GE-4 AND GE-2 UNIT-4

1.A.) Cannizzaro's Reaction and Its Mechanism

Cannizzaro's reaction is a redox reaction where two molecules of a non-enolizable aldehyde
(having no α-hydrogen) react with concentrated base to form a molecule of alcohol and
a salt of carboxylic acid.
General Reaction:
conc. NaOH
2 R−CHO −−−−−−−→ R−CH2 OH + R−COO− Na+

Mechanism:
1. Nucleophilic attack: The hydroxide ion attacks the carbonyl carbon of one alde-
hyde molecule to form a tetrahedral alkoxide intermediate:

R−CHO + OH− → R−CH(OH)O−

2. Hydride transfer: The alkoxide intermediate acts as a hydride donor and transfers
a hydride ion (H-) to a second aldehyde molecule:

R−CH(OH)O− + R−CHO → R−COO− + R−CH2 O−

3. Protonation: −
The alkoxide ion (R−CH2 O ) formed from reduction is protonated
by water to give the nal alcohol:

R−CH2 O− + H2 O → R−CH2 OH + OH−

Net result: One aldehyde molecule is oxidized to a carboxylate ion, while the other
is reduced to a primary alcohol. This reaction is signicant in organic synthesis and
demonstrates an internal redox process.
Important: Only aldehydes lacking α-hydrogens, like benzaldehyde and formalde-
hyde, undergo Cannizzaro reaction eciently.

1.B.) Benzoin Condensation: Reaction and Mechanism

Benzoin condensation is a carboncarbon bond forming reaction between two aromatic
−
aldehydes (usually benzaldehyde) in the presence of a cyanide ion (CN ) as a catalyst
to give an α-hydroxy ketone called benzoin. This reaction is an example of nucleophilic
catalysis.
General reaction:
KCN
2 C6 H5 CHO −−−→ C6 H5 CH(OH)COC6 H5

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Mechanism:
1. Cyanide attack: The nucleophilic CN− attacks the carbonyl carbon of benzalde-
hyde to form a cyanohydrin intermediate.

2. Carbanion formation: The α-hydrogen on the cyanohydrin is slightly acidic and

is abstracted by base to form a carbanion stabilized by resonance.

3. Nucleophilic attack on second aldehyde: The carbanion acts as a nucleophile

and attacks the carbonyl carbon of another benzaldehyde molecule, forming a new
CC bond.

4. Protonation and elimination: The resulting alkoxide intermediate is protonated

to form a hydroxy ketone. Finally, CN− is eliminated, regenerating the catalyst and
forming benzoin.

Key Features:
ˆ Requires aldehydes without α-hydrogens (usually aromatic).

ˆ Cyanide ion acts both as a nucleophile and as a base.

ˆ Product is an α-hydroxy ketone.

Applications: Benzoin condensation is widely used in organic synthesis for con-

structing carbon frameworks and in the synthesis of heterocycles and pharmaceuticals.

2.A.) Distinguishing 1°, 2° and 3° Alcohols by Victor

Mayer's Test
°
° °
Victor Mayer's test is a classical chemical test used to distinguish primary (1 ), secondary
(2 ), and tertiary (3 ) alcohols based on their reaction with chromyl chloride (CrO2 Cl2 ).

Principle:
When alcohols react with chromyl chloride, they form colored complexes that undergo
dierent reactions upon reduction with water and acid. These dierences depend on the
structure of the alcohol, enabling their identication.

Procedure and Observation:

1. To a few drops of alcohol in a dry test tube, add a few drops of chromyl chloride
(CrO2 Cl2 ).
2. Warm gently and then add water followed by acidication.
3. Observe the color of the organic layer and any precipitate formed.

2
Results:
ˆ Primary (1°) alcohols: React with CrO2 Cl2 to form a deep red complex (chromyl
chloride complex). Upon hydrolysis with water and acid, aldehydes are produced,
and the red color disappears.

ˆ Secondary (2°) alcohols: Form a similar red chromyl chloride complex, but upon
hydrolysis, ketones are formed instead of aldehydes. The red color also disappears
after acidication.

ˆ Tertiary (3°) alcohols: Do not react with chromyl chloride due to the absence of
hydrogen on the carbon bearing the OH group. No red color is formed, and the
mixture remains colorless.

Conclusion:
°
° °
Victor Mayer's test relies on the formation of a red chromyl chloride complex with 1
and 2 alcohols but not with 3 alcohols. The dierence in the product formed upon
hydrolysis allows distinguishing between primary (aldehydes) and secondary (ketones)
alcohols. Thus, this test eciently dierentiates all three classes of alcohols.

2.B.) PinacolPinacolone Rearrangement

The PinacolPinacolone rearrangement is an acid-catalyzed molecular rearrangement in
which a 1,2-diol (vicinal diol), upon heating with a strong acid, undergoes dehydration
and rearrangement to yield a ketone. This reaction is particularly useful in organic
synthesis for converting glycols into more reactive carbonyl compounds.

General Reaction:
H+, ∆
(CH3 )2 C(OH)−C(OH)(CH3 )2 −−−−→ (CH3 )3 C−CO−CH3
In this example, pinacol is rearranged to pinacolone.

Mechanism:
1. Protonation: One of the hydroxyl groups is protonated by acid, making it a good
leaving group.

2. Loss of water: Water is eliminated, leading to the formation of a carbocation

adjacent to the other hydroxyl-bearing carbon.

3. Rearrangement (1,2-shift): A methyl or hydride group migrates from the neigh-

boring carbon to stabilize the carbocation (1,2-shift), forming a more stable carbo-
cation intermediate.

4. Deprotonation: Finally, deprotonation of the oxonium ion gives the corresponding

ketone (pinacolone).

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Key Points:
ˆ The rearrangement proceeds via a carbocation intermediate, favoring the most sta-
ble one.

ˆ The migrating group is usually the one that gives greater carbocation stability.

ˆ The reaction demonstrates a typical example of a molecular rearrangement.

Applications: This rearrangement is widely used in synthetic organic chemistry to

convert diols to ketones, especially in the synthesis of natural products and pharmaceu-
ticals.

3.A.) Reaction and Mechanism of 1,2-Diphenylbutane

with Lead Tetraacetate (Pb(OAc)4)
1,2-Diphenylbutane contains a 1,2-diol moiety when oxidized to its diol form (via cis-
dihydroxylation). Lead tetraacetate Pb(OAc)4 is a selective reagent that cleaves 1,2-diols
oxidatively to give carbonyl compounds (aldehydes or ketones).

Reaction:
Ph−CH(OH)−CH(OH)−CH2 CH3 +Pb(OAc)4 → Ph−CHO+CH3 CH2 −CO−Ph+Pb(OAc)2
Product: The oxidative cleavage of the vicinal diol gives two fragments  benzalde-
hyde and 1-phenylpropan-2-one.

Mechanism:
1. Formation of lead diacetate ester: The hydroxyl groups of the 1,2-diol coordi-
nate with Pb(OAc)4 , forming a cyclic diester intermediate with lead.

2. Homolytic cleavage: The CC bond between the two hydroxyl-bearing carbons
breaks homolytically, resulting in the formation of two carbonyl compounds.

3. Release of lead acetate: The Pb(II) is released as Pb(OAc)2 as a by-product.

Key Points:
ˆ Pb(OAc)4 is a strong oxidizing agent and selectively cleaves 1,2-diols.

ˆ The reaction proceeds through a cyclic intermediate involving the PbO coordina-
tion.

ˆ It is widely used for structural determination and oxidative cleavage in synthetic

organic chemistry.

Conclusion: The reaction of 1,2-diphenylbutane with Pb(OAc)4 is a typical exam-

ple of oxidative cleavage of vicinal diols, yielding carbonyl compounds useful in further
transformations.

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3.B.) GattermannKoch Reaction and Its Mechanism
(270 Words)
The GattermannKoch reaction is a formylation reaction used to introduce a formyl
group (CHO) into an aromatic ring. It involves the reaction of benzene with carbon
monoxide and hydrogen chloride in the presence of a Lewis acid catalyst such as AlCl3
and a co-catalyst CuCl.

General Reaction:
AlCl3/CuCl
C6 H6 + CO + HCl −−−−−−−→ C6 H5 CHO
Benzene is converted into benzaldehyde under these conditions.

Mechanism:
1. Generation of formyl cation (HCO+ ): Carbon monoxide reacts with HCl in
the presence of AlCl3 and CuCl to form the electrophilic formyl cation:

CO + HCl + AlCl3 + CuCl −−→ [HCO]+

2. Electrophilic substitution: The formyl cation then undergoes electrophilic aro-

matic substitution with benzene to form a resonance-stabilized sigma complex (are-
nium ion).

3. Restoration of aromaticity: Loss of a proton from the sigma complex regenerates

the aromatic ring and gives benzaldehyde as the nal product.

Key Features:
ˆ It is applicable mainly to benzene and activated aromatic compounds.

ˆ The reaction does not work well with deactivated rings or strongly electron-withdrawing
groups.

ˆ It is an important method for synthesizing aromatic aldehydes.

Conclusion: The GattermannKoch reaction is an ecient electrophilic substitution

technique for introducing formyl groups into aromatic rings using CO and acid catalysts.

4.A.) Aldol Condensation: Reaction and Mechanism (270

Words)
Aldol condensation is an important carboncarbon bond-forming reaction that occurs
between aldehydes or ketones containing at least one α-hydrogen in the presence of dilute
base or acid.

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General Reaction (Base-catalyzed):
OH− ∆
→ CH3 CH−CHCHO + H2 O
2 CH3 CHO −−−→ CH3 CH(OH)CH2 CHO −
Here, two molecules of acetaldehyde condense to form β -hydroxy aldehyde (aldol),
which upon heating loses water to give α, β -unsaturated aldehyde.

Mechanism:
1. Enolate ion formation: The base abstracts an α-hydrogen to generate an enolate
ion.
CH3 CHO + OH− −−→ CH2 − CHO + H2 O

2. Nucleophilic attack: The enolate ion attacks the carbonyl carbon of a second
molecule of aldehyde to form a new CC bond.

CH2 − CHO + CH3 CHO −−→ CH3 CH(OH)CH2 CHO

3. Dehydration: On heating, the β -hydroxy aldehyde undergoes elimination of water

to form an α, β -unsaturated carbonyl compound.

CH3 CH(OH)CH2 CHO −−→ CH3 CH−CHCHO + H2 O

Key Points:
ˆ Both aldehydes and ketones with α-hydrogens undergo this reaction.

ˆ The reaction forms CC bonds and builds more complex structures.

ˆ Acid-catalyzed aldol condensation follows a similar path via enol intermediates.

Applications: Aldol condensation is widely used in synthetic organic chemistry and

in the synthesis of intermediates for dyes, perfumes, and pharmaceuticals.

4.B.) WolKishner Reduction: Reaction and Mecha-

nism (270 Words)
The WolKishner reduction is a chemical reaction that reduces aldehydes or ketones to
alkanes using hydrazine (NH2 NH2 ) and a strong base like KOH under high-temperature
conditions (usually in ethylene glycol). It is widely used when the carbonyl group needs
to be completely removed.

General Reaction:
∆
R2 C−O + NH2 NH2 + KOH −
→ R2 CH2 + N2 + H2 O

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Mechanism:
1. Hydrazone formation: The ketone or aldehyde rst reacts with hydrazine to
form a hydrazone.

R2 C−O + NH2 NH2 −−→ R2 C−NNH2 + H2 O

2. Deprotonation and rearrangement: Under basic and high-temperature condi-
tions, the hydrazone is deprotonated to form a diazene anion intermediate.

3. Loss of nitrogen gas: The diazene rearranges and eliminates nitrogen gas (N2 ),
forming a carbanion.

4. Protonation: The carbanion abstracts a proton from water or the solvent to yield
the alkane.
R2 CH− + H2 O −−→ R2 CH2 + OH−

Key Points:
ˆ Suitable for heat-stable substrates.

ˆ Removes carbonyl groups without aecting other sensitive functionalities.

ˆ Often used in conjunction with the Clemmensen reduction in synthetic planning.

Conclusion: The WolKishner reduction is an eective method for converting car-

bonyl compounds into alkanes by using hydrazine under strongly basic conditions with
the evolution of nitrogen gas.

5.) Preparation of 1°, 2°, and 3° Alcohols Using Grignard

Reagents (500 Words)
Grignard reagents (RMgX) are organomagnesium halides formed by reacting alkyl or
aryl halides with magnesium in dry ether. They are strong nucleophiles and react with

° ° °
various carbonyl compounds to form alcohols after acidic hydrolysis. The type of alcohol
formed (1 , 2 , or 3 ) depends on the nature of the carbonyl compound used.

1. Formation of Primary (1°) Alcohols:

Primary alcohols are obtained when Grignard reagents react with formaldehyde (HCHO).
The reaction proceeds as follows:

3 H O+
R−MgX + HCHO −−→ R−CH2 OMgX −−−→ R−CH2 OH
Mechanism:
1. The Grignard reagent attacks the electrophilic carbon of formaldehyde.

2. An alkoxide intermediate is formed.

3. Acidic hydrolysis gives a primary alcohol.

Example:
3 H O+
CH3 MgBr + HCHO −−→ CH3 CH2 OMgBr −−−→ CH3 CH2 OH

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2. Formation of Secondary (2°) Alcohols:
Secondary alcohols are prepared by the reaction of Grignard reagents with aldehydes

 
other than formaldehyde.
R-MgX + R'-CHO R-CH(OMgX)-R' [H3O+] R-CH(OH)-R'
Mechanism:
1. Nucleophilic addition of Grignard reagent to aldehyde.

2. Formation of a secondary alkoxide.

3. Hydrolysis yields a secondary alcohol.

Example:
3 H O+
CH3 MgBr + CH3 CHO −−→ CH3 CH(OMgBr)CH3 −−−→ CH3 CH(OH)CH3

3. Formation of Tertiary (3°) Alcohols:

 
Tertiary alcohols are obtained by reacting Grignard reagents with ketones.
R-MgX + R'-CO-R R-C(OMgX)(R')(R) [H3O+] R-C(OH)(R')(R)
Mechanism:
1. Grignard reagent attacks the carbonyl carbon of a ketone.

2. A tertiary alkoxide intermediate is formed.

3. Acid hydrolysis gives a tertiary alcohol.

Example:
3 H O+
CH3 MgBr + CH3 COCH3 −−→ CH3 C(OMgBr)(CH3 )(CH3 ) −−−→ CH3 C(OH)(CH3 )(CH3 )

Important Notes:
ˆ All reactions must be carried out under anhydrous conditions to prevent decompo-
sition of the Grignard reagent.

ˆ The product alcohol depends on the type of carbonyl compound used:

 Formaldehyde 
Primary alcohol

 Aldehyde (except formaldehyde)  Secondary alcohol

 Ketone 
Tertiary alcohol

ˆ Grignard reagents are very versatile and useful in building complex alcohol struc-
tures in organic synthesis.

Conclusion: Grignard reagents serve as a powerful tool in organic chemistry for the
preparation of all three types of alcohols. By selecting the appropriate carbonyl com-
pound, one can synthesize primary, secondary, or tertiary alcohols with high specicity.

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6.) Classication of Alcohols and Tests to Distinguish
Them (500 Words)
Alcohols are organic compounds containing one or more hydroxyl (  OH) groups attached
to a saturated carbon atom. Based on the number of alkyl groups attached to the

° ° °
carbon bearing the  OH group, alcohols are classied into three categories: primary
(1 ), secondary (2 ), and tertiary (3 ) alcohols.

1. Primary (1°) Alcohols

In a primary alcohol, the hydroxyl group is attached to a carbon atom which is bonded to
only one other alkyl group. The general structure is R  CH2 OH. An example is ethanol
(CH3 CH2 OH).

2. Secondary (2°) Alcohols

In secondary alcohols, the hydroxyl group is attached to a carbon atom that is bonded
to two alkyl groups. The general structure is R2 CHOH. An example is isopropanol
(CH3 CHOHCH3 ).

3. Tertiary (3°) Alcohols

In tertiary alcohols, the  OH group is connected to a carbon atom that is attached to
three alkyl groups. The general structure is R3 COH. An example is tert-butyl alcohol
((CH3 )3 COH).

Distinguishing Tests for Alcohols

1. Lucas Test
° °
The Lucas test is a qualitative test used to distinguish between 1 , 2 , and 3 ° alco-
hols based on their reactivity with Lucas reagent, which is a mixture of concentrated
hydrochloric acid (HCl) and anhydrous zinc chloride (ZnCl2 ).
Procedure: Each alcohol is added to the Lucas reagent in a test tube.
Observations:
ˆ °
Tertiary (3 ) alcohols react immediately at room temperature, producing turbidity
(cloudiness) due to the formation of an insoluble alkyl halide.

ˆ °
Secondary (2 ) alcohols show turbidity within 5 minutes.

ˆ °
Primary (1 ) alcohols show little or no turbidity at room temperature.

Reaction (example for 3 alcohol): °

(CH3 )3 COH + HCl −−→ (CH3 )3 CCl + H2 O
Conclusion: The rate of turbidity formation helps distinguish the type of alcohol.
2. Victor Meyer's Test
This test is more complex but gives a reliable distinction among the three types of
alcohols.
Steps:

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 1. The alcohol is converted to the corresponding alkyl iodide using red phosphorus
and iodine.

2. The alkyl iodide is then treated with silver nitrite to form a nitroalkane.

3. The nitroalkane is then reacted with nitrous acid and alkali.

Observations:
ˆ Primary alcohols give a blood-red color.

ˆ Secondary alcohols give a blue color.

ˆ Tertiary alcohols do not produce any color.

Conclusion: The color developed after treatment with nitrous acid helps identify
the nature of the alcohol.

Final Remark
Both Lucas and Victor Meyer tests are widely used in organic chemistry labs to distinguish
between primary, secondary, and tertiary alcohols. While Lucas test is simpler and faster,
Victor Meyer test oers more denitive results.

7. short notes on:

1 (i)wolf-kishner and (II)gatterman explained earlier
7.III.) Short Note on Iodoform Test
The Iodoform test is a qualitative chemical test used to identify the presence of methyl

ketones (CH3  CO ) or ethanol (CH3 CH2 OH) and other compounds containing the methyl
group adjacent to a carbonyl or hydroxyl group.
In this test, the organic compound is treated with iodine (I2 ) in the presence of a base
such as sodium hydroxide (NaOH). If the compound contains a methyl ketone group or
ethanol, a pale yellow precipitate of iodoform (CHI3 ) is formed, which has a characteristic
antiseptic smell.

CH3 COCH3 + 3 I2 + 4 NaOH −−→ CHI3 (yellow ppt · ) + CH3 COONa + 3 NaI + 3 H2 O

The test is positive for compounds such as acetone, ethanol, and other methyl ketones,
but negative for other types of ketones and alcohols. It is a useful diagnostic tool in
organic chemistry for the identication of specic functional groups.

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8.) Statements and Equations of Important Organic Re-
actions
8.a) Reimer-Tiemann Reaction
Statement: The Reimer-Tiemann reaction is used to formylate phenols at the ortho
position. When phenol is treated with chloroform (CHCl3 ) in the presence of a strong base
such as sodium hydroxide (NaOH), salicylaldehyde (o-hydroxybenzaldehyde) is formed.
Equation:
C6 H5 OH + CHCl3 + 3 NaOH −−→ C6 H4 (OH)CHO + 3 NaCl + 2 H2 O

8.b) Benzoin Condensation

Statement: Benzoin condensation is a reaction where two molecules of aromatic alde-
hydes (typically benzaldehyde) condense in the presence of a catalyst like cyanide ion

(CN ) to form benzoin, an alpha-hydroxy ketone.
Equation:
CN−
2 C6 H5 CHO −−−→ C6 H5 −CH(OH)−CO−C6 H5


8.c) Cannizzaro Reaction

Statement: The Cannizzaro reaction is a redox reaction where non-enolizable aldehydes
(without alpha-hydrogen) undergo simultaneous oxidation and reduction in the presence
of concentrated alkali, producing an alcohol and a carboxylic acid salt.
Equation (using benzaldehyde):
2 C6 H5 CHO + NaOH −−→ C6 H5 CH2 OH + C6 H5 COONa

8.d) Aldol Condensation

Statement: Aldol condensation involves the reaction of aldehydes or ketones having at
least one alpha-hydrogen in the presence of dilute base to form beta-hydroxy aldehydes or
ketones (aldols), which on heating undergo dehydration to give alpha,beta-unsaturated
aldehydes or ketones.
Equation (using acetaldehyde):
NaOH ∆
→ CH3 CH−CHCHO + H2 O
2 CH3 CHO −−−−→ CH3 CH(OH)CH2 CHO −

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