2023 Aldehydes - Ketones Handout 2023

Aldehydes & Ketones
Chapter 6
Dr. Seham ALTERARY

Chem 340- 2nd semester 1437-1438
Chapter 6; Aldehydess& Ketoness
Chapter out lines

 Definition & General Structure Aldehydes.
Common Names for Aldehydes.
 IUPAC Nomenclature of Aldehydes.
 Definition & General Structure Ketones.
Common and IUPAC Naming of Ketones.
 Physical Properties of Aldehydes and Ketones.
 Preparation of Aldehydes and Ketones.

 Reactions of Aldehydes and Ketones.

What are aldehydes and ketones?

Aldehydes and ketones are simple compounds which contain a
carbonyl group - a carbon-oxygen double bond.
O
1) Aldehydes C
R H
General formula: RCHO or RCH=O
The aldehyde group is always at the end of a chain, so it will
always take number 1.
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 aChem
benzene ring.
340- 2nd semester 1437-1438
Common Names for Aldehydes

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.
Acid
Formic acid Acetic acid Propionic acid Butyric acid Valeric acid
Aldehyde
Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde Valeraldehyde

• Aromatic aldehydes are usually designated as derivatives of the
simplest aromatic aldehyde, Benzaldehyde.
Examples:
Benzaldehyde
H O
O
(o-hydroxybenzaldehyde) p-Methoxybenzaldehyde
m-Nitrobenzaldehyde Salicylaldehyde
Chem 340- 2nd semester 1437-1438 Anisic aldehyde
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-.
• Name the substituents attached to the chain in the usual way.

IUPAC Naming
Common: Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde

IUPAC: Methanal Ethanal Propanal Butanal
Examples Cl H
O
O
2-chloropropanal 2-pentenal
CH3 O
CH3CH2CHC HO O
H
2-Methyl butanal 3-hydroxypropanal
2) Ketones
O
General formula: RCOR’ (R and R’=alkyl or aryl) C
R R
 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“.
Common & IUPAC Naming
Common: Dimethylketone Diphenylketone Methylphenylketone

acetone Benzophenone acetophenone
IUPAC: Propanone diphenylmethanone 1-phenylethanone

Examples: O
O
O CH3 C CH CH3
CH3CH2 C CH3
Methyl isopropylketone
Ethylcyclopentylketone
Cyclobutanone 1-Cyclopentyl propanone
3-Methylbutan-2-one
Physical Properties of Aldehydes and Ketones
A. Boiling Points
Because of polarity of carbonyl groups, aldehydes and ketones are polar
compounds.
Dipole-dipole attractions, although important, are not as strong as intractions due
to hydrogen bonding.
  O C
O C
 
C O C O
 
O C O C
 
C O C O
Dipole-dipole interaction amang carbonyl compounds

As a result, the boiling points of aldehydes and ketones are higher than those of
nonpolar alkanes, but lower than those of alcohols.
B. Solubility in water
The lower aldehydes and ketones are soluble in water because they form
hydrogen bonds with water.
 
 O   O 
H H H H
 O  O
 C  C
R H R R'
Intermolecular hydrogen bonding Intermolecular hydrogen bonding
between water and aldehydes 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.
Preparation of Aldehydes and Ketones

The major methods for preparing aldehydes an ketones are:
1. Oxidation of alcohols
2. Ozonolysis of alkenes.
3.Hydration of alkynes
4.Friedel-Crafts acylation

1. Oxidation of alcohols
The oxidation of primary alcohols, using mild oxidizing agents yields
aldehydes. [O] represents the oxidizing agent used.
O
1° alcohol [O]
CH3CH2OH CH3CH An Aldehyde
Mild oxidizing agent [O] = CrO3/ pyridine or Cu/ heat

When strong oxidizing agents are used, the aldehydes are very easily
oxidized to further carboxylic acids.
O O
[O]
1° alcohol CH3CH2OH CH3CH CH3COH
A carboxylic acid
Strong oxidizing agents [O] = H2Cr2O7
Secondary alcohols, are converted either into ketones on treatment

with both mild or strong oxidizing agent.
OH O
2° [O]
CH3CHCH3 CH3CCH3
A Ketone
alcohol
[O] = may be CrO3/ pyridine ; Cu/ heat or H2Cr2O7
 For oxidizing a tertiary alcohol, Nothing happens.
OH
[O] No Reaction
3° alcohol CH3CCH3
CH3
This reaction also illustrates the importance of differentiating
between primary, secondary, and tertiary alcohols.
2. Ozonolysis of alkenes
Results in aldehydes or ketones depending on structure of the alkene
used.
General equation
R R R R
(1) O3
C C C O + O C
R H (2) Zn, H2O R H
Examples
H
1) O3
2) Zn, H2O O + O
O O
1) O3
2) Zn, H2O H C CH2CH2 C H
3.Hydration of alkynes: Addition of water

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.
General equation
HgSO4/ H2SO4
R C C R + H2O
Enol form Keto form

Less stable More stable
Such isomers, differing only in the placement of a hydrogen atom, are

called tautomers. Chem 340- 2nd semester 1437-1438
Examples
HgSO4/ H2SO4
a) H3C C + H2O H3C C OH H3C C O
CH3
CH2
CH
Propyne Acetone
C CH
HgSO4/ H2SO4
b) + H2O
1-Cyclohexyl acetylene
OH O
C CH C CH3
H
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.
The reaction involves treatment of an aromatic ring with an acylchloride,
O , in the presence of AlCl3, which acts as a catalyst.
C
R Cl
General equation
O O
AlCl3
+ R C Cl C R + HCl
Examples O O
AlCl3
+ CH3CH2 C Cl C CH2CH3 + HCl
Propionyl chloride Ethyl phenyl ketone

Chem 340- 2nd semester 1437-1438 Propiophenone
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-
4. Tollen’s Test: Silver mirror test.
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.
9- Aldol condensation reaction.
10 - Cannizzaro reaction.
1. Addition of metal hydrides: Formation of alcohols.
Metal Hydrides; LiAlH4, NaBH4
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).
H2/ Ni
Low Pressure
Lithium aluminum hydride; LiAlH4 is a very strong reducing agent that will
reduce many functional groups in addition to aldehydes and ketones.
O OH
LiAlH4
H
Sodium borohydride; NaBH4 is a much weaker reducing agent that
basically will reduce only aldehydes and ketones to alcohols.
1)NaBH4
O 2)H2O OH
Conclusion
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.
Exercise: Choose the best reagent for the following reactions.
H2/Ni
or LiAlH4
A] or OH
O
NaBH4 / CH3OH
Propanal Propanol
NaBH4 / CH3OH OH
O
B]
3-Phenyl-prop-2-en-1-ol
3-Phenyl-prop-2-en-1-al
O OH
H2/Ni LiAlH4
C] or
Cyclopent-2-enone Cyclopentanol
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.
General equation 1. In case of formaldehyde:
O
1) Dry Ether
RMgBr + C RCH2OH
H H 2) H3O+
Grignard reagents react with formaldehyde to produce primary alcohols.

Example: O
1) Dry ether
CH3MgBr + C +
CH3CH2OH
2) H3O
H H 1° Alcohol
Formaldehyde Ethanol
2. In case of other aldehyde:
General equation
O OH
1) Dry Ether
RMgBr + C R C H
H R' 2) H3O+
R'
Grignard reagents react with aldehyde to produce secondary alcohols.
Examples:
O
OH
C
1) Dry ether
CH3CH2MgBr + CH3 CH3 C CH2CH3
2) H3O+
H H
Aldehyde 2° Alcohol
Acetaldehyde 2-Butanol
General equation 3. In case of Ketones:
O OH
1) Dry Ether
RMgBr + C + R C R'
R' R'' 2) H3O
R''
Grignard reagents react with ketones to produce tertiary alcohols.
Examples:
O
CH3
CH3MgBr +  1) Dry ether OH
2) H3O+
ketones 3° Alcohol
cyclohexanone cyclohexyl methyl alcohol
3-Oxidations of aldehydes and ketones
a.Oxidation under acidic conditions/ H+
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.
O O
C H KMnO4 /H+ C OH

Benzaldehyde Benzoic acid
Peroxy acids, such as peroxybenzoic acid (C6H5CO3H) are used to
oxidize ketones to esters.
O O
O CH3
CH3
C6H5 C OOH Oxygen insertion
CH3Cl
O occurs between
cyclohexylmethylketone cyclohexylacetate carbonyl carbon
Chem 340- 2nd semester 1437-1438 and larger group.
The iodoform test b. Under alkaline conditions/ OH-
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. O OH
The compounds containing CH3C or CH3CH , give iodoform test.
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.
The General equation
O
CH3C R +3I2 + 4NaOH CHI3 + CH3COO- Na+ + 3H2O + 3NaI
+ve Iodoform(CHI3) result =

-ve
is a pale yellow substance.
Iodoform
Examples:
O O
a) CH3C H + 3I2 NaOH CHI3 H C
+
ONa
acetaldehyde
O
O
b) CH3C + 3I2 NaOH
CHI3 + C
ONa
acetophenone
O O
c) CH3C CH3 + 3I2 NaOH CHI3 + CH3 C

ONa
acetone
Exercise:
Which of the following compounds will give a positive result +ve toward
iodofrom test:
Compounds Results Why ??
HCHO -ve, No yellow ppt Has no CH3CO
CH3CHO +ve, gives yellow ppt Has CH3CO
CH3COCH3 +ve, gives yellow ppt Has CH3CO
O
-ve, No yellow ppt Has no CH3CO

Reaction Mechanism of haloform
Overall reaction
O O
excess X2 + CHX3
R CH3 NaOH R ONa
 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.

Reaction Mechanism of haloform
Reaction Mechanism
O
O
H H
NaOH
H Br Br
H H
NaOH
OH
Br Br O
O O
OH H
H H
Br Br
NaOH Br Br
O Br
O O H + Br C
O O
Br Br Br OH Br Br
Br OH Br
Br Br
Br Br
O Br
O Na + Br C H
Br
Mechanism Description
 OH from sodium hydroxide will attract the –hydrogen add create
the enolate intermediat.
 The enolate collapse back dawn and the 1st halogen adds to the
molecule.
 The reaction happens twice till the three halogens are added.
 The presence of 3 halogen atoms on the carbon C δ+ O
makes it δ+ and difficult to act as leaving group. Br
Br
Br
 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.
 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.
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
General Equation
O O
+ 2 Ag(NH3)2OH 2 Ag + + H2O + 3 NH3
R H R O NH4
Metalic silver is deposted Ammonium salt
in a thin mirror coating of carboxylic acid
Example O O
H AgO2 OH + Ag
NH3/ H2O

Experiment Observation Conclusion

Tollen’s test The colourless solution Aldehyde
produces a grey precipitate of
silver, or a silver mirror on the
test tube.
Tollen’s test No change in the colourless Ketone

solution

5. Addition of Hydrogen cyanide: Formation of cyanohydin.

The nucleophilic addition of hydrogen cyanide (HCN) to aldehydes or
ketones affords Cyanohydrin.
General equation
O OH
HCN, -CN
R H or R' R H or R'
CN
aldehydes or ketones Cyanohydrin
(Cyanohydrin: A molecule containing an -OH group and a -CN group

bonded to the same carbon.
Examples:
O OH
-
HCN, CN
a) C H C H
CN
Benzaldehyde Benzaldehyde cyanohydrin
O
HO CN
HCN, -CN
b)
Cyclohexanone Cyclohexanone cyanohydrin

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.
OH
1) LiAlH4
C H
2) H2O
OH CH2NH2
C H 2-Amino-1phenyl-ethanol
OH
CN H3 O+
C H
heat
COOH
2-hydroxy-2-phenylacetic acid
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.
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.
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.
General equation
An alkynol
The addition of acetylides ions to aldehydes and ketones yields an
alkynol.
(An alkynol: is an alcohol on carbon adjacent to triple bond.)

Examples: H
H
a) CH3 C C H3O+
Na + C O CH3 C C C OH
H
H
Formaldehye An alkynol, 1° alcohol
CH3
CH3
H3O+
b) CH3 C C Na + C O CH3 C C C OH
H
H
Acetaldehye An alkynol, 2° alcohol
O
CH3 C C OH
c) CH3 C H3O+
C Na +
Cyclohexanone
An alkynol, 3° alcohol
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).
O OH
R C H + R' OH H+
General equation R C OR'
An Aldehyde An alcohol A hemiacetal

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 .
OH OR"
General equation R C OR' + R" OH H+ (anhyd.) R C OR'

H H
A hemiacetal An alcohol Acetals
Example
O OH OCH3
C H + CH3 OH H+ H+(anhyd.)
CH3 CH3 C OCH3 CH3 OCH3
C
CH3OH
H H
Ethanal Methanol 1-Methoxyethanol 1,1-Dimethoxyethanol

(A hemiacetal) (An acetal)
A.2 Hemiketals
The addition of one mole of an alcohol to the carbonyl group of a ketone
yields a hemiketal.
O OH
General equation R C R" + R' OH H+

R C OR'
R"
A Ketone An alcohol A hemiketal

B.2 Ketals
The reaction of hemiketal with alcohols to form ketals is seldom works.
OH OR'"
R C OR' + H+ (anhyd.)
R'" OH R C OR'
R" 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.
8- Addition of Ammonia and Ammonia Derivatives
Nitrogen nucleophiles such as ammonia and its derivatives H2N - Z add
to carbonyl group of aldehydes and ketones.
The reaction is reversible and catalyszed by acid.
The net result is replacement

of the >C = O group with >C = N - Z group
a) The Reaction with Hydroxylamine

Aldehydes and ketones react with hydroxylamine to form oximes.
R R
+
C O + H2 NOH H
C NOH + H2O
R' (H) R' (H)
Aldehyde Hydroxylamine Oxime
or Ketone
b) The Reaction with Hydrazine

Aldehydes and ketones react with hydrazine to form hydrazones.
With aldehydes
CH3 CH3
C O + H2 NNH2 H+ C NNH2 + H2O
H H
Acetaldehyde Hydrazine Acetaldehyde
hydrazone
With ketones
CH3 CH3
C O + H2 NNH2 H+ C NNH2 + H2O
CH3 CH3
Hydrazine Actone
Acetone
Chem 340- 2nd semester 1437-1438 hydrazone
c) The Reaction with ammonia NH3

Like ammonia derivatives ammonia also reacts with aldehydes (except
formaldehyde) and ketones to form the products called imines.
CH3 CH3 OH CH3

-H2O
C O + NH3 C C NH
H H NH2 H
Acetaldehyde Ammonia Acetaldehyde Acetaldimine
ammonia

Summary
Structure and names of nitrogen nucleophiles that react with
carbonyl compounds:
Nitrogen derivative
Nitrogen Nucleophile
of carbonyl compounds
Ammonia NH3 C N H Imine
C O+ Hydrazine NH2NH2 C N NH2 Hydrazone
Hydroxylamine NH2OH C N OH Oxime

http://web.chem.ucla.edu/~harding/notes/notes_14D_enolates.pdf
9- Aldol condensation
O O OH O
R Dilute Alkali R
H + R H H
R
O O HO O
Dil. Ba(OH)2
+
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.
 The reactions are reversible
- With Aldehydes, the equilbrium favors product
- With ketones, the equilbrium favors the sarting materials.
Aldol condensation Reaction Mechanism
Step 1. Ionization of base Na
NaOH + OH
Step 2. Formation of acceptor electrophile
O ONa
R + Na R H
H
Step 3. The base removes an acidic alpha hydrogen from one aldehyde
molecule; yielding a resonance stabilized enolate ion (nucleophile).
O O
R OH R
H + H
Step 4. The enolate ion attacks a second aldehyde molecule in

nucleophilic addtion reaction to give a tetrahydral alkoxide ion
intermediate.
O ONa O OH O
ONa + R H2O
R R
R H H H NaOH H
R R
Step 5. Protonation of the alkoxide ion intermediate yields neutral aldol
product and regenerate the base catalyst.
Note that:
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

Ketol condensation Reaction Mechanism
Step 1. Ionization of base
NaOH Na + OH
Step 2. Formation of acceptor electrophile
O ONa
+ Na
Step 3. Formation of donar enolate nucleophile
O O
OH
+
Step 4. The enolate ion attacks a second ketone molecule giving a
tetrahydral alkoxide ion intermediate.
O ONa NaO O HO O
H H2O
H +
NaOH
Step 5. Protonation of the alkoxide ion intermediate yields neutral

ketol product and regenerate the base catalyst.
In similar manner dehydrates takes place in ketols to the

α,β -unsaturated compound.
Note That:
 The aldol product cannot be isolated.

 Dehydration is favorable because the product is stabilized
by conjugation of the alkene with the carbonyl group.

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

Reaction Mechanism of Cannizzaro Reaction

Home Work
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.

Q.2. Give the IUPAC name for the following.

O
A) O B)
Br
…………………………………… ……………………………………
Q.3 Arrange these compounds in order of increasing

Boiling point.
Acetone Propan-1-ol Propanal n-Butane Methoxyethane
(i) (ii) (iii) (iv) (v)

Thank you
For your attention

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Aldehydes & Ketones

Dr. Seham ALTERARY

Chapter out lines

 Physical Properties of Aldehydes and Ketones.

 Preparation of Aldehydes and Ketones.

Chem 340- 2nd semester 1437-1438

What are aldehydes and ketones?

Common Names for Aldehydes

Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde Valeraldehyde

IUPAC Nomenclature of Aldehydes

Chem 340- 2nd semester 1437-1438

Common: Formaldehyde Acetaldehyde Propionaldehyde Butyraldehyde

 Common name: listing the alkyl substitutents attached to the

Common & IUPAC Naming

Common: Dimethylketone Diphenylketone Methylphenylketone

IUPAC: Propanone diphenylmethanone 1-phenylethanone

Dipole-dipole interaction amang carbonyl compounds

Preparation of Aldehydes and Ketones

Chem 340- 2nd semester 1437-1438

Mild oxidizing agent [O] = CrO3/ pyridine or Cu/ heat

Secondary alcohols, are converted either into ketones on treatment

3.Hydration of alkynes: Addition of water

Enol form Keto form

Such isomers, differing only in the placement of a hydrogen atom, are

1-Cyclohexyl ethanadehyde 1-Cyclohexyl ethananone

Propionyl chloride Ethyl phenyl ketone

Reactions of Aldehydes and Ketones

General equation 1. In case of formaldehyde:

Grignard reagents react with formaldehyde to produce primary alcohols.

Grignard reagents react with aldehyde to produce secondary alcohols.

Grignard reagents react with ketones to produce tertiary alcohols.

CH3C R +3I2 + 4NaOH CHI3 + CH3COO- Na+ + 3H2O + 3NaI

+ve Iodoform(CHI3) result =

c) CH3C CH3 + 3I2 NaOH CHI3 + CH3 C

Compounds Results Why ??

HCHO -ve, No yellow ppt Has no CH3CO

CH3CHO +ve, gives yellow ppt Has CH3CO

CH3COCH3 +ve, gives yellow ppt Has CH3CO

Chem 340- 2nd semester 1437-1438

 This reaction happen when you have terminal ketone.

 Haloform could be chloroform, bromoform and Iodoform.

Chem 340- 2nd semester 1437-1438

Chem 340- 2nd semester 1437-1438

Experiment Observation Conclusion

Tollen’s test No change in the colourless Ketone

Chem 340- 2nd semester 1437-1438

5. Addition of Hydrogen cyanide: Formation of cyanohydin.

aldehydes or ketones Cyanohydrin

(Cyanohydrin: A molecule containing an -OH group and a -CN group

Benzaldehyde Benzaldehyde cyanohydrin

Cyclohexanone Cyclohexanone cyanohydrin

Chem 340- 2nd semester 1437-1438

Also, hydrolysis of the CN group with acidic water gives a hydroxy

(An alkynol: is an alcohol on carbon adjacent to triple bond.)

An Aldehyde An alcohol A hemiacetal

General equation R C OR' + R" OH H+ (anhyd.) R C OR'

Ethanal Methanol 1-Methoxyethanol 1,1-Dimethoxyethanol

General equation R C R" + R' OH H+

A Ketone An alcohol A hemiketal

a hemiketal An alcohol ketals

The reaction is reversible and catalyszed by acid.

The net result is replacement

a) The Reaction with Hydroxylamine