A2 Chemistry
Aldehydes and
Ketones
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ALDEHYDES and KETONES
Collectively known as CARBONYL compounds
H
Aldehydes General functional group is C
O
Abbreviated –CHO
Named using (name of corresponding alkane….al)
H H H
H C C C CH3CH2CHO Propanal
H H O
H H
H C C CH3CHO Ethanal
H O
H H H H
H C C C C CH3CH2CH2CHO Butanal
H H H O
C C C
Ketones General functional group is
O
Abbreviated C-CO-C
Named using (name of corresponding alkane….one)
H H
H C C C H CH3COCH3 Propanone
H O H
H H H H
H C C C C C H CH3COCH2CH2CH3 Pentan-2-one
H O H H H
H H H
H C C C C H CH3COCH2CH3 Butanone
H O H H
PHYSICAL PROPERTIES
1. Boiling points HIGHER than similar Mr hydrocarbons
because stronger dipole-dipole forces are present between aldehyde
and ketone molecules.
2. Boiling points LOWER than similar Mr alcohols / acids
because stronger hydrogen bonds are present between alcohol and
acid molecules.
3. Provided Mr not too large, aldehydes and ketones are relatively
soluble in water because the O atoms can
hydrogen bond to H in water.
PREPARING ALDEHYDES
= first oxidation products of PRIMARY alcohols
H H
R-C-O-H + [O] R-C + H2O
H O
[O] provided by acidified dichromate(VI), Cr2O72-.
Reaction mixture heated and IMMEDIATELY distilled
to avoid further oxidation to the carboxylic acid.
H OH
R-C + [O] R-C
O O
eg Naming the organic products, write equations for oxidations of :
(a) ethanol (b) 2-methylpropan-1-ol
eg Naming the organic products, write equations for oxidations of :
(a) ethanol (b) 2-methylpropan-1-ol
H H
(a)
CH3-C-O-H + [O] CH3-C + H2O
H O Ethanal
H OH
CH3-C + [O] CH3-C Ethanoic acid
O O
(b) H H H H
CH3-C C-O-H + [O] CH3-C C + H2O
H3C H CH3 O
2-Methylpropanal
H H H OH
CH3-C C + [O] CH3-C C 2-Methylpropanoic
acid
CH3 O CH3 O
PREPARING KETONES
= oxidation products of SECONDARY alcohols
H
R1-C-O-H + [O] R1-C-R2 + H2O
R2 O
[O] provided by acidified dichromate(VI), Cr2O72-.
Reaction mixture heated under reflux
since further oxidation does not occur.
ketones are not reductants since not oxidisable.
Used in chemical tests to distinguish aldehydes from
ketones, since aldehydes are reductants.
eg Naming products, write equations for oxidations of :
(a) propan-2-ol (b) 3-methylbutan-2-ol
eg Naming products, write equations for the oxidations of :
(a) propan-2-ol (b) 3-methylbutan-2-ol
(a) H
CH3-C-O-H + [O] CH3-C-CH3 + H2O
CH3 O
Propanone
(b) H
CH3-C-O-H + [O] CH3-C-CH(CH3)CH3 + H2O
CH(CH3)CH3 O
3-Methylbutan-2-one
DETECTING & IDENTIFYING ALDEHYDES & KETONES
Unknown organic
compound
NH-NH2
+ 2,4-dintrophenylhydrazine NO2
dissolved in conc. H2SO4
(Brady’s reagent) R1
+ O=C
Orange ppt. if compound R2
is an aldehyde or ketone NO2
Ppt. is the HYDRAZONE
derivative of the aldehyde
or ketone R1
Isolate the hydrazone
NH-N=C
R2
derivative, purify by
recrystallisation from
NO2
ethanol and measure its + H2O
melting point
NO2
Identify the particular aldehyde or ketone by
matching melting point to databook values
DISTINGUISHING ALDEHYDES FROM KETONES
Test 1 Test 2 Test 3
Dichromate test Fehling’s Test Silver Mirror Test
Heat with ORANGE Heat with BLUE Heat with COLOURLESS
acidified Cr2O72- alkaline Cu2+ ( + alkaline Ag+ ( + NH3)
NaOH)
For Aldehyde :
ORANGE GREEN BLUE SOLN COLOURLESS SOLN
SOLN [Cr3+(aq)] BRICK-RED PPT SILVER MIRROR [Ag(s)]
[Cu2O(s)]
ALL ARE REDUCTIONS OF METAL ION BY ALDEHYDE
Cr(+6) (+3) Cu(+2) (+1) Ag(+1) (0)
ALDEHYDE IS OXIDISED TO THE CAROXYLIC ACID
For Ketone :
Remains ORANGE Remains BLUE Remains COLOURLESS
REDUCTION OF ALDEHYDES & KETONES
= reverse of oxidation of alcohols NB (2) preferred to
reduce aldehydes &
Reducing agents = ketones – (1) and (3)
also reduce acids etc
(1) H2 gas with Ni catalyst
all represented by
or (2) NaBH4 followed by water [H]
or (3) LiAlH4 in dry ether
Applicable to both aldehydes and ketones
R1 R1 H
C=O + 2[H] C
R2 R2 OH
Acid ALDEHYDE primary alcohol
KETONE secondary alcohol
Predict the reduction product(s) of :
1. Propanal 2. Butan-2-one
H H
CH3 CH2 C OH CH3 CH2 C CH3
H OH
Propan-1-ol Butan-2-ol
3. Butan-2,3-dione 4. Hexanoic acid
H H CH3CH2CH2CH2CH2CHO
CH3 C C CH3 (hexanal)
OH OH then
CH3CH2CH2CH2CH2CH2OH
Butan-2,3-diol
(hexan-1-ol)
H
5. Cyclohexanone OH Cyclohexanol
MECHANISM OF REDUCTION
Stage 1 : Nucleophile (:H-) attacks +C of C=O
:H- from NaBH4 H
+
C C
O- :O-
Stage 2 : Protonation of O- by water
H
H Primary or
secondary alcohol
C C formed
OH + :OH-
:O- H OH
= NUCLEOPHILIC ADDITION
NUCLEOPHILIC ADDITION OF HCN
common to both aldehydes and ketones
- :CN = the nucleophile, attacks +ve C of +C=O
R1 R1 CN
C=O + HCN C
R2 R2 OH
2-hydroxynitriles
Note : HCN provided by mixing K+CN- with dil.
H2SO4 because HCN is so weak that the
concentration of :CN- would be very low.
Predict the product(s) of HCN reacting with:
1.Methanal 2. Propanone
H CN CH3 CN
C C
H OH CH3 OH
2-hydroxyethanenitrile 2-hydroxy-2-methylpropanenitrile
3. Ethanal 4. Cyclohexanone
CN
H CN
C OH
CH3 OH
2-hydroxypropanenitrile 1-cyanocyclohexanol
MECHANISM OF NUCLEOPHILIC ADDITION OF HCN
Stage 1 : Nucleophile (:CN-) attacks +C of C=O
:CN- CN
+
C C
O- :O-
Stage 2 : Protonation of O- by H2SO4
CN
CN Note: Exactly
parallel to
C C reduction
OH + HSO4-
:O- H OSO3H
OPTICAL ACTIVITY OF 2-HYDROXYNITRILES
If R1 and R2 not the same,
CN
2- hydroxynitrile will be
R1 C R2 optically active because
it contains C bonded to 4
OH different groups
= a CHIRAL or
ASYMMETRIC carbon atom
stereoisomers which are non-superimposable mirror images
of eachother
rotate plane-polarised light EQUALLY but OPPOSITE
Measured by polarimeter (see “isomerism” notes)
Optical isomers (“enantiomers”) of 2-hydroxynitriles
OH HO
C C
CN NC
R1 R1
R2 R2
mirror
A 50:50 mixture of such optical isomers is called a
RACEMATE. This is OPTICALLY INACTIVE because
rotational effects CANCEL.
Why does aldehyde / ketone + HCN reaction produce a racemate?
R1 R2 Aldehydes and ketones are PLANAR (flat) around the
C=O carbon
CN- nucleophile may (50:50 chance) attack from
C “front” or “back” of this plane
50:50 mixture of 2 different optical isomers
O
R2 R2
“Back” “Front”
gives: gives:
C C
R1 CN R1 OH
OH NC
NB Racemisation provides evidence to support the proposed
nucleophilic addition mechanism.
THE IODOFORM REACTION
Test for methyl aldehydes and ketones.
Heat with I2 dissolved in aq. NaOH
CH3 C R Also applies to alcohols of the
R = H (aldehyde) or type:
O CnH2n+1
CH3 CH R
+ 3I2 + 4OH-
OH
i.e. ethanol or any secondary methyl
alcohol
-
O C R
CHI3 + These are oxidised to the corresponding
O methyl aldehyde or ketone by the
alkaline I2
+ 3I- + 3H2O
CH3-CH(OH)-R + I2 + 2OH-
CHI3 = triiodomethane =
“iodoform” = bright yellow
CH3-CO-R + 2I- + 2H2O
precipitate
SAMPLE QUESTIONS
A. CH3CH2CHO B. (CH3)2CHCHO C. CH3CH2COCH2CH3
Name compounds A – C
A. Propanal B. 2-Methylpropanal C. Pentan-3-one
By selecting from A – C, select all the compounds which satisfy the following
requirements.
(i) Could be reduced to a secondary alcohol.
ketone C only
(ii)Could be oxidised to a carboxylic acid.
aldehyde A and B only
(ii)C be reduced to a primary alcohol.
aldehyde A and B only
(iii) Would produce a precipitate when treated Brady’s reagent.
Carbonyl compound A, B and C
Name the compound formed when (a) propanal (b) methanal is treated with
HCN.
(a) 2-hydroxybutanenitrile (b) 2-hydroxyethanenitrile
State the conditions for carrying out these reactions.
+ KCN and dil. H2SO4 at room temperature
Write an equation for each reaction.
H CN
(a) CH3CH2CHO + HCN C
CH3 CH2 OH
H CN
(b) HCHO + HCN C
H OH
Are the products optically active? Explain.
Neither is optically active because:
(a) racemisation will occur
(b) the product does not contain a chiral C (R1 = R2 = H)
Aldehydes and ketones can be reduced to alcohols by lithium
tetrahydridoaluminate(III), LiAlH4.
State the conditions under which this reagent is used.
In dry ether under reflux without heat
P. CH3CH(OH)COOH Q. CH3COCOOH
P may be produced from Q by reduction, but this cannot be achieved with
lithium tetrahydridoaluminate(III).
What will be the product if this reagent is used?
C=O and COOH in Q will both be reduced
propan-1,2-diol (CH3CH(OH)CH2OH)
How would you obtain P from Q?
Use a milder reducing agent
NaBH4 in water
The End
