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Chapter out lines Definition & General Structure Aldehydes.
Common Names for Aldehydes.
IUPAC Nomenclature of Aldehydes.
Physical Properties of Aldehydes and Ketones.
Preparation of Aldehydes and Ketones.
Definition & General Structure Ketones.
Common and IUPAC Naming of Ketones.
Reactions of Aldehydes and Ketones.
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
1) Aldehydes
The aldehyde group is always at the end of a chain, so it will
always take number 1.
General formula: RCHO or RCH=O
Aldehydes and ketones are simple compounds which contain a
carbonyl group - a carbon-oxygen double bond.
What are aldehydes and ketones?
In aldehydes, the carbonyl group has a hydrogen atom attached
to it together with either
- a second hydrogen atom
- or, more commonly, a hydrocarbon group which might be an alkyl
group or one containing a benzene ring.
C
O
HR
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Common names for aldehydes are derived from the common names
of carboxylic acids. They often reflect the Latin or Greek term for
the original source of the acid or the aldehyde.
Common Names for Aldehydes A
cid
Ald
ehyd
e
Propionic acid Butyric acid Formic acid Acetic acid
Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Valeric acid
Valeraldehyde
• Aromatic aldehydes are usually designated as derivatives of the
simplest aromatic aldehyde, Benzaldehyde.
H O
O
p-Methoxybenzaldehyde
Anisic aldehyde m-Nitrobenzaldehyde Salicylaldehyde (o-hydroxybenzaldehyde)
Examples:
Benzaldehyde
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
• Name the substituents attached to the chain in the usual way.
IUPAC Nomenclature of Aldehydes
• Select the longest carbon chain containing the carbonyl carbon.
• The -e ending of the parent alkane name is replaced by
the suffix -al.
• The carbonyl carbon is always numbered “1.” (It is not necessary to
include the number in the name.)
• The CHO group is assigned the number “1” position and takes
precedence over other functional groups that may the present such as
–OH, C=C .
• If the presence of another functional group demands the use
of a suffix, the aldehyde group is named with the prefix formyl-.
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
IUPAC Naming
Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde
Methanal Ethanal Propanal Butanal
Common:
IUPAC:
Examples
2-pentenal
O
H
CH3CH2CHC
H
OCH3
2-Methyl butanal
2-chloropropanal
O
Cl
3-hydroxypropanal
OHO
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
General formula: RCOR’ (R and R’=alkyl or aryl)
Common name: listing the alkyl substitutents attached to the
carbonyl group, followed by the word ketone.
IUPAC system: relpace the ending –ane by the suffix –one. The
chain is numbered in such a way as give the lowest number to the
C=O group.
If another group has priority, then the ketone group is called
"oxo“.
2) Ketones
C
O
RR
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
IUPAC:
Common:
acetone acetophenone Benzophenone
Diphenylketone Dimethylketone Methylphenylketone
Propanone diphenylmethanone 1-phenylethanone
1-Cyclopentyl propanone
Methyl isopropylketone
CH3C CH
O
CH3
CH3
3-Methylbutan-2-one
Ethylcyclopentylketone
Cyclobutanone
CH3CH2 C
OExamples:
Common & IUPAC Naming
O
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Physical Properties of Aldehydes and Ketones A. Boiling Points
CO
C O
CO
C O
CO
C O
CO
C O
Because of polarity of carbonyl groups, aldehydes and ketones are polar
compounds.
As a result, the boiling points of aldehydes and ketones are higher than those of
nonpolar alkanes, but lower than those of alcohols.
Dipole-dipole attractions, although important, are not as strong as intractions due
to hydrogen bonding.
Dipole-dipole interaction amang carbonyl compounds
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
B. Solubility in water The lower aldehydes and ketones are soluble in water because they form
hydrogen bonds with water.
C
O
HR
OH H
C
O
R'R
OH H
Intermolecular hydrogen bonding
between water and aldehydes
Intermolecular hydrogen bonding
between water and ketones.
Aldehydes and ketones with less than six carbons are essentialy
insoluble in water.
The higher aldehydes and ketones are soluble in organic solvents such as;
benzene, ether, and carbontetrachlorid.
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Preparation of Aldehydes and Ketones
The major methods for preparing aldehydes an ketones are:
2. Ozonolysis of alkenes.
4.Friedel-Crafts acylation
1. Oxidation of alcohols
3.Hydration of alkynes
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
1. Oxidation of alcohols
The oxidation of primary alcohols, using mild oxidizing agents yields
aldehydes. [O] represents the oxidizing agent used.
When strong oxidizing agents are used, the aldehydes are very easily
oxidized to further carboxylic acids.
[O] = CrO3/ pyridine or Cu/ heat
1° alcohol An Aldehyde
Mild oxidizing agent
CH3CH2OH[O]
CH3CH
O
[O] = H2Cr2O7 Strong oxidizing agents
1° alcohol
A carboxylic acid
CH3CH2OH[O]
CH3CH
O
CH3COH
O
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
No Reaction
For oxidizing a tertiary alcohol, Nothing happens.
3° alcohol
OH
CH3CCH3
CH3
[O]
This reaction also illustrates the importance of differentiating
between primary, secondary, and tertiary alcohols.
Secondary alcohols, are converted either into ketones on treatment
with both mild or strong oxidizing agent.
2°
alcohol A Ketone
CH3CHCH3
OH[O]
CH3CCH3
O
[O] = may be CrO3/ pyridine ; Cu/ heat or H2Cr2O7
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
2. Ozonolysis of alkenes
1) O3
2) Zn, H2OCH2CH2 C
O
HCH
O
1) O3
2) Zn, H2OO +
H
O
Examples
General equation
Results in aldehydes or ketones depending on structure of the alkene
used.
(1) O3
(2) Zn, H2OC C
R
HR
R R
RC O
H
RCO+
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
R C C R + H2OHgSO4/ H2SO4
Water adds to alkynes in the presence of dilute sulfuric acid and
murcuric sulfate catalyst. to yield an enol. However the initially formed
enol reacts further to produce a ketone.
Such isomers, differing only in the placement of a hydrogen atom, are
called tautomers.
Enol form Keto form
General equation
More stable Less stable
3.Hydration of alkynes: Addition of water
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Examples
H3C C
CH
+ H2OHgSO4/ H2SO4a)
Propyne
H3C C
CH2
OH H3C C
CH3
O
Acetone
C CH
+ H2OHgSO4/ H2SO4b)
1-Cyclohexyl acetylene
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
C CH
H
OH
C CH3
O
1-Cyclohexyl ethanadehyde 1-Cyclohexyl ethananone
4- Friedel-Crafts acylation
A general method for preparing ketones that contain an aromatic ring is
the Friedel-Crafts acylation reaction.
General equation
Examples
+ CH3CH2 C Cl
O
AlCl3 C CH2CH3 + HCl
O
Propionyl chloride
Propiophenone
Ethyl phenyl ketone
+ R C Cl
O
AlCl3 C R + HCl
O
The reaction involves treatment of an aromatic ring with an acylchloride,
, in the presence of AlCl3, which acts as a catalyst.
C
O
ClR
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Reactions of Aldehydes and Ketones Aldehydes and ketones undergo nucleophilic addition reaction
to the carbon-oxygen double bond. 1. Addition of metal hydrides: Formation of alcohols.
2. Addition of Grignard Reagents : Formation of alcohols.
3-Oxidations of aldehydes and ketones:
a.Oxidation under acidic conditions/ H+
b. Under alkaline conditions/ OH-
5. Addition of Hydrogen cyanide: Formation of cyanohydin. 6- Nucleophilic addition of Acetylide ions:
7- Nucleophilic Addition of Alcohols:
Formation of Hemiacetals and Acetals.
8- Addition of Ammonia and Ammonia Derivatives.
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
4. Tollen’s Test: Silver mirror test.
9- Aldol condensation reaction.
10 - Cannizzaro reaction.
Catalytic hydrogenation reduces aldehydes to produce 1° alcohols & ketones
to produce 2° alcohols.
(conditions are very similar to those used to reduce alkene double bonds).
Lithium aluminum hydride; LiAlH4 is a very strong reducing agent that will
reduce many functional groups in addition to aldehydes and ketones.
Sodium borohydride; NaBH4 is a much weaker reducing agent that
basically will reduce only aldehydes and ketones to alcohols.
1. Addition of metal hydrides: Formation of alcohols.
Metal Hydrides; LiAlH4, NaBH4
H2/ Ni
Low Pressure
O
LiAlH4
H
OH
O OH
1)NaBH4
2)H2O
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Exercise: Choose the best reagent for the following reactions.
Although the same result may be achieved by catalytic hydrogenation, or
LiAlH4 , but NaBH4 has the advantage of selectively reducing of unsaturated
aldehydes and ketones into unsaturated alcohols.
H2/Ni
LiAlH4
NaBH4 / CH3OH OH
Propanol
O
Propanal
A] or
or
Conclusion
NaBH4 / CH3OH
H2/Ni LiAlH4 or C]
O
Cyclopent-2-enone
OH
Cyclopentanol
OH
3-Phenyl-prop-2-en-1-ol
B]
3-Phenyl-prop-2-en-1-al
O
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
2. Addition of Grignard Reagents : Formation of alcohols.
Grignard reagents are strong nucleophiles that they can serve as nucleophilic
addition to carbonyl group.
Treatment of an aldehyde or ketone with Grignard reagent followed by water
forms an alcohol with new C-C bond.
Grignard reagents react with formaldehyde to produce primary alcohols.
1. In case of formaldehyde:
CH3MgBr + C
O
HH
1) Dry ether
2) H3O+
CH3CH2OH
General equation
Example:
RMgBr + C
O
HH
1) Dry Ether
2) H3O+
RCH2OH
Formaldehyde Ethanol
1° Alcohol
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
2. In case of other aldehyde:
Grignard reagents react with aldehyde to produce secondary alcohols.
General equation
Examples:
2° Alcohol Aldehyde
RMgBr + C
O
R'H
1) Dry Ether
2) H3O+ C
OH
R'
HR
Acetaldehyde 2-Butanol
CH3CH2MgBr + C
O
H
CH3
1) Dry ether
2) H3O+C
H
OH
CH3 CH2CH3
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
General equation 3. In case of Ketones:
Examples:
Grignard reagents react with ketones to produce tertiary alcohols.
O
1) Dry ether
2) H3O+
CH3MgBr + OH
CH3
3° Alcohol ketones
cyclohexanone cyclohexyl methyl alcohol
RMgBr + C
O
R''R'
1) Dry Ether
2) H3O+ C
OH
R''
R'R
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
3-Oxidations of aldehydes and ketones
Aldehydes can be oxidized to carboxylic acid with both mild and strong
oxidizing agents.
Typical oxidizing agents for aldehydes include either potassium permanganate
(KMnO4) or potassium dichromate (K2Cr2O7) in acid solution.
C H
O
KMnO4 /H+
C OH
O
Benzaldehyde Benzoic acid
Peroxy acids, such as peroxybenzoic acid (C6H5CO3H) are used to
oxidize ketones to esters.
a.Oxidation under acidic conditions/ H+
CH3
O
CH3Cl
C
O
OOHC6H5O
O
CH3
cyclohexylmethylketone cyclohexylacetate
Oxygen insertion
occurs between
carbonyl carbon
and larger group.
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
The iodoform test
CH3C
O
CH3C
OH
HThe compounds containing or , give iodoform test.
CH3C
O
R +3I2 + 4NaOH CHI3 + CH3COO- Na+ + 3H2O + 3NaI
The General equation
The iodoform test is a test for the existence an acetyl group, or
a group that can be oxidized to an acetyl group which will give a positive
iodoform test.
+ve Iodoform(CHI3) result =
is a pale yellow substance.
These type of methylketones can be distinguished from other non-methyl
ketone by their reaction with iodine; I2 in a basic solution; NaOH to yield
iodoform (CHI3) as a yellow colored precipitate.
b. Under alkaline conditions/ OH-
-ve
Iodoform
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Examples:
3I2NaOH+ CHI3 CH3C
O
H + C
O
ONaHa)
acetaldehyde
NaOHCHI3 + C
O
ONa
3I2+ CH3C
O
b)
acetophenone
3I2NaOH+ CHI3 CH3C
O
CH3 + C
O
ONaCH3
c)
acetone
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Exercise:
Which of the following compounds will give a positive result +ve toward
iodofrom test:
HCHO
Compounds
CH3CHO
CH3COCH3
O
Results Why ??
-ve, No yellow ppt
+ve, gives yellow ppt
Has no CH3CO
Has no CH3CO
Has CH3CO
Has CH3CO
-ve, No yellow ppt
+ve, gives yellow ppt
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Reaction Mechanism of haloform Chapter 6; Aldehydess& Ketoness
R CH3
Oexcess X2
NaOH R ONa
O+ CHX3
Overall reaction
This reaction happen when you have terminal ketone.
Haloform could be chloroform, bromoform and Iodoform.
Note that
α-hydrogens are more acidic due to the inductive effect
near by the halogen. As there are excess of halogen; the
halogen will replace all the methyl hydrogens.
Chem 340- 2nd semester 1437-1438
O
H
Br
OH
NaOH
O
H
Br
OHO
H
BrBrNaOH
O
Br
Br
Br Br
Br Br
OBr
BrBr
OH
O
Br
BrOH Br
O
O
H C
Br
Br
Br
+
O
O
C
Br
Br
Br
+ HNa
O
H
H
HNaOH
O
H
H Br Br
Reaction Mechanism of haloform Chapter 6; Aldehydess& Ketoness
Reaction Mechanism
Chem 340- 2nd semester 1437-1438
OH from sodium hydroxide will attract the –hydrogen add create
the enolate intermediat.
Chapter 6; Aldehydess& Ketoness
The enolate collapse back dawn and the 1st halogen adds to the
molecule.
The reaction happens twice till the three halogens are added.
OBr
BrBr
The presence of 3 halogen atoms on the carbon
makes it δ+ and difficult to act as leaving group. C δ+
In the presence of more molecules of NaOH in the solution the OH
will attack the C δ+ forming tetrahydral unstable intermediat.
The –ve oxygen will collapse back dawn to reform the double bond
and kick out the :CBr3 instead of OH.
Mechanism Description
The :CBr3 anion abstracts a proton from either the solvent or
the carboxylic acid formed in the previous step, and forms the
haloform and carboxylate ion.
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
4. Tollen’s Test: Silver mirror test. Tollen’s reagent (Ag(NH3)2
+ / OH- is a weak oxidant
Aldehydes are readily oxidized to carboxylic acids by Tollen’s
reagent to produce a silver mirror on the inside of a clean test tube.
Ketones are not oxidized by Tollen’s reagent.
https://www.youtube.com/watch?v=7I-y3I3VzM8
video link
R H
O
+ 2 Ag(NH3)2OH 2 Ag +R O NH4
O
+ H2O + 3 NH3
H
O
AgO2
NH3/ H2O
OH
O
+ Ag
General Equation
Example
Ammonium salt
of carboxylic acid Metalic silver is deposted
in a thin mirror coating
Chem 340- 2nd semester 1437-1438
Experiment Observation Conclusion
Tollen’s test The colourless solution
produces a grey precipitate of
silver, or a silver mirror on the
test tube.
Aldehyde
Tollen’s test
No change in the colourless
solution
Ketone
Chapter 6; Aldehydess& Ketoness
5. Addition of Hydrogen cyanide: Formation of cyanohydin.
The nucleophilic addition of hydrogen cyanide (HCN) to aldehydes or
ketones affords Cyanohydrin.
(Cyanohydrin: A molecule containing an -OH group and a -CN group
bonded to the same carbon.
General equation
aldehydes or ketones Cyanohydrin
R H or R'
O
HCN, -CNR H or R'
OH
CN
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Examples:
Benzaldehyde Benzaldehyde cyanohydrin
a) C HHCN, -CN
O
C H
OH
CN
b)
O
HCN, -CN
HO CN
Cyclohexanone Cyclohexanone cyanohydrin
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Cyanohydrins are very useful because the CN group can be converted to
other functional groups.
For example: reduction with LiAlH4 followed by water reduces the
CN group to a primary amine. Thus an aminoalcohol product is formed.
Also, hydrolysis of the CN group with acidic water gives a hydroxy
carboxylic acid product. This affords us with an important method of
synthesizing α-hydroxy-carboxylic acids.
C H
OH
CN
1) LiAlH4
2) H2O
H3O+
heat
C H
OH
CH2NH2
C H
OH
COOH
2-Amino-1phenyl-ethanol
2-hydroxy-2-phenylacetic acid
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
6- Nucleophilic addition of Acetylide ions:
Acetylide ions are another example of organometallic reagents; it can be
thought of as “organo sodium reagents”. They are good nucleophiles.
The addition of acetylides ions to aldehydes and ketones yields an
alkynol.
(An alkynol: is an alcohol on carbon adjacent to triple bond.)
General equation
Acetylide ions can also used to attack carbonyl group, The net effect of
the reaction of organometallic reagents with an aldehyde or ketone is the
addition of the components R and H across the C=O double bond.
.
An alkynol
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Examples:
b)
CH3 C C Na + C O
H
H
H3O+
CH3 C C C OH
H
H
a)
An alkynol, 1° alcohol Formaldehye
CH3 C C Na + C O
CH3
H
H3O+
CH3 C C C OH
H
CH3
Acetaldehye An alkynol, 2° alcohol
c) CH3 C C Na +
O
H3O+
OHCH3 C C
Cyclohexanone An alkynol, 3° alcohol
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
7- Nucleophilic Addition of Alcohols:
Formation of Hemiacetals and Acetals A.1 Hemiactals The addition of one mole of an alcohol to the carbonyl group of an aldehyde
yields a hemiacetal. (hemi, Greek, half).
An Aldehyde A hemiacetal An alcohol
R C
O
H + R' OH H+
CR OR'
OH
H
General equation
B.1 Acetals When hemiacetals are treated with an addition mole of an alcohol in
the presence of anhydous acid, they are converted to acetals .
CR OR'
OH
H
CR OR'
OR"
H
H+ (anhyd.)R" OH+General equation
A hemiacetal An alcohol Acetals Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Example
The addition of one mole of an alcohol to the carbonyl group of a ketone
yields a hemiketal.
A.2 Hemiketals
Ethanal Methanol 1-Methoxyethanol
(A hemiacetal)
+ CH3OHCH3OH
CH3 C
O
H CCH3
OH
H
OCH3H+
H+(anhyd.)
CCH3
OCH3
H
OCH3
1,1-Dimethoxyethanol
(An acetal)
+ R' OH H+
CR OR'
OH
R"
R C
O
R"
A hemiketal A Ketone
General equation
An alcohol
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
B.2 Ketals
The reaction of hemiketal with alcohols to form ketals is seldom works.
CR OR'
OH
R"
H+ (anhyd.)R'" OH+ CR OR'
OR'"
R"
a hemiketal An alcohol ketals
The Conclusion
The hemiacetal and the hemi ketal are compounds that have an
alkoxy group (OR) & hydroxy group (OH) that are attached to
the same carbone.
The acetals & the ketals are compounds that have two
alkoxy groups (OR) on the same carbon. Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Nitrogen nucleophiles such as ammonia and its derivatives H2N - Z add
to carbonyl group of aldehydes and ketones.
8- Addition of Ammonia and Ammonia Derivatives
The reaction is reversible and catalyszed by acid.
a) The Reaction with Hydroxylamine
Aldehydes and ketones react with hydroxylamine to form oximes.
C O
R
R' (H)
+ H2 NOH H+
C NOH + H2O
R
R' (H)
Hydroxylamine Oxime
The net result is replacement
of the >C = O group with >C = N - Z group
Aldehyde
or Ketone Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Aldehydes and ketones react with hydrazine to form hydrazones.
b) The Reaction with Hydrazine
With aldehydes
With ketones
H++ H2 NNH2
C O
H
CH3
+ H2OC NNH2
H
CH3
Acetaldehyde Hydrazine Acetaldehyde
hydrazone
H++ H2 NNH2 + H2O
C O
CH3
CH3
C NNH2
CH3
CH3
Acetone Hydrazine Actone
hydrazone Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
c) The Reaction with ammonia NH3
Like ammonia derivatives ammonia also reacts with aldehydes (except
formaldehyde) and ketones to form the products called imines.
+ NH3 C
H
CH3 OH
NH2
C O
H
CH3
C NH
H
CH3-H2O
Acetaldehyde Ammonia Acetaldehyde
ammonia
Acetaldimine
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Summary
Structure and names of nitrogen nucleophiles that react with
carbonyl compounds:
+
Nitrogen Nucleophile Nitrogen derivative
of carbonyl compounds
NH3Ammonia Imine
C N NH2NH2NH2Hydrazine Hydrazone
NH2OHHydroxylamine Oxime
C HN
C OHN
C O
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
http://web.chem.ucla.edu/~harding/notes/notes_14D_enolates.pdf
Chem 340- 2nd semester 1437-1438
9- Aldol condensation
Chapter 6; Aldehydess& Ketoness
Aldol means aldehyde and alcohol groups on the same molecule.
May occur between two aldehydes (aldols) or two ketones
(ketols) in the presence of catalytic base.
Reaction ONLY possible between two components having
α-hydrogen.
- With Aldehydes, the equilbrium favors product
- With ketones, the equilbrium favors the sarting materials.
The reactions are reversible
HR
O
HR
O
+Dilute Alkali
HR
O
R
OH
O
+Dil. Ba(OH)2
O OHO
Chem 340- 2nd semester 1437-1438
NaOH Na + OH
Chapter 6; Aldehydess& Ketoness
Aldol condensation Reaction Mechanism Step 1. Ionization of base
Step 2. Formation of acceptor electrophile
HR
O+ Na
HRONa
Step 3. The base removes an acidic alpha hydrogen from one aldehyde
molecule; yielding a resonance stabilized enolate ion (nucleophile).
HR
O
+OH
HR
O
Step 4. The enolate ion attacks a second aldehyde molecule in
nucleophilic addtion reaction to give a tetrahydral alkoxide ion
intermediate.
HRONa
HR
O+
HR
O
R
ONa
HR
O
R
OH
NaOH
H2O
Step 5. Protonation of the alkoxide ion intermediate yields neutral aldol
product and regenerate the base catalyst.
Chem 340- 2nd semester 1437-1438
The aldol products formed often undergoes dehydration to form
conjugated systems. This reaction is a type of nucleophilic
addition
In some cases, the adducts obtained from the Aldol Addition can
easily be converted (in situ) to α,β-unsaturated carbonyl
compounds, either thermally or under acidic or basic catalysis
Note that:
Chapter 6; Aldehydess& Ketoness
Chem 340- 2nd semester 1437-1438
O ONaH
H +
ONaO
NaOH
H2OOHO
Ketol condensation Reaction Mechanism
NaOH Na + OH
Step 1. Ionization of base
Step 2. Formation of acceptor electrophile
O
+OH
O
Step 3. Formation of donar enolate nucleophile
O+ Na
ONa
Chapter 6; Aldehydess& Ketoness
Step 4. The enolate ion attacks a second ketone molecule giving a
tetrahydral alkoxide ion intermediate.
Step 5. Protonation of the alkoxide ion intermediate yields neutral
ketol product and regenerate the base catalyst.
Chem 340- 2nd semester 1437-1438
Dehydration is favorable because the product is stabilized
by conjugation of the alkene with the carbonyl group.
In similar manner dehydrates takes place in ketols to the
α,β -unsaturated compound.
The aldol product cannot be isolated.
Chapter 6; Aldehydess& Ketoness
Note That:
Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
10- Cannizzaro Reaction
Upon treatment with strong bases (e.g. in aqueous NaOH)
and heating, non-enolizable aldehydes undergo redox
disproportionation to give corresponding alcohols and
carboxylic acids in 1:1 ratio.
General equation
Examples
2
2
Chapter 6; Aldehydess& Ketoness
Reaction Mechanism of Cannizzaro Reaction
Chem 340- 2nd semester 1437-1438
Chem 340- 2nd semester 1437-1438
Home Work Chapter 6; Aldehydess& Ketoness
Q.1 Each of the following compounds was prepared by an aldol
condensation followed by dehydration. In each case, select the
structure of the starting material from the list of choices in the box
below.
Chem 340- 2nd semester 1437-1438
Q.2. Give the IUPAC name for the following.
Chapter 6; Aldehydess& Ketoness
O
Br
O
…………………………………… ……………………………………
A) B)
Acetone Propan-1-ol Propanal n-Butane Methoxyethane
(i) (ii) (iii) (iv) (v)
Q.3 Arrange these compounds in order of increasing
Boiling point.