Il il
5 oxopentanoic acid CHS C CH zCHz C OH
i
s u 3 z
1
dHowto differentiate c 4 oxopentanoicacid
whether an oxo
compound is an
aldehyde or ketone
If oxo group is on the
last1terminalcarbon then
it's an aldehydegroup otherwise
it's a ketonegroup

Aldehydes and ketones are functional group isomers of each other

C3h60

f
Aldehyde ketones

CH3CHz C H 113C C CH3

propanal lol propanone
O

Main intermolecular force in aldehydes and ketones is the permanent

dipole permanent dipoleforce of attraction
i
i
R R R R
I est s I St s ist s I St s
C O mum C O i C O mu C 0
I 1 I 1
H H R R
Aldehydes ketones
SOLUBILITY in water
lower aldehydes basically the first two methanol andethanol are
soluble in water as they can form hydrogenbonds with water

St O gt
un H H waters H is
5O electrondeficient
StIl est
c C
a
ooo
et
Stt H

in waterdecreases as the number of carbons increase as VDW

Solubility forces start to dominate
ID ID

est
Il
As lengthof the Os
carbon chainincreases ID ID forces increasingly
become the more prominentintermolecularforce
28-06-22

BOND ANGLES SHAPES

0
120 O
C I l 1200 H
H or H C ry 1
120 CH C f 109.5
trigonalplanar trigonal t l n
planar H tetrahedral

C O to 1a bond
s
H
spa spzhybridized
H y
C O s c O
spz I
2
H
o bond
H a bond
s
REACTIVITY NucleophilicAddition

H St s H
C O Nu C o
H V H
Nu Heterolysis ReactiveIntermediate
Nucleophile

USES
Ketones have a sweetsmell like esters
Aldehydes have a stringent sharp unpleasant odour

o H C H methanol aka Formalin solution

used to preserve biological specimens

Aldehydes ketones are used for foodflavorings and perfumes

Cn
H
benzaldehyde
almondflavor to spearmint
flavour

CH3 O
l n
CHs CH2 g CH C H
Chanel No 5 perfume

0 O
H H
CH s C C CH3 Stalesweatsmell

O
Il
CHz CH C H Component of bonfires
that makes youreyeswater
 REACTIONS
i Reactions that are common to both aldehydes and ketones
nucleophilic Addition Aldehydes

Reagent HCN hydrogencyanide

conditions trace amount of Nacn as catalyst
The catalystincreases the rate ofreaction by providing
more CN ion

OverallRxns Aldehyde traceamounts pchiralcarbon

of NaCN 3 El
CH3CHO t HCN CH3CH OH CN
AP nitrile
2 hydroxypropane

spound
thathave the OH
Heterolysis
groupand the CN
group bondedto
Mechanism H C IN the samecarbon
Dative
S
D Heterolysis
O OH
cest l I
I n l HC C H H3C C H t CN
tbc H 1 I catalyst
alive CN CN Regenerated
a
Nc
nucleophile intermediate

chared carbon Cst of the aldehyde is

The partiallypositivelyattracts
electrondeficient and the en nucleophile
The CN ion makes dative bond with the Cst and
a as a result
the c O double bond breaks heterolytically
The T1 electrons in the C O bond move to the oxygen atom
creating an intermediate with a full negativecharge
The negatively charged oxygen to
dativebond with HCN
getsprotonated bymaking a
 The H C bond in HCN breaks heterolytically toregenerate the CN
ion and the product cyanohydrin is formed
30-06-22
reducedto
nitrile Amines
Hydrolisedto
carboxylicAcid
chiral carbons
Example Hydrolysis of nitrile
OH OH
HCl 1Htlaqs I
CHS CH CN CH3 CH COOH
heatunder 2 hydroxypropanoicacid
reflux aka lactic acid

OH OH
I i 1
c i
Hoo H i ti COOH
Hz Hz

Nole cannot use Na ethanol

as reducingagentas
Reduction ofnitrile Na would react with
OH OH the alcohol
I NaBHu l
Hz CH CN Hzo CHS CH CH2mHz

Nucleophilic Addition ketones

OverallRxn OH
traceamount 1
of Nach s CH3 C
CH3COCH3 t HCN CN
reagent rtp
CH3
Z hydroxy 2 methylpropane
nitrile
A Heterolysis
Mechanism NH CIN
05JHelerolysis o
O
11 Dah OH
cest l 1
tbc Gt3 HzC C CH3 Hsc C CH z t CN
I 1
alive CN CN
nc
 intermediate

OH
I
I
CHz C CH3 CN

Hydrolysis Reduction
Ht ag NaBHy H2O
reflux s
OH OH
I I
CH3 C COOH Hz C CH2MHz
I 1
Ctb Ctb

Reduction Aldehydes t ketones

by iemetal hydrides
NaBHysodium borohydride H2O
reducedto Lialtly lithium aluminum hydride
Aldehydes s 10alcohols anhydrous ether
CHzCHO NaBHy rtp
H2o
CHSCH20H
toalcohol toverystrong
reducingagent
used to
mainly acids reduce
Reducedto carboxylic
ketones s 20 alcohols
CH3COCH3
naBHy rtp
S CHIH OH CH3
H2O 20alcohol

catalytic Hydrogenation usingHaig as a reducingagent

0 OH
i ni catalyst 1
CH C CH t Hz s CH3 CH CH
ketone 5dm pressure 20alcohol
 Condensation Rainsof the carbonyl
group forbothaldehydes ketones

compounds based on hydrazine can add across the carbonylgroup

This is used todistinguish aldehydes and ketones fromotherfunctional

groups
Reagent 2,4 DNPH
2,4 dinitrophenylhydrazine ag

eo uo
N N Hydrazine phenyl
H l when benzene is
I H a
H H substituent its called
phenyl

Dinitro two nitro groups NO2

Combining all these above components

NO2
Reagent 3
z
1 4
In aqueoussolution
N N no
H l 1
H H

Ran with Aldehydes

i
CHz H noz CHz noz
i X h
c O t N N no C N N no
l l l
H H
I H H H
i
Hydrazone
Orange
comes out or Yellowppt
as H2O
2xn with ketones
i
CHz H n 2 CHz noz
i X hC
c O t N N no N N no
l I i
CH3 H
X H CH3 H
i
Orange
comes out or Yellowppt
as H2O

REACTIONS SHOWN BY ALDEHYDES ONLY

i ToHens Reagent test Silver Mirror Test

R c II aldehydesbehave as reducingagents as
they have
a H atom at the end

A reducingagent is oxidised itself

Aldehydes are oxidised to carboxylic acids
Reagent Ammoniacal Silver Nitrate Totten'sReagent

Token'sreagenthasto be preparedfreshly in labs andusedimmediately

as the Ag gets oxidised readily
Start with Agnos Diamminesif
agNaOH 99 NH3 slowly
Ag Lag 2
from Ag 20 until
Blackppt pptjust AgLNH3 2 OH
Agnos dissolves 99
Tokens
Reagent
Aligand is a species that uses its saline
lone pair to make a dativebond HN Ag c NH
with a centralmetal atom
NH3 behaves as a ligand
 THE REACTION

0 O
Il 11
R C H t 2CAgCNH3 2 TOH wwardmembaaths
Ag s R t C O NHyt
Silver mirror H2O
r or blackppt t 3MHz

i r
un
um
ECHO
I waterbath
Tollens C U O 0
Reagent id
R C H s R C OH Acid

Ag NHs
u
Heat O
11
R C O NHut
Ammonium salt of
the carboxylicacid
reduced oxidised
Agt Ages
Silver
Agzo
Black
Mirror ppt
n
Both are J
positive
tests

2 Fehlings Solution test Benedict's test

Reagent Cason ag and NaOH ag
ie Alkaline arson Laq

reduced
Cukaq s cuz 0 s
Blue Solution Brick red observation
ppl
Positive for aldehydes only
 O 0
oxidised NaOH
CH3 C H s CHz C OH CHKOO Nat
reducingagent salt
heat in
CHzCHO t 2cm aq t SOHCaq waterbath CH COO t Cui t 31120
Ehling'ssolution
ppl
Brick red

3 Iodoform test
Aldehydes give a positiveiodoform test when a carbonyl group and a
methylgrouparebondedto the same carbon
o Ethanal is the onlyaldehydethatgives a positiveiodoform test
i o ii
i
iii i e H

All methyl ketones show a positiveiodoformtest

an can a

CHsCHz CHIH doesnotreturn a positive iodoform test

missingmethylgroup

Reactions
Aldehyde
0
11 rtp
CHz C H t 312 t 4NaOH CHI Ls t HCOONat t 31420
Lag ag opale
yellowppt t 3NaI
iodoform
tri iodomethane

ketone
O
Il
CHs C CH t 312 t 4NaOH CHI3 s t Gt3COO Nat
t 31120
ppt
Note Iodoform test was
only in the syllabus from 2016 onwards
02-07-22

0
IS A CARBONYL COMPOUND C

add 2,4 DNPH

orangeppt
Tollens Fehling's
reagent No Rin c Solution
t
KETONE
SilverMirror Brio Redppt
1
ALDEHYDE

Distinguish between
O 0 OH
11 11 I
CHsCHz C H CHz C CH CH3CHzCHz
propanol propanone propanol
Aldehyde ketone 10Alcohol
Tollens Reagent iodoform Nacs
SilverMirror yellowppl Bubblesof colorless gaswhich
extinguishes a burningsplint with
a popsound

CHzCHzCH3 CHz CHz

propane ethene
Alkane Alkene
addBra ag in the dark add Brae aq in the dark
No Rin Bromine will be decolorised
 Q
CH3GHzOH CHz C H
ethanol ethanal
Alcohol Aldehyde
i Nacs 1 2,4 DNPH
Hzgas orangeppt
2 Socle z Fehling's
whitefumesof Brick redppt
HCl
3 Tollens
Silver Mirror

note cannot use KzCreon1 Ht as it wouldoxidizeboth of thesecompounds

05-07-22