Aldehyde and Ketones F

Aldehydes and ketones : Introduction
 In nature, many substances found in living organisms are aldehydes or ketones.

 The aldehyde pyridoxal phosphate, for instance, is a coenzyme involved in a large
number of metabolic reactions.

 Ketone hydrocortisone is a steroid hormone secreted by the adrenal glands to
regulate fat, protein, and carbohydrate metabolism.
 In the chemical industry, simple aldehydes and ketones are produced in large amounts
for use as solvents and as starting materials to prepare a host of other compounds.
Aldehydes and ketones: Structure
 Aldehydes have the general formula R–CHO and ketones, R–CO–R. Both contain
the polar carbonyl group:
-
O
+
C 
Electronic Structure of the Carbonyl
H 
H
airs
C O C  O
lone p
H
H
Aldehydes and ketones: Isomerism
 The normal aldehyde in Cn will be a functional isomer of normal ketones in Cn

e.g CH3-CH2-CO-CH3 and CH3-CH2-CH2-COH
Aldehydes and ketones: Nomenclature
Common system
 Aldehydes are named using the name of the corresponding acid where -ic acid is
replaced by the suffix –aldehyde or by referring to alcohol.
E.g. HCOH: Formaldehyde or formic aldehyde or methyl aldehyde.
CH3COH: Acetaldehyde or acetic aldehyde or ethyl aldehyde
CH3CH2COH: Propionaldehyde
CH3CH2CH2COH: Butyraldehyde or butyric aldehyde or butyl aldehyde
 Simple ketones (If R and R’ groups are simple) are named by giving the alkyl or
aryl group names followed by the word ketone, in the alphabetical order.
E.g. CH3CH2COCH3 : ethyl methyl ketone (butanone)
CH3CH(CH3)COCH(CH3)CH3 : diisopropyl ketone (2,4-dimethylpentan-3-one)
Common system
 Some ketones are named by their popular name:
E.g. Acetone (dimethyl ketone): CH3COCH3
Acetophenone (methyl phenyl ketone):
 The Greek letters, alpha (α), beta (β), gamma (γ), delta (δ), and so on, are used to
indicate the point of attachment in branched-chain aldehydes;
 The α-carbon is the C adjacent to the –CHO group and corresponds to C-2 in
IUPAC system.
e.g. CH3CH(CH3)CH2COH: β-methylbutyraldehyde or 3-methylbutanal
IUPAC system
 Acyclic aldehydes and ketones are named by substituting -e of the alkane by -al
for aldehyde or by –one for ketone.
E.g.: O O O O
H H H3C H H3C CH3 H3C C4H9

Methanal or Ethanal or propanone Hexan-2-one
Formaldehyde acetaldehyde
 For aldehydes, the parent chain must contain the –CHO group and the –CHO
carbon is numbered as carbon 1 and the index of position of the function is
O O
omitted.
H H
Pentanedial or
Glutaldehyde
IUPAC system
 For ketone, the parent chain is the longest one containing the –CO– group and the
numbering begins at the end closest to the –CO– group.
E.g.:
 Very simple ketones do not require a locator number.
phenylethanone propanone
IUPAC system
 Dissymmetrical ketones are named by considering 2 separate chains:
The main chain (the one which contains the CO group) is named as a ketone while
the other chain is named as alkyl group.
Chain numbering normally starts from the end nearest the carbonyl group.
phenylethanone 2,2-dimethyl-1-phenylpropanone
 In numbering, carbonyl function has priority over hydrocarbon, alcohol and ether
functions.
IUPAC system
Examples
CH2= CH-CO-CH3
But-3-en-2-one or 3-buten-2-one
CH3-CHOH-CH2-CHO
butan-3-ol-al or 3-hydroxybutanal
C6H5-CCl=CH-CHO
3-chloro-3-phenyl-2-propenal or 3-chloro-3-phenylprop-2-enal
CH3-CO-CH2-COH(CH3)-CH(OCH3)-C≡CH
4-hydroxy-5-methoxy-4-methyl-6-heptyn-2-one
IUPAC system
 In cyclic ketones, the carbonyl group is assigned position number1, and this number
is not cited in the name, unless more than one carbonyl group is present.
IUPAC system
 Cyclic aldehydes are named by adding the carbaldehyde end or the name of
open chain aldehyde to the name of the cycle and considering the cycle as a
substituent.
IUPAC system
 In molecules containing functional groups with higher priority (such as carboxylic
acid) than aldehydes/ketones functional groups, the carbonyl is named as “oxo"
substituent.
E.g.:
 Aldehyde function has priority over Ketone function whose position is indicated by
the suffix –oxo.
IUPAC system
 When it is necessary to refer to the RCO– group as a substituent, the word acyl is
used and the name ending –yl is attached, e.g.,
O O O O
C C C C
R H H3C Ph
An acyl group Formyl Acetyl Benzoyl
E.g.:
O O
HO
4-formyl-2-oxocyclohexanecarboxylic acid 4-formylcyclohexanecarboxylic acid

Aldehydes and ketones: Physical properties
 Except gaseous methanal, up to C11, aldehydes and ketones are liquids while the
higher are solid.
 Aldehydes have a strong pungent odour while ketones smell sweet.
 As the size of the aldehydes increases the odour becomes more pleasant (i.e.
cinnamon) while for ketones, most of the higher homologs have rather bland odors.
 Odours in nature may be used to communicate between insects (pheromones).
 Since they have pleasant ordor, aldehydes are used in perfumes and artificial
flavorings.
 Since they are polar, they are used as polar solvents. Their non-polar alkyl chain
permits their use as non-polar solvents too.
 Aldehydes and ketones are definitely more volatile and have lower boiling points
than the corresponding alcohols due to the inability to form H bonds between their
molecules.
 Aldehydes and ketones have higher boiling points than similar sized alkenes due to
the greater polar character of the carbonyl group (C=O) than ethylenic bond
(C=C).
E.g. compounds with similar molecular weights
 Aldehydes and ketones are generally soluble in water due to their ability to form H
bond with water molecules.
 The first terms (for e.g. methanal, ethanal and propanone) are miscible with water
in all proportions but solubility falls with chain length.
 Due to the higher dipole moments in ketones than in aldehydes, ketones have higher
water solubility and boiling points than the corresponding aldehydes.
O O
H H Carbonyl group-water
H H
O O O O
H bond H bond
C C C C
R R R R R H R H
Aldehydes and ketones: Chemical properties
 The polarity of the carbonyl group has a profound effect on its chemical reactivity, compared
with simple polar bonds of alcohols and the non-polar double bonds of alkenes.
 The presence of unsaturated carbonyl -CO- explains the great activity of aldehydes and
ketones as their many common characters.
 Aldehydes and ketones are much alike in many of their reactions.
 Aldehydes are typically more reactive than ketones due to the following factors:
 The carbonyl carbon in aldehydes is less sterically hindered than in ketones (a hydrogen atom is
smaller than any other organic group).
 The carbonyl carbon in aldehydes generally has more partial positive charge than in ketones due to
the electron-donating nature of alkyl groups. Aldehydes only have one e-donor group while ketones
have two.
 The increase in chain length of the alkyl group enhances the shielding effect (steric hindrance)
of the carbonyl group and hence their reactivity decrease.
Different behavior: oxidation

 When oxidized, they behave differently: Aldehydes and Ketones are combustible,
but their controlled oxidation leads to different products.

 The difference in reactivity towards oxidation is the chief reason why aldehydes and
ketones are classified in separated families.

 The usual strong oxidants like air oxygen (O2), chromic acid and KMnO4, oxidise
aldehydes, but not ketones:

RCHO + O2→ RCOOH
E.g.:
RCOR + O2→ no reaction

E.g.: CH3COCH2CH3 + → no reaction

 Milder oxidizing agents oxidise aldehydes (but not ketones) into acids (this confers a
reducing character to the aldehydes). For example:
 Reduction of Tollen’s reagent (with silver ammonia ion Ag(NH3)2+) with formation
of a silver mirror. This is a silver mirror test.
RCHO + 2Ag+ + 3OH- → RCOOH + Ag + 2H2O
 Reduction of Fehling's solution (solution of CuSO4 + double tartrate of Na and K)

with formation of red precipitate Cu2O.
RCHO + 2Cu2+ + 5OH- → RCOOH + Cu2O + 3H2O

 When hot, HNO3 acid, chromic acid and KMnO4 cause the decomposition of the
molecule of ketones into a mixture of carboxylic acid.
 The adjacent C to the carbonyl group with higher H atoms than the other goes
with the carbonyl group.
KMnO4/H+
e.g. CH3COCH2CH3 → CH3COOH + CH3COOH
Boil
If the adjacent C to the carbonyl group has the same H atoms, the carbonyl
group remains with the smaller alkyl group.
e.g. CH3CH2CH2COCH2CH3 → 2CH3CH2COOH

 Seleniun oxide (SeO2) oxidizes aldehydes and ketones on the methyl group
adjacent to the carbonyl group into dicarbonyl compounds.
e.g.
CH3CH2COH + SeO2 → CH3COCOH + Se + H2O
CH3CH2COCH3 + SeO2 → CH3COCOCH3 + Se + H2O
CH3CH2CH2COCH2CH3 + SeO2 → CH3CH2COCOCH2CH3 + Se + H2O
Different behavior: Iodoform reaction

 This reaction is used to identify the presence of CH3CO- in aldehydes and ketones (on the
methyl group adjacent to the carbonyl group).
Using iodine and sodium hydroxide solution
 Iodine solution is added to a small amount of aldehyde or ketone, followed by just
enough sodium hydroxide solution to remove the colour of the iodine. If nothing happens
in the cold, it may be necessary to warm the mixture very gently.
 A positive result is the appearance of a very pale yellow precipitate of triiodomethane
(previously known as iodoform) - CHI3.
Excess of OH-
Different behavior: Iodoform reaction

 A positive result - the pale yellow precipitate of triiodomethane (iodoform) is also given
by an alcohol containing the methyl group adjacent to the C carrying –OH group.
Summary of the reactions during

the triiodomethane (iodoform)
reaction with alcohols.
Tertiary alcohols can not undergo such type of

reaction since they do not possess H atom on
the C carrying -OH group.
Common Reactions:
1. Nucleophilic addition reaction
 Aldehydes and ketones undergo nucleophilic addition reactions via their carbonyl
group (Simple fixation of the reactant on carbonyl, i.e by opening the double
bond).
 Aldehydes are more reactive than ketones in nucleophilic addition reactions for
both steric and electronic reasons.
 These nucleophilic addition reactions are catalysed by either acids or bases.
1. Nucleophilic addition reaction
 Some negatively charged

nucleophiles: Cyanide ion CN-;
Alkoxide ion RO-; carbanion R3C-;
Hydride ion H-; and hydroxyl OH-
 Some uncharged nucleophiles:
ammonia, alcohol (ROH); water;
amine.
1.1. Addition of hydride reagents: reduction

 Hydrogenation by hydrogen in presence of Ni or Pt (25°C) or reducing agents
(NaBH4, LiAlH4) leads to the corresponding alcohol:
Aldehyde mechanism
Ketone mechanism
1.2. Addition of Grignard Reagents

 Just as aldehydes and ketones undergo nucleophilic addition with hydride ion
to give alcohols, they undergo a similar addition with Grignard reagents, R- +MgX.
 Aldehydes give secondary alcohols on reaction with Grignard reagents in ether solution,
and ketones give tertiary alcohols.
Mechanism
1.2. Addition of Grignard Reagents

 Addition to formaldehyde gives primary alcohols  Addition to carbon dioxide gives
carboxylic acids
 Addition to aldehydes gives secondary alcohols
 Addition to ketones gives tertiary alcohols

1.3. Addition of water (Hydration)

 The rate of hydration is slow in pure water, but is catalysed by both base and acid:
O OH
C + H2O C
OH
 Hydration forms unstable hydrates R-
a geminal (gem) diol CH(OH)2 or R-C(OH)2-R’: (these are
stabilized by using trichlorinated
O OH aldehydes or ketones):
H C H + H2O H C H
OH
0.1% 99.9% OH

CCl3 - C - CH3+ H + OH  CCl3-C-CH3
O OH
CH3 C CH3 + H2O CH3 C CH3 O  OH
OH trichloracetone trichloracetone hydrate
99.9% 0.1%
1.3. Addition of water (Hydration)

Base-catalysed hydration: Acid-catalysed hydration:
H OH H
-
O O OH O H O OH OH OH
+ H
C C C + HO C C C C
OH OH O
HO O H H
H H
HO is a better nucleophile than H2O H2 O
OH
C + H3 O
OH
-
OH OH O
is a better electrophile than +
C C C
1.4. Reaction with monosodic sulphite solution

 In the presence of a monosodic sulphite solution (NaHSO3), aldehydes and
methylketone give well-crystallised bisulphitic compounds whose hydrolysis regenerates
aldehydes and ketones. This transformation is used to purify aldehydes and ketones.
1.5. Reaction with hydrocyanic acid (HCN)

 With aldehydes and methyl ketones, we get alcohol nitriles, called cyanohydrins.
The cyanohydrins are hydrogenated into α-hydroxyacids.
OH H+ OH
C=O + HCN → C → C
CN COOH
cyanohydrin α-hydroxyacids
1.5. Addition of Acetylides

 Aldehydes and ketones react with acetylide anions to form alkoxides, which, upon
protonation, give propargyl alcohols.
(propargyl group: HC≡C-CH2-)
 The triple bond in the propargyl alcohol can be modified by using the reactivity of the
alkyne.
E.g. Markovnikov and anti-Markovnikov hydration of the triple bond leads to formation of the
hydroxy-substituted ketone and aldehyde, respectively, after enol-keto tautomerization.
1.6. Condensations of Aldehydes and Ketones: The Aldol Reaction

 Aldehydes and ketones with an hydrogen atom undergo a base-catalyzed carbonyl
condensation reaction called the aldol reaction.
 The product is a b-hydroxy-substituted carbonyl compound.
 Aldehydes can react on themselves (aldolisation)

E.g.:
 Ketones react on themselves (ketolisation)

E.g.:

 Aldol condensations between different carbonyl reactants are called crossed or mixed
aldol condensation.
E.g.:
Ketone Aldehyde
Aldehyde Aldehyde

H at α-C in aldehydes is more acidic and more reactive towards basic species.
 The presence of alkyl groups in ketones (weakly electron donating) tend
to destabilise the formed anions making ketone less reactive.

1.6.1. Aldolisation
E.g.:
1.6.2. Ketolisation
O O

CH3  C  CH3  B CH2  C  CH3  BH
O 

O O O

CH2  C  CH3  CH3  C   CH3 CH3  C  CH2  C  CH3
CH3
BH  OH O
CH 3  C  CH 2  C  CH 3 Cetol
CH 3 CH 3
1.6.3. Crossed aldol condensation

O O

CH3C + B CH2C + BH
H H
O
O   O O

CH2C + CH3  C   CH3 CH 3  C  CH 2 C BH 
H CH3 H
OH O
CH 3  C  CH 2 C
CH3 H Aldol
1.6.3. Crossed aldol condensation

 Mixed aldols in which both reactants can serve as donors and acceptors generally give
complex mixtures of both dimeric (homo) aldols and crossed aldols.
 Because of this, most mixed aldol reactions are usually not performed unless one reactant
has no alpha hydrogens.
 To reduce the number of mixture of products in mixed aldol reactions, consider 2 factors:
1. Aldehydes are more reactive acceptor electrophiles than ketones, and formaldehyde is more
reactive than other aldehydes.
2. Aldehydes lacking alpha-hydrogens can only function as acceptor reactants, and this reduces
the number of possible products by half.
E.g.;
1.6.4. Reactions of crotonisation

 The b-hydroxy aldehydes and b-hydroxy ketones formed in aldol reactions are
easily dehydrated to yield a,b-unsaturated products, or conjugated enones (ene + one).
 In fact, it’s this loss of water that gives the aldol condensation its name, because water
condenses out of the reaction and the reaction is referred as crotonisation.
 Most alcohols are resistant to dehydration by dilute acid or base because hydroxide ion
is a poor leaving group, but b-hydroxy carbonyl compounds dehydrate easily because of
the carbonyl group.
 The reaction can be catalyzed by both acid and base
1.6.4. Reactions of crotonisation
Example of crotonisation reaction

2. Addition reactions with elimination of water or condensation reactions

2.1. Addition of Alcohols (Formation of Acetals)
 Mixed Aldehydes and ketones react with alcohol by heating in presence of acidic
or basic catalyst to yield hemiacetals/hemiketals then acetals/ketals.
 In presence of anhydrous HCl, aldehydes react more easily than ketones.
O OR
H
C + 2 ROH C + H2O
OR
an acetal
 Acetal formation is similar to the hydration reaction outlined in the previous slide.
 Like water, alcohols are weak nucleophiles that add to aldehydes and ketones only
slowly under neutral conditions.

 Aldehydes/ketones react with alcohol in presence of acidic or basic catalyst to yield
hemiacetals/hemiketal, then acetals/ketals with excess of alcohol.
H
H
Mechanism O
C
O
C
OH
C
-H
OH
C
O O
O H R R
H R a hemiacetal
H R
H2O H R O
O OH2
-H2O
C C C C
E.g.: OCH2CH3
O O O O
R R R R CH3CHOH 2 CH3CH2OH H3C C H
an oxonium ion H2O
Ethanal Ethanol OCH2CH3
Acetal
OR OCH2CH3
C + H3O CH3COCH3 2 CH3CH2OH H3C C CH3
H2O
OR Ethanone Ethanol OCH2CH3
acetal Ketal

 In molecules which have both OH and C=O groups on different carbon atoms, an
intramolecular addition reaction can occur, producing a cyclic hemiacetal or
hemiketal. These kinds of reactions are very important in carbohydrate chemistry.
E.g
2.1. Addition of Amine containing compounds

 Ammonia and primary amines, R′NH2, add to aldehydes and ketones to yield imines
also know as Schiff base, R2C=NR’. While secondary amines leads to enamine (ene +
amine) O
C
C
H
RNH2 R2NH
(prim. amine) (sec. amine)
R R R
N N
C + H2O C + H2O
C C
H
an imine an enamine
(ene + amine)

Mechanism of imine formation:
O O OH OH2
H
C C C C
R N H R N R N
RNH2 H H H
C C
B = RNH2 or H2O N + BH N
R R H
B
 A high concentration of acid in first step would also result in protonation of the basic
amine nitrogen atom and thereby reduce its effectiveness as a nucleophile.
 Hence imines form fastest under weakly acidic conditions.
Mechanism of enamine formation:
O OH OH2
H
C a H C H C H
C R2N C R2N C
R2NH
R R R R
N N
+ BH C H
C
C C
B

 With hydroxylamine NH2 - OH, we obtain the oximes,
R-C=O + H2N - OH R-CH=N-OH
-H2O aldoxime
H
CH3 CH3
C=O + H2N - OH C=N-OH
- H2O
CH3 CH3 ketoxime

 With Hydrazine (NH2 - NH2) to form "hydrazones" which can be further converted to the
corresponding alkane by reaction with base and heat.
 These two steps can be combined into one reaction called the Wolff-Kishner Reduction
which represents a general method for converting aldehydes and ketones into alkanes.

 With phenylhydrazine (C6H5 - NH-NH2) to form phenylhydrazone
+ H2O
 With Semicarbazide (NH2 - CO-NH-NH2) to form semicabazone
E.g.:

 With 2,4-Dinitrophenylhydrazine
 This reaction can be used to qualitatively detect the carbonyl group. This is
known as 2,4-DNP test or Brady’s test.
 If the carbonyl compound is aromatic, then the precipitate will be red; if
aliphatic, the precipitate will have a more yellow color.
 The reaction between 2,4-dinitrophenylhydrazine and a generic ketone to form
2,4-dinitrophenylhydrazone is shown below:
RR'C=O + C6H3(NO2)2NHNH2 → C6H3(NO2)2NHN=CRR' + H2O

 With 2,4-Dinitrophenylhydrazine
3. Substitution reaction
3.1. Alpha Halogenation of Aldehydes and Ketones
 Aldehydes and ketones are halogenated at their positions by reaction with
Cl2, Br2, or I2 in acidic solution.

 Bromine in acetic acid solvent is most often used.
 The reaction is a typical α-substitution process that proceeds through an enol

intermediate.

 Aldehydes Iodoform (triiodomethane) test is used to identify the presence of a
CH3CO- group in aldehydes and ketones.

(Iodoform, CHI3).
 Using iodine and sodium hydroxide solution or potassium iodide and sodium chlorate
(I) solutions with similar results.
 If no precipitate is formed in the cold, it may be necessary to warm the mixture very gently

 Iodoform (triiodomethane) test is also used to identify the presence of a CH3CH(OH)-
group in alcohols.
(Iodoform, CHI3).
 If no precipitate is formed in the cold, it may be necessary to warm the mixture very gently

 PCl5 provides geminal dichlorinated derivatives by elimination of oxygen:
CH3 - C=O
+ PCl5 POCl3 +CH3 - CHCl2
H
CH3 - CO-CH3 +PCl5 POCl3 +CH3 - CCl2 - CH3

4. Reduction of the carbonyl group

 Aldehydes and ketones are reduced into primary and secondary alcohols
respectively.
 This reaction can occur with Hydrogen in presence of catalysts like Pt, Pd, Ni,
copper chromite or with nascent H from LiAlH4 or NaBH4.
RCHO + H2 → RCH2OH
RCOR’ + H2 → RCHOHR’
 Aldehydes and ketones are reduced into hydrocarbons
 By Clemmensen reduction: uses amalgamated Zn/Hg and HCl
RCHO + Zn/Hg + HCl → RCH3+ H2O + ZnCl2 + HgCl2

RCOR + Zn/Hg + HCl → RCH2R’ + H2O + ZnCl2 + HgCl2
4. Reduction of the carbonyl group

 Aldehydes and ketones are reduced into hydrocarbons
 By Wolff-Kishner reduction: uses hydrazine (N2H4) and sodium ethoxide
RCHO + N2H4, then C2H5ONa → RCH3 + H2O + N2

RCOR + N2H4, then C2H5ONa → RCH2R’ + H2O + N2
Aldehydes and ketones: Preparation
1. Oxidation of alcohols (see alcohols section)

PCC
R CH2OH R CHO
CH2Cl2
prim. alcohol aldehyde
PCC: Pyridinium chlorochromate
OH O
[O]
R CH R' R C R
sec. alcohol ketone
2. Catalytic hydrogenation
o
 In presence of reduced Cu or Ag at 300 C
 Aldehydes are obtained from primary alcohols
RCH2OH → RCHO + H2
 Ketones are obtained from secondary alcohols
RCHOHR’ → RCOR’ + H2
3. Oxidative Cleavage of Alkenes (see alkene section)

R R' O O R R'
O3 R R' Zn
C C C C C O + O C
O HOAc
H R'' H R'' H R''
ozonide aldehyde ketone
4. Hydrolysis of the geminal dihalogenated derivatives of alkanes

 By heating at 150°C in the presence of Pb hydroxide or CaCO3
Cl H-OH OH O
R-CH + R-CH R-C
Cl H-OH -2HCl OH - H2Ò H
Unstable Aldehyde hydrate

4. Hydrolysis of the geminal dihalogenated derivatives of alkanes

 By heating at 150°C in the presence of Pb hydroxide or CaCO3
R – C - R
Cl Cl R-C- R R- C- R
H - OH -2HCl - H2O
OH OH O
+
5. Hydration of alkynes (see alkynes section)
 Acetylene and alkynes in presence of mercuric sulfate and sulfuric acid yield
aldehydes and ketones.
4. Pyrolysis of acids (or their salts)

 The thermal decomposition of calcium salts of carboxylic acids yield aldehydes and
ketones.
RCOOCaOOCR’ → RCOR’ + CaCO3
5. Preparation by hydroformylation or oxosynthesis

 The hydroformylation produces an aldehyde or a mixture of aldehydes if the
alkene is or not symmetrical in the conditions of 120 to 200°C, pressure of 200atm,
presence of catalyst such as CO2(CO)8 for example.
4. Friedel–Crafts acylation of an aromatic ring (see aromatic compound section)

O
O C
CH3
AlCl3
CH3C
Cl Heat
Aldehydes and ketones: Application
Aldehydes
 Formaldehyde is a gas. With 40% solution in water, it forms Formalin which is used
in preserving biological specimens.
 Formaldehyde is used in embalming, tanning, preparing glues and polymeric
products, as germicides, insecticides, and fungicides for plants. It is also used in
drug testing and photography.
 When reacted with phenol, formaldehyde forms Bakelite, which is used in plastics,
coatings, and adhesives.
 Acetaldehyde is largely used for the production of acetic acid and pyridine
derivatives.
 Benzaldehyde is used in perfumes, cosmetic products, and dyes. It is added to
provide almond flavor to food products and also used as a bee repellent.
Aldehydes and ketones: Application
Ketones
 The most common ketone is acetone which is an excellent solvent for a number of
plastics and synthetic fibers.
 In the household, acetone is used as a nail paint remover and paint thinner.
 In medicine, it is used in chemical peeling and for acne treatments.
 Methyl ethyl ketone (MEK), chemically butanone, is a common solvent. It is used in
the production of textiles, varnishes, plastics, paint remover, paraffin wax, etc.
 MEK is also used as a welding agent for plastics due to its dissolving properties.
 Cyclohexanone is another important ketone which is primarily used in the
production of nylon.
Exercises
1. The following compounds (CH3CH2CH2CH3, CH3OCH2CH3, CH3CH2CH2OH, CH3COOH,

CH3CH2CHO, (CH3)2C=CH2) have almost the same molecular mass. However, they have
different boiling points and different water solubilities.
a) Arrange them according to their increasing boiling points and explain why.
b) Arrange them according to their increasing water solubility and explain why.
2. Write the formula and/or give a name to the following compounds :
a) ditertiobutyl ketone
b) CH3-CH2- (CH)2-CO-CH3
c) 1-Cyclobutylpropanone
d) (CH3)2-C=CH-CHO
e) 2-ethylhex-3-en-5-ynal
f) cyclopentylethanal
Exercises
3. Transform
a) pentan-3-one into 3-chloropentane b) pentan-3-one into propanoic acid
c)1-butyne into hex-3-yn-2-one d) CH3C(CH3)CHCH3 into CH3COOH
e) CH3CH2CH2CH3 into CH3CH2COCH3
4. Write the balanced equations, naming all organic compounds, for the reaction of
phenylacetaldehyde with:
(a) Tollens’ reagent (b)CrO3/Sulfuric acid
(c)Cold dilute KMnO4 (d)LiAlH4
(e)NaBH4 (f)C6H5MgBr, then water
(g)Phenylhydrazine
(h)HC≡CLi, thenH2O (i) Cyanide ion, H+
(j)Ethylamine (k)Ethanol
(l) Hydrazine, KOH, Heat
Exercises
3. Transform
a) pentan-3-one into 3-chloropentane b) pentan-3-one into propanoic acid
c)1-butyne into hex-3-yn-2-one d) CH3C(CH3)CHCH3 into CH3COOH
e) CH3CH2CH2CH3 into CH3CH2COCH3
4. Write the balanced equations, naming all organic compounds, for the reaction of
phenylacetaldehyde with:
(a) Tollens’ reagent (b)CrO3/Sulfuric acid
(c)Cold dilute KMnO4 (d)LiAlH4
(e)NaBH4 (f)C6H5MgBr, then water
(g)Phenylhydrazine
(h)HC≡CLi, thenH2O (i) Cyanide ion, H+
(j)Ethylamine (k)Ethanol
(l) Hydrazine, KOH, Heat
Exercises
5. Give the structural formula of :

(a) Acetone (b) Benzaldehyde
(c) Isobutyl methyl ketone (d) Acetophenone
(e) 4-methylpental (f) Phenylacetaldehyde
(g) Benzophenone (h) 3-methyl-2pentanone
(i) 3-hydroxypentanal
6. There are two −NH2 groups in semicarbazide. However, only one is involved in the
formation of semicarbazones. Explain why.
Answer: The lone pair on NH2 group directly attached to the carbonyl carbon is
involved in resonance. As a result, electron density of this NH2 group decreases;
therefore this NH2 group does not act as a nucleophile. The lone pair of other
NH2 group, which is attached to NH, is not involved in resonance; hence this -
NH group acts as a nucleophile.

Aldehyde and Ketones F

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Aldehydes and ketones : Introduction

 In nature, many substances found in living organisms are aldehydes or ketones.

number of metabolic reactions.

Electronic Structure of the Carbonyl

 The normal aldehyde in Cn will be a functional isomer of normal ketones in Cn

H H H3C H H3C CH3 H3C C4H9

 Very simple ketones do not require a locator number.

4-formyl-2-oxocyclohexanecarboxylic acid 4-formylcyclohexanecarboxylic acid

Different behavior: oxidation

but their controlled oxidation leads to different products.

ketones are classified in separated families.

aldehydes, but not ketones:

RCOR + O2→ no reaction

Different behavior: oxidation

 Reduction of Fehling's solution (solution of CuSO4 + double tartrate of Na and K)

Different behavior: oxidation

Different behavior: oxidation

Different behavior: Iodoform reaction

(previously known as iodoform) - CHI3.

Different behavior: Iodoform reaction

Summary of the reactions during

Tertiary alcohols can not undergo such type of

1. Nucleophilic addition reaction

 Some negatively charged

1.1. Addition of hydride reagents: reduction

1.2. Addition of Grignard Reagents

1.2. Addition of Grignard Reagents

 Addition to aldehydes gives secondary alcohols

 Addition to ketones gives tertiary alcohols

1.3. Addition of water (Hydration)

1.3. Addition of water (Hydration)

1.4. Reaction with monosodic sulphite solution

1.5. Reaction with hydrocyanic acid (HCN)

1.5. Addition of Acetylides

1.6. Condensations of Aldehydes and Ketones: The Aldol Reaction

 Aldehydes can react on themselves (aldolisation)

 Ketones react on themselves (ketolisation)

1.6. Condensations of Aldehydes and Ketones: The Aldol Reaction

1.6. Condensations of Aldehydes and Ketones: The Aldol Reaction

to destabilise the formed anions making ketone less reactive.

1.6.3. Crossed aldol condensation

1.6.3. Crossed aldol condensation

1.6.4. Reactions of crotonisation

1.6.4. Reactions of crotonisation

Example of crotonisation reaction

2. Addition reactions with elimination of water or condensation reactions

2.1. Addition of Alcohols (Formation of Acetals)

2.1. Addition of Alcohols (Formation of Acetals)

2.1. Addition of Amine containing compounds

2.1. Addition of Amine containing compounds

2.1. Addition of Amine containing compounds

2.1. Addition of Amine containing compounds

2.1. Addition of Amine containing compounds

 With Semicarbazide (NH2 - CO-NH-NH2) to form semicabazone

2.1. Addition of Amine containing compounds

2.1. Addition of Amine containing compounds

Cl2, Br2, or I2 in acidic solution.

 The reaction is a typical α-substitution process that proceeds through an enol

3.1. Alpha Halogenation of Aldehydes and Ketones

CH3CO- group in aldehydes and ketones.

3.1. Alpha Halogenation of Aldehydes and Ketones

3.1. Alpha Halogenation of Aldehydes and Ketones