IAL Chemistry Unit 4 Reactions

1. Reaction between carbonyl compound and hydrogen cyanide

Reagents: HCN, NaOH

Condition: pH 8.0
Reaction: CH3CHO + HCN  CH3CHOHCN
Mechanism:

Note: As the carbonyl group is planar, the nucleophile may attack from any direction, hence producing a
racemic mixture of Dextrorotatory and Levorotatory enantiomers.

2. Oxidation of Carbonyl compounds.

Reagents:
For Ketones: Alkaline KMnO4 or concentrated HNO3
For Aldehydes: Acidified K2Cr2O7 or Na2Cr2O7, or weak oxidizing agents such as Tollens reagent,
Fehling’s solution, Benedict’s solution
Conditions:
For Ketones: Heat with HNO3
For Aldehydes: H2SO4 or warm with weak oxidizing agent.
Reaction: Ketone: CH3CH2COCH3 + [HNO3 + Heat]  CH3CH2COOH + CH3COOH
Aldehyde: K2Cr2O7 or Na2Cr2O7: CH3CHOH + [K2Cr2O7/Na2Cr2O7 + H2SO4]  CH3COOH
Weak oxidizing agent: CH3CHO + [O]  CH3COOH
3. Reduction of Carbonyl compounds.
Reagents: LiAlH4, Ether as solvent
Conditions: Reagent must be kept dry (that’s where ether comes in)
Reaction: Aldehydes: CH3CHO + 2[H]  CH3CH2OH
Ketones: CH3COCH3 + 2[H]  CH3CH(OH)CH3
Note: Reaction takes place in two steps. In the first step, an H+ ion attaches to the δ+ carbon atom. It
is carried out in an ether solution as the reagent must be kept dry. In the second step, an aqueous
solution of acid is added to protonate the O- ion formed in the first step.
4. Addition-Elimination Reaction (with Brady’s reagent)
Reagent: 2, 4-dinitro phenyl hydrazine
Conditions: Concentrated HCl, warm at 50°C on water bath.
Reaction:

Observation: Yellow precipitate formed in case of aliphatic carbonyl group, orange in case of
aromatic.
Note: This is an important reaction, as it can be used to identify carbonyl compounds.
5. Iodoform reaction
Reagents: I2, NaOH
Conditions: Warm
Reaction: 2-Step: CH3CO-R + 3I2 + 3NaOH  R-CO-CI3 + 3NaI + 3H2O
R-CO-CI3 + NaOH  CHI3 + R-COONa
1-Step: CH3CO-R + 3I2 + 4NaOH  CHI3 + R-COONa + 3NaI + 3H2O
Observation: Pale yellow precipitate of iodoform, CHI3.
Note: This reaction is only feasible with compounds having a methyl carbonyl group (CH3-CO-), or
compounds which produce this group on oxidation. Examples are methyl ketones, ethanol, ethanol,
methyl secondary alcohol. This is a crucial method of identifying methyl carbonyl group containing
compounds.
6. Preparation of Carboxylic acid
Method 1: Oxidation of primary alcohols or aldehydes with a mixture of H2SO4 and K2Cr2O7.
Condition: Heat under reflux.
Reaction: CH3CH2CH2OH + [O]  CH3CH2CH2CHO + H2O
CH3CH2CH2CHO  CH3CH2COOH
Note: The primary alcohol is first oxidized to an aldehyde, and then to the carboxylic acid.
Method 2: Hydrolysis of ester
Reagents: NaOH, HCl
Condition: Boil
Reaction: CH3COOC2H5 + NaOH + [Heat]  CH3COONa + CH3CH2OH
CH3COONa + HCl  CH3COOH + NaCl
Note: Boiling the ester with concentrated aqueous NaOH gives the sodium salt of the carboxylic
acid. This, on treatment with HCl, gives the corresponding carboxylic acid.
Method 3: Hydrolysis of nitriles
 Condition: Heat under reflux
Reagents: dilute H2SO4
Reaction: CH3CN + H2SO4 + H2O  CH3COOH + (NH4)2SO4
Note: If the nitrile is heated under reflux with aqueous NaOH, the salt of the carboxylic acid is
formed. Subsequent addition of strong acid produces the carboxylic acid.
Reaction: CH3CN + NaOH + H2O  CH3COONa + NH3
CH3COONa + HCl  CH3COOH + NaCl
7. Reaction of carboxylic acid with water
Reaction: CH3COOH + H2O  CH3COO- + H3O+
Note: The -OH group in carboxylic acid is more acidic than the -OH group in alcohols. This is
because in carboxylic acids, the C=O group pulls electrons away from the -OH group, making the
hydrogen atom more δ+, and therefore easier to remove it as H+ ion.
8. Reaction of carboxylic acid with NaOH, Na2CO3 and NaHCO3
Carboxylic acid reacts with hydroxides, carbonates and bicarbonates to form their
corresponding salt.
Reaction: CH3COOH + NaOH  CH3COONa + H2O
2CH3COOH + Na2CO3  2CH3COONa + H2O + CO2
CH3COOH + NaHCO3  CH3COONa + H2O + CO2
9. Reaction of carboxylic acid with PCl5
Reagents: PCl5
Reaction: CH3COOH + PCl5  CH3COCl + POCl3 + HCl
Observation: Steamy fume
Note: Thionyl chloride, SOCl3, gives the same reaction.
Reaction: CH3COOH + SOCl3  CH3COCl + SO2 + HCl
Observation: Steamy fume
This reaction is used to make acid chloride from carboxylic acid.
10. Reduction of carboxylic acid
Reagent: LiAlH4, ether as solution
Condition: Dry conditions
Reaction: CH3COOH + 4[H]  CH3CH2OH + H2O
Note: Carboxylic acids are much harder to reduce than carbonyl compounds. Carboxylic acids
are not reduced by H2 gas in presence of Ni/Pt catalyst.
Reaction: CH2=CHCOOH + [LiAlH4]  CH2CHCH2OH
CH2=CHCOOH + H2 + [Ni/Pt]  CH3CH3COOH
11. Reaction of carboxylic acid with halogens
Reagent: Cl2, Br2, I2
Condition: UV ray, boiling carboxylic acid
Reaction: CH3COOH + Cl2 + [UV]  CH2ClCOOH + HCl
CH3CH2COOH + Cl2 + [UV]  CH3CHClCOOH + HCl
Note: Reaction follows free radical substitution mechanism.
12. Esterification
Reagent: Alcohol, H2SO4 or HCl
Conditions: H2SO4 or HCl acting as catalyst
 Reaction: R-COOH + R’-OH ↔ R-COO-R’ + H2O
CH3COOH + CH3CH2OH ↔ CH3COOCH2CH3 + H2O
Mechanism: CH3COOH + H2SO4  HSO4- + CH3CHOOH2+  CH3C+O + H2O
CH3CH2OH + CH3C+O  CH3COOCH2CH3 + H+
H+ + HSO4-  H2SO4
13. Preparation of acid chloride
Reagent: PCl5 or PCl3 or SOCl2
Reaction: CH3COOH + PCl5  CH3COCl + POCl3 + HCl
3CH3COOH + PCl3  3CH3COCl + H3PO3
CH3COOH + SOCl2  CH3COCl + SO2 + HCl
14. Reaction of acid chloride with water
Reaction: CH3COCl + H2O  CH3COOH + HCl
Mechanism:

15. Reaction of acid chloride with alcohols

Reagent: Alcohol
Conditions: Room temperature
Reaction: CH3COCl + CH3CH2OH  CH3COOCH2CH3 + HCl
Note: This is a more efficient esterification reaction, as the reaction between carboxylic acid and
alcohol is reversible. The maximum yield of the reaction between carboxylic acid and alcohol is
70%, while this reaction goes to completion owing to the fact that it is a one-way reaction. The
alcohol must be dry for this reaction, or the acid chloride will react with the H2O.
16. Reaction of acid chloride with ammonia
Reagent: NH3
Conditions: Room temperature
Reaction: CH3COCl + NH3  CH3CONH2 + HCl
Note: The lone pair electron on the NH3 is used as a nucleophile to attack the C=O group.
17. Reaction of acid chloride with amides
Reagent: Amides
Condition: Room temperature
Reaction: CH3COCl + CH3NH2  CH3CONHCH3 + HCl
Note: The product of this reaction is N-methyl ethanamide. The “N” indicates that the methyl
group is attached to the nitrogen atom.
18. Reduction of acid chloride
Reagents: LiAlH4, ether as solution
Condition: Dry condition
Reaction: CH3COCl + 4[H]  CH3CH2OH + HCl
19. Hydrolysis of ester
Reagents: Water andH2SO4 or HCl in case of acid hydrolysis, NaOH and HCl in case of alkali
hydrolysis
 Conditions: Heat under reflux
Acid Hydrolysis: CH3COOCH2CH3 + H2O ↔ CH3COOH + CH3CH2OH
Alkali Hydrolysis: CH3COOCH2CH3 + NaOH  CH3COONa + CH3CH2OH
CH3COONa + HCl  CH3COOH + NaCl
Note: Acid hydrolysis is a reversible process, and has a lower yield. Alkali hydrolysis produces the
salt of the carboxylic acid, which on treatment with a dilute strong acid after cooling the solution
produces the carboxylic acid. The yield is higher in this process as the reaction is one-way.
20. Transesterification
Reagent: Organic acid or alcohol
Condition: HCl/H2SO4
Reaction with organic acid: CH3COOCH2CH3 + HCOOH ↔ HCOOCH2CH3 + CH3COOH
Reaction with alcohol: CH3COOCH2CH3 + CH3OH ↔ CH3COOCH3 + CH3CH2OH
21. Synthesis of biodiesel
Reagent: Alcohol
Condition: Heat with alcohol in presence of NaOH catalyst
Reaction:

Note: The NaOH is dissolved in the alcohol. This solution is then added to the triglycerides and
heated. After the reaction is complete, the fatty acids (triglycerides) are converted to methyl or
ethyl esters and the glycerol is separated as by-product.
22. Synthesis of soap
Reagents: NaOH
Condition: Heat under reflux
Reaction:

23. Synthesis of polyester

Reagents: dicarboxylic acid and diol for Terylene, di acid chloride and diol for PET
Reaction for synthesis of Terylene:
 Reaction for synthesis of PET:

Note: These are condensation polymerization reactions. H2O or HCl are eliminated as during
these reactions.
24. Synthesis of homopolymeric ester

Reaction: n CH2CH(OH)COOH 
Note: For the synthesis of homopolymeric ester, the monomer must contain two functional
groups on either side of the molecules that can react with each other.
25. Combustion of benzene
15
Reaction (excess O2): C6H6 + 2
O2  6CO2 + 3H2O
3
(limited O2): C6H6 + 2O2  6C + 3H2O
Observation: Smoky flame.
Note: This observation can be used to identify the presence of benzene ring in an organic
compound.
26. Reaction of benzene with chlorine
Reagent: Cl2
Conditions: UV ray
Reaction:

Note: The reaction takes place with the chlorine free radicals that are formed via this reaction:
Cl2 + (UV)  2Cl•
27. Reaction of benzene with hydrogen
Reagent: H2
Conditions: 140°C, Nickel catalyst
Reaction:
28. Reaction of benzene with halogen
Reagent: Cl2
Conditions: Room temperature, FeCl3/AlCl3/FeBr3 as catalyst
Reaction:

Mechanism:

29. Nitration of benzene

Reagents: HNO3
Condition: 60°C, H2SO4 catalyst
Reaction:

Mechanism:
 Note: If the temperature exceeds 60°C, a second -NO2 group is substituted in the 3- position.

30. Friedel-Craft acylation of benzene

Reagents: CH3Cl
Conditions: Dry conditions, AlCl3 catalyst
Reaction:

Mechanism:

31. Friedel-Craft alky acylation of benzene

Reagent: CH3COCl
Conditions: Dry condition, AlCl3 catalyst
Reaction:

Mechanism:
32. Friedel-Craft aryl acylation of benzene
Reagent: Benzoyl chloride
Condition: Dry conditions, AlCl3 catalyst
Reaction:

33. Sulfonation of benzene

Reagent: H2SO4
Condition: 120°C in case of concentrated aqueous H2SO4, room temperature in case of fuming
H2SO4
Reaction:

Mechanism: (Not in syllabus)

34. Reaction of toluene with chlorine

Reagent: Cl2
Condition: UV ray
Reaction:

35. Nitration of toluene

Reagent: HNO3
Conditions: 50°C, concentrated H2SO4
Reaction:

36. Hydrogenation of toluene

 Reagent: H2
Condition: 150°C, Nickel catalyst
Reaction:

37. Sulfonation of toluene

Reagent: Fuming H2SO4
Condition: Room temperature
Reaction:

38. Friedel-Craft alkylation of toluene

Reagent: CH3Cl
Condition: AlCl3
Reaction:

39. Friedel-Craft acylation of toluene

Reagent: CH3COCl
Condition: AlCl3
Reaction:

40. Reaction of phenyl ethanone with Brady’s reagent

Reagent: 2, 4-dinitro phenyl hydrazine
Condition: Concentrated HCl, warm at 50°C on water bath
Reaction:

Observation: Orange precipitation.

41. Reaction of phenyl ethanone with HCN

Reagent: HCN, NaOH
Condition: pH 8.0
Reaction:
42. Reduction of phenyl ethanone
Reagent: LiAlH4, ether as solution
Condition: Dry conditions
Reaction:

43. Iodoform reaction of phenyl ethanone

Reagent: I2, NaOH
Condition: Warm
Reaction:

Observation: Pale yellow precipitate of CHI3 formed.

44. Reaction of bromine with phenol
Reagent: Bromine water
Condition: RTP
Reaction:

Note: If the reaction is carried out in a non-polar solvent such as CS2 or CCl4, a mixture of 2-
bromo phenol and 4-bromo phenol forms.

45. Nitration of phenol

Reagent: HNO3
Reaction with dilute reagent:

Reaction of concentrated reagent:

46. Reaction of phenol with sodium

Reagent: sodium metal
Reaction:

Observation: Effervescence
47. Reaction of phenol of NaOH
Reagent: NaOH
Reaction:
 Note: This is an acid-base neutralization reaction. Phenol is a weak acid, and is weaker than
carbonic acid or carboxylic acid, and hence does not react with NaHCO3 or Na2CO3.
48. Reaction with acid chloride
Reagent: CH3COCl
Reaction:

49. Preparation of benzoic acid by hydrolysis of phenyl nitrile

Reagent: benzonitrile, HCl
Reaction:

50. Nitration of benzoic acid

Reagents: HNO3, H2SO4
Condition: Warm
Reaction: