Aldehyde and Ketones CH-6

Kaysons Education Ketons and Aldehydes
Chapter
Ketones and Aldehydes
6
Day – 1
Ketones and Aldehydes

Carbonyl Compounds
We will study compounds containing the carbonyl group (C = O) in detail because they are of
central importance to organic chemistry, biochemistry and biology. Some of the common types of
carbonyl compounds are listed in table.
Carbonyl compounds are everywhere. In addition to their uses as reagents and solvents,
they are constituents of fabrics, flavorings, plastics and drugs. Naturally occurring carbonyl
compounds include proteins, carbohydrates, and nucleic acids that make up all plants and animals.
In the next few chapters, we will discuss the properties and reactions of simple carbonyl
compounds. Then, in chapter 23 and 24, we apply this carbonyl chemistry to carbohydrates,
nucleic acids, and proteins.
The simplest carbonyl compounds are ketones and aldehydes. A ketone has two alkyl (or
aryl) group bonded to the carbonyl carbon atom. An aldehyde has one alkyl (or aryl) group and
one hydrogen atom bonded to the carbonyl carbon atom.
Ketone:- Two alkyl groups bonded to a carbonyl group.
Aldehyde:-One alkyl group and one hydrogen bonded to a carbonyl group.
Page 208
Ketones and aldehydes are similar in structure, and they have similar properties. There are some
differences, however, particularly in their reactions with oxidizing agents and with nucleopiles. In
most cases, aldehydes are more reactive then ketones, for reasons we discuss shortly.
Some Common Classes of Carbonyl Compounds

Class General Formula Class General Formula
Ketones Aldehydes
Carboxylic acids Acid chlorides
Esters Amides
Structure of the Carbonyl Group

The carbonyl carbon atom is sp2 hybridized and bonded to three other atoms through coplanar
sigma bonds oriented about 120o apart. The unhybridized p orbital overlaps with a p orbital of
oxygen to form a pi bond. The double bond between carbon and oxygen is similar to an alkene C
= C double bond, except that the carbonyl double bond is shorter, stronger, and polarized.
The double bond of the carbonyl group has a large dipole moment because oxygen is more
electronegative then carbon, and the bonding electrons are not shared equally. In particular, the
less tightly held pi electrons are pulled more strongly towards the oxygen atom, giving ketones
and aldehydes larger dipole moments than most alkyl halides and ethers. We can use resonance
forms to symbolize this unequal sharing of the pi electrons.
Page 209
The first resonance form is more important because it involves more bonds and less charye
separation. The contribution of the second structure is evidenced shown below.
This polarization of the carbonyl group contributes to the reactivity of ketones and aldehydes. The
positively polarized carbon atoms acts as an electrophile (Lewis acid), and the negatively
polarized oxygen acts as a nucleophile (Lewis base).
Nomenclature of ketones and Aldehydes

Systematic names of ketones are derived by replacing the final –e in alkane name with –one. The
“alkane” name becomes “alkanone.” In open–chain ketones, we number the longest chain that
includes the carbonyl carbon from the end closed to the carbonyl group, and we indicate the
postion of the carbonyl group by a number. In cyclic ketones, the carbonyl carbon atom is
assigned the number 1.
Systematic names for aldehydes are derived by replacing the final –e of the alkane name with –al.
An aldehyde carbon is at the end of a chain, so it is number 1. If the aldehyde group is attached to
a large unit (usually a ring), the suffix –carbaldehyde is used.
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A ketone or aldehyde group can also be named as a substituent on a molecule with another
functional group as its root. The ketone carbonyl is designated by the prefix oxo-, and the –– CHO
group is named as a formyl group. Carboxylic acids frequently contain ketone or aldehyde groups
named as substituents.
Common Names:- As with other classes of compounds, ketones and aldehydes are often called by
common names instead of their systematic IUPAC names. Ketones common names are formed by
naming the two alkyl groups bonded to the carbonyl group. Substituent locations are given using
Greek letters, beginning with the new the carbonyl group.
some ketones have historical common names. Dimethyl ketone is always called acetone, and alkyl
phenyl ketones are usually name as the acyl group followed by the suffix –phenone.
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Common names of aldehydes are derived from the common names of carboxylic acids (Table).
These names often reflect the Latin or Greek term for the original source of the acid or the
aldehyde. Greek letters are used with common names of aldehydes to give the location of
substituents. The first letter (α) is given to the carbon atom next to the carbonyl group.
Common Names of Aldehydes

Carboxylic Acid Derivation Aldehyde
formica, “ants”
acetum, “sour”
protos pion, “first fat”
butyrum, “butter”
gum benzoin, “blending”
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Nomenclature
Structure Common name IUPAC name
Aceto-phenone 1-phenylethan-1-one
4-methylcyclohexanone
3-hydroxybutanal
5-oxopentanoicacid
3-oxopentanal
2-formyl benzoic acid
cyclohexanecarbaldehyde
CH3CH2CH2CHO butyraldehyde butanal

CH2 = CH CHO acrolein Prop-2-en-l-ol
Vanillin 4-nhydroxy-3-methoxy
benzaldehyde
mesityloxide 4-methyl pent-3-ene-2-

one
Tr-cinnamaldehyde (2E)-3-phenyl prop-2-en-

1-ol
Page 213
3-formyl pentan- Propane-1,2,3-

1,5-dial tricarboldehyde
Physical Properties
Bond length bond energy
1.23 745 KJ/mole
C C 1.34 611 KJ/mole
Dipole moment:- High dipole moment

compound
dipole 2.9 D 2.7 D 1.9 D 1.9 D
Hydrogen bond:-
No H-bond with itself but can form H-bond with water or alcohol. So it is a good solvent.
Formaldehyde:-
Is gas so mixed with water 40% aqueous solution called formalin
Acetaldehyde:- bp 20o
Acetone:-
Industrial solvent nearly 3 billion kg/year many Aldehydes and Ketones are used as flaouring
agent.
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Day – 2
Preparation & Aldehyde and Ketone

(A) Oxidation →
(1) Alcohols: PCC (Pyridinium Chloro-chromate) and PDC (Phyridinium di-chromate) oxidize
Alcohol to aldehyde – no further oxidation takes place. If we use KMnO4 or K2Cr2O7 then 1o
alcohol will give acid 2o alcohol ketone.
(2)Oppenauer oxide: - use Aluminum t – butoxide for 2o alcohols → Ketone is formed; Here
even unsaturated alcohols can be oxidized without braking double bond.
(B) Reducation
Rosenmund Reduction:- Reduction Acid Chloride and ester (Only for aldehydes)
 BaSO4 acts as a poison and prevents further reduction of Aldehyde to Alcohols

 Quinolene and sulfur are also used, they are better poising agents.
 Lithium tri-tert- butoxyaluminuim hydride LiAlH (O– t-C4H9)3 or Sn(C4H9)3H can also be
used.
(2):- For esters to Aldehydes we use NaAlH4 or Di – isobutyl aluminum hydride (DIBAH)
Illustration
Find A,(B),(C),(D) and E
Page 215
A = CH3 CHO
B = CH3 COOH
C = CH3 CO Cl
D = CH3 CHO
E=
Illustration
Find A,(B),(C),(D) and E
(C) Hydroboration Oxidation

Terminal Alkyne + BH3 + Oxidation → Aldehyde
Non-Terminal Alkyne + BH3 + Oxidation → Ketone
(D) Decarboxylation of Calcium Salts of Carboxylic Acids
Good method for preparation of formaldehyde and Ketones but not good for other aldehydes.
Note:– If Calcium salt of dibasic acids are used then cyclic Ketones are formed.
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Example:-
(E) OXO Process
(F) Wacker Process
Example:-
Page 217
(G) Qzonolysis
(H) From RCN and RMgX
(I) From Carboxylic Acid

(A):- (Aldehyde) RCOOH RCHO
(B):- (Keaton) – Use Organolithium.
(J) Friedel craft’s Acylation
(K) Gateman Koch Synthesis
(L) Stephen’s Reaction
(M) Etard Reaction
Page 218
Chemical Properties
(A):- Oxidation: Aldehydes are good reducing agents as they get easily oxidised to RCOOH
(except HCHO which oxidises to CO2) by weak oxidized agents like:-
 Tollen‟s reagent (Ammonical AgNO3) to form Silver mirror
 Fehling‟s Solution (Alkaline Cu++) All aldehydes except Benzaldehyde reduce fehling‟s
solution to Cu+( red ppt)
 Aldehyd also Reduce Benedict‟s solution (Cu+2 with citrate ion)

 Ketones are oxidized by Caro‟s Acid (H2SO5) or peroxybenzoic acid (C6 H5 CO3H) to
esters.
 Haloform Test It is only given by acetaldehyde, and methyl Ketones.
This group is a must for this tesr.
a
Genrally Iodine is used, it gives Iodoform (Yellow Colour)
This test is also given by alcohols which on oxidation give acedaledhyde or Methyl Ketones.
Example:-
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(B) Reduction of Carbonyls

1:- CHO is red reduced to 1o alcohol but C = C is not effected by LiAlH4
> C = O is reduced to 2o Alcohol.
2:- NaBH4:- same a LiAlH4 but it also does not Effect C= C double bond.
3:- Hydrogen + metal (Ni) changes
CHO → 1o alcohol > C = O → 2o alcohol C = C → C – C

4:- Clemmenson‟s Reduction – (Better for Keatone then Aldehyde)
5:- Use Red P + HI to get Alkanes
6:- Wolf Kishner Reduction. Reduction by hydrazine (NH2NH2) with KOH
7:- Ketones when Reduced with neutral or alkaline medium KMnO4 gives Pinnacoles
(Symmetrical 1 – 2diols).
Ex:-1
Ex:- 2
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Day – 3
(C) Addition Reaction (Nucleophillic)
Reactivity HCHO > RCHO > RCOR
Electron withdrawing group (-I effect) makes C more +ve and so increases reactivity.
∵ of CH3 (+I) effect and also steric hindrance
(1):- Addition of HCN > C = O + HCN ⇌
Cyanohydrin. All aldehydes from cyano-hydrins but in ketones only acetone, Butanone,3
pentanone form cyanohydrin.
(2):- Addition of grignard’s Reagent:-
(a) R” can not be H always CH3 or greater

(b) R and R‟ can be H also.
(c) If R =R‟ = H (Formaldehyde) ⟶ 1O alcohol
If R = H and R‟ CH3 (Aldehyde) ⟶ 2O alcohol
If R and R‟ CH3 (Ketone) ⟶ 3O alcohol
(3):- Addition of Ammonia and it’s Derivatives
Page 221
N NH C NH2
Important Note:- HCHO reacts with NH3 to give Urotropine: 6HCHO + 4NH3 (CH2)6N4 + 4H2O
Ex:-
(D) Cannizzaro Reaction

Aldehydes that do not have - hydrogen undergo Cannizzaro‟s reaction in which two molecules
of aldehyde react with each other in presence of alkali. While one molecule is reduced to alcohol
the other gets oxidized to salt of corresponding acid.
2HCHO + NaOH → CH3 OH + HCOONa
(50%)
1:- When HCHO is reached with other aldehyde capable of cannizzoro‟s Reaction then HCHO
undersoci oxidation while other Aldehyhe undersoci reduction. This is called crossed C.R.
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2:- Same aldehyde – Disproportconation. Diff Aldehyde – Redox

3:- In case of two aldehydes on same molecule and none has hydrogen then Intramolecular (C)
R tales place
Mechanism
(E) Aldol Condensation

Two or more MacLean of same or different carbonyl compounds containing - hydrogen atom
unite together in presence of dilute base such as NaOH , Ba(OH)2 or K2CO3 etc to form Aldols
(aldehyde + alcohol)
1:- Reaction takes place between (a) same or different Aldehyde or Ketone. At least one molecule
should contain ∝ - hydrogen
2:- A new carbon to carbon linkages is formed.
3:- Aldol looses water on heating to from - unsaturated carbonyl.
Example:- 1
Example:-2
Example:- 3
Page 223
Crossed Aldol Condensation

Aldehyde and ketones (with Hyd.) reacts in presence of dill NaOH then it is crossed. Aldol
condensation. Here of ketones takes part.
Overall Rxn:-
Mechanism
(1):- If two aldehydes take part in reaction then - H of that aldehyde will take pant which is
more acidic. Ie. in CH3CHO and C2 H5 CHO ∝ H of CH3 CHO take pant
(2):- If a comp and has two or more carbonyl groups intramolecular aldol condensation takes place
preferred product will have 5-6 member ring.
Ex:-1
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Ex:- 2
Claisen Condensation
Aromatic aldehyde + Aliphatic Aldehyde or ketone → ∝,β unsaturated aldehyde or ketone
Tischenko Reaction Aldehyde in presence of Aluminium ethoxide [Al(OC2H5)3] is

simultaneously oxidized as well on reduced. alcohol and acid which further react with each other
to give ester.
Illustration
Find A, B, C, D and E
Solution
As „A‟ undergoes Cannizaro‟s Reaction it does not have hydrogen. It is aliphatic aldehyde.
C = Two moles of (CH3)3–C–CH2 OH

D = (CH3)3 C–CHO + (CH3)3 –C–CH2OH
With NaBH4 → No Reaction
Illustration
Find A, B, C.
Solution
Aldol Cond.
Page 225
(4):- Additions of Alcohols
 Hemiacetal is very reactive of easily forms acetal

 Acetal is stable in Alkali but converts into aldehyde and alcohol in acid medium . so acetal is
used as protecting group for aldehyde in basic medium. b. In acid medium mercoptans (thio
alcohols) are used. Use C2H5SH in place of C2H5 OH
Example:-
Page 226
Aromatic Aldehyde and Ketone

Preperation
(A) From Toluene:-
(B) Frieda Craft‟s Acylation:-
(C) Gateman KOCH Synthesis:-
(D) Gatterman Aldehyde Synthesis:-
(E) From RMg X:-
Page 227
(F) Oxidation of Benzyl Chloridel:-
(G) Using Diazonium Salt:-
Chemical Properties
(A) Oxidation:-
(B) Reduction:-
(C) Canizzaro‟s Reaction:-
(D)Benzoin Condensation:-
Crucible Aided Condenser
(E) Perkin Reaction:-

1. Ar – CHO + Anhydride → ∝ β unsaturated acid Should have ∝ - hydrogen
Page 228
2. Ar – CHO + cyclic anhydride → - unsaturated acid
Claisen Schmitt Condensation
Knoevenagel Cond.
Reformatsky Reaction
Page 229
Day – 4
Illustration
Addition of water to alkynes occurs in acidic medium and in the presence of Hg2+ ions as a
catalyst. Which of the following products will be formed on addition of water to but-1-yne under
these conditions?
Solution
The correct option is b.
Illustration
Which of the following compounds is most reactive towards nucleophilic addition reactions?
Solution
The correct option is (i).
Illustration
The correct order of increasing acidic strength is _____________.
(a) Phenol < Ethanol < Chloroacetic acid < Acetic acid
(b) Ethanol < Phenol < Chloroacetic acid < Acetic acid
(c) Ethanol < Phenol < Acetic acid < Chloroacetic acid
(d) Chloroacetic acid < Acetic acid < Phenol < Ethanol
Solution
The correct option is (c).
Illustration
Compound can be prepared by the reaction of _____________.
(a) Phenol and benzoic acid in the presence of NaOH

(b) Phenol and benzoyl chloride in the presence of pyridine
(c) Phenol and benzoyl chloride in the presence of ZnCl2
(d) Phenol and benzaldehyde in the presence of palladium
Solution
The correct option is (b).
Illustration
The reagent which does not react with both, acetone and benzaldehyde.
(a) Sodium hydrogensulphite (b) Phenyl hydrazine

(c) Fehling‟s solution (d) Grignard reagent
Solution
Page 230
Illustration
Cannizaro‟s reaction is not given by _____________.
Solution
The correct option is (d).
Illustration
Which product is formed when the compound is treated with concentrated aqueous KOH solution?
Solution
Illustration
Complete the following reaction sequence.
Solution
Illustration
Oxidation of ketones involves carbon-carbon bond cleavage. Name the products formed on
oxidation of 2, 5-dimethylhexan-3-one.
Solution
Page 231
Illustration
Compound „A‟ was prepared by oxidation of compound „B‟ with alkaline KMnO 4. Compound „A‟
on reduction with lithium aluminium hydride gets converted back to compound „B‟. When
compound „A‟ is heated with compound B in the presence of H2SO4 it produces fruity smell of
compound C to which family the compounds „A‟, „B‟ and „C‟ belong to?
Solution
„A‟ is a carboxylic acid, „B‟ is an alcohol and „C‟ is an ester.
Illustration
Structure of „A‟ and type of isomerism in the above reaction are respectively.
(i) Prop–1–en–2–ol, metamerism

(ii) Prop-1-en-1-ol, tautomerism
(iii) Prop-2-en-2-ol, geometrical isomerism
(iv) Prop-1-en-2-ol, tautomerism
Solution
The correct option is (d).
Illustration
Compounds A and C in the following reaction are __________.
(a) identical (b) positional isomers

(c) functional isomers (d) optical isomers
Solution
Illustration
Which is the most suitable reagent for the following conversion?
(a) Tollen‟s reagent (b) Benzoyl peroxide

(c) I2 and NaOH solution (d) Sn and NaOH solution
Solution
Illustration
Fehling‟s solution can make distinction between:
Page 232
Solution
The correct option is a.
CH3CHO and C6H5CHO.
Illustration
A can be:
(a) (b)
(c) (d)
Solution
The correct option is (a).
Illustration
A and B are:
(a)
(b)
Page 233
(c) both
(d) none is correct
Solution
The correct option
Illustration
A and B are:
(a) CH3COCH3 (b) (CH3)3 COH, (CH3)2 C = CH2
(c) (CH3)2CHOH, CH3CH = CH2 (d) none is correct

Solution
The correct option is (CH3)3 COH, (CH3)2 C = CH2.
Illustration
An alkene „A‟ (Mol. formula C5H10) on ozonolysis gives a mixture of two compounds „B‟ and
„C‟. Compound „B‟ gives positive Fehling‟s test and also forms iodoform on treatment with I2 and
NaOH. Compound „C‟ does not give Fehling‟s test but forms iodoform. Identify the compounds
A, B and C. Write the reaction for ozonolysis and formation of iodoform from B and C.
Solution
Other isomers of „A‟ will not give products corresponding to the given test.
Illustration
An aromatic compound „A‟ (Molecular formula C8H8O) gives positive 2, 4-DNP test. It gives a
yellow precipitate of compound „B‟ on treatment with iodine and sodium hydroxide solution.
Compound „A‟ does not give Tollen‟s or Fehling‟s test. On drastic oxidation with potassium
permanganate it forms a carboxylic acid „C‟ (Molecular formula C 7H6O2), which is also formed
along with the yellow compound in the above reaction. Identify A, B and C and write all the
reactions involved.
Page 234
Solution
Illustration
Write down functional isomers of a carbonyl compound with molecular formula C 3H6O. Which
isomer will react faster with HCN and why? Explain the mechanism of the reaction also. Will the
reaction lead to the completion with the conversion of whole reactant into product at reaction
conditions? If a strong acid is added to the reaction mixture what will be the effect on
concentration of the product and why?
Solution
Compound I will react faster with HCN due to less steric hinderance and electronic reasons than
II.
No, It is a reversible reaction. Hence equilibrium is established.
Addition of acid inhibits the reaction because the formation of –CN ions is prevented.
Page 235

Aldehyde and Ketones CH-6

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Kaysons Education Ketons and Aldehydes

Ketones and Aldehydes

Ketone:- Two alkyl groups bonded to a carbonyl group.

Aldehyde:-One alkyl group and one hydrogen bonded to a carbonyl group.

Some Common Classes of Carbonyl Compounds

Carboxylic acids Acid chlorides

Structure of the Carbonyl Group

Nomenclature of ketones and Aldehydes

Common Names of Aldehydes

protos pion, “first fat”

gum benzoin, “blending”

2-formyl benzoic acid

CH3CH2CH2CHO butyraldehyde butanal

mesityloxide 4-methyl pent-3-ene-2-

Tr-cinnamaldehyde (2E)-3-phenyl prop-2-en-

3-formyl pentan- Propane-1,2,3-

C C 1.34 611 KJ/mole

Dipole moment:- High dipole moment

dipole 2.9 D 2.7 D 1.9 D 1.9 D

Preparation & Aldehyde and Ketone

 BaSO4 acts as a poison and prevents further reduction of Aldehyde to Alcohols

(C) Hydroboration Oxidation

Non-Terminal Alkyne + BH3 + Oxidation → Ketone

(D) Decarboxylation of Calcium Salts of Carboxylic Acids

(E) OXO Process

(F) Wacker Process

(H) From RCN and RMgX

(I) From Carboxylic Acid

(B):- (Keaton) – Use Organolithium.

(J) Friedel craft’s Acylation

(K) Gateman Koch Synthesis

(L) Stephen’s Reaction

(M) Etard Reaction

 Tollen‟s reagent (Ammonical AgNO3) to form Silver mirror

 Aldehyd also Reduce Benedict‟s solution (Cu+2 with citrate ion)

 Haloform Test It is only given by acetaldehyde, and methyl Ketones.

This group is a must for this tesr.

(B) Reduction of Carbonyls

CHO → 1o alcohol > C = O → 2o alcohol C = C → C – C

5:- Use Red P + HI to get Alkanes

6:- Wolf Kishner Reduction. Reduction by hydrazine (NH2NH2) with KOH

(C) Addition Reaction (Nucleophillic)

Reactivity HCHO > RCHO > RCOR

(1):- Addition of HCN > C = O + HCN ⇌

(2):- Addition of grignard’s Reagent:-

(a) R” can not be H always CH3 or greater

(D) Cannizzaro Reaction

2:- Same aldehyde – Disproportconation. Diff Aldehyde – Redox

(E) Aldol Condensation

Crossed Aldol Condensation

Tischenko Reaction Aldehyde in presence of Aluminium ethoxide [Al(OC2H5)3] is

C = Two moles of (CH3)3–C–CH2 OH

(4):- Additions of Alcohols

 Hemiacetal is very reactive of easily forms acetal

Aromatic Aldehyde and Ketone

(B) Frieda Craft‟s Acylation:-

(C) Gateman KOCH Synthesis:-

(D) Gatterman Aldehyde Synthesis:-

(E) From RMg X:-

(F) Oxidation of Benzyl Chloridel:-

(G) Using Diazonium Salt:-

(C) Canizzaro‟s Reaction:-

(E) Perkin Reaction:-

2. Ar – CHO + cyclic anhydride → - unsaturated acid