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Alcohols Phenols and Ethers appeared 23 times across 3 years — 2.7% of Chemistry. This question is from Cleavage of C-O Bond in Ethers.

Year 2026 2025 2024 Total
Questions 7 5 11 23

The major product(P) in the following reaction is
Cleavage of C-O Bond in Ethers diagram for Q67 - JEE Main 2024 Morning
Reaction showing an aromatic ether with a vinyl group reacting with excess HBr.

Solution & Explanation

Core Logic

The substrate has two reactive functional groups towards HBr (in excess):

  • An aromatic ether (anisole-type) linkage: -O-CH₂-CH₃
  • An isolated alkene (vinyl) group attached to the aromatic ring: -CH=CH₂
  • Reaction 1: Ether Cleavage The ether linkage reacts with HBr. Protonation of the ether oxygen occurs first, forming an oxonium ion. The Br^- ion then attacks the less hindered (and sp³ hybridized) alkyl group (SN2 mechanism), specifically the ethyl group. The C(aryl)-O bond is much stronger due to partial double bond character from resonance, so it does NOT break. This yields a phenol group on the ring and ethyl bromide (CH₃-CH₂-Br).

    Reaction 2: Electrophilic Addition to Alkene The vinyl group (-CH=CH₂) undergoes electrophilic addition with HBr. Protonation yields the more stable secondary benzylic carbocation (Markovnikov's rule). The Br^- then attacks this carbocation to form a 1-bromoethyl group attached to the ring.

Step 1: Detailed Mechanism

Cleavage of C-O Bond in Ethers diagram for Q67 - JEE Main 2024 Morning
Reaction showing an aromatic ether with a vinyl group reacting with excess HBr.

Cleavage of C-O Bond in Ethers diagram for Q67 - JEE Main 2024 Morning
Reaction showing an aromatic ether with a vinyl group reacting with excess HBr.

Final product: The ring retains an -OH group (phenol) at the original ether position, and the vinyl group is converted into a -CH(Br)-CH₃ group.

Pattern Recognition

Excess HBr with an aryl-alkyl ether always cleaves the alkyl C-O bond to give phenol + alkyl bromide. Never break the aryl C-O bond.

Chapter Mix

Class 12 Chemistry: Alcohols Phenols and Ethers Class 11 Chemistry: Hydrocarbons

Cleavage of C-O Bond in Ethers diagram for Q67 - JEE Main 2024 Morning
Reaction showing an aromatic ether with a vinyl group reacting with excess HBr.

More Alcohols Phenols and Ethers Previous-Year Questions — Page 2

Q66 jee_main_2026_24_january_evening Classification of Alcohols
From the following, how many compounds contain at least one secondary alcohol? (I)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
(II)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
(III)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
(IV)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
(V)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
(VI)
Classification of Alcohols diagram for Q66 - JEE Main 2026 Evening
Various organic structures displaying alcohol functional groups.
Choose the correct answer from the options given below:
  • A. Five
  • B. Three
  • C. Four
  • D. two

Solution

Core Logic

A secondary alcohol features a hydroxyl group (-OH) attached to a carbon atom that is bonded to two other carbon atoms (2° carbon). Evaluating the structures based on visual analysis: Compounds II, IV, and V contain at least one hydroxyl group on a 2° carbon. Therefore, 3 compounds feature a secondary alcohol.

Pattern Recognition

Spot the carbon carrying the -OH group. Count the C-C bonds attached to it. 1 = Primary, 2 = Secondary, 3 = Tertiary. Phenols are aromatic and distinct from secondary alcohols.

Chapter Mix

Class 12 Chemistry: Alcohols, Phenols and Ethers

Q54 jee_main_2026_28_january_morning Kolbe Schmitt Reaction
Consider the following reaction sequence Compound (x) [76.6%C, 6.38%H, vapour density 47] (i)CO₂,NaOH,120°C,high pressure (ii)H₃O⁺ Compound (y) (Major Product) Compound (y) develops characteristic colour with neutral FeCl₃ solution. Identify the INCORRECT statement from the following for the above sequence.
  • A. Both compounds x and y will dissolve in NaOH.
  • B. Compound y will dissolve in NaHCO₃ and evolve a gas.
  • C. Compound x is more acidic than compound y.
  • D. Both compounds x and y will burn with sooty flame.

Solution

Core Logic

Based on empirical data for (x): Molar Mass = 2 × Vapour Density = 2 × 47 = 94~g/mol. C = 76.6% (76.6/12) ≈ 6.38 H = 6.38% (6.38/1) ≈ 6.38 O = 17.02% (17.02/16) ≈ 1.06 Ratio C:H:O ≈ 6:6:1 C₆H₆O (Phenol).

Step 1: Identifying Compounds

Compound (x) is Phenol. It reacts with CO₂/NaOH via Kolbe-Schmitt reaction to form Salicylic Acid as the major product (Compound y).

Kolbe Schmitt Reaction of Phenol to Salicylic Acid
Kolbe Schmitt Reaction of Phenol to Salicylic Acid

Step 2: Checking Options

(1) Both Phenol and Salicylic acid dissolve in NaOH. (True) (2) Salicylic acid (y) has a -COOH group and dissolves in NaHCO₃, evolving CO₂ gas. (True) (3) Salicylic acid (y) is much more acidic than Phenol (x) due to the presence of the carboxylic acid group and intramolecular hydrogen bonding in its conjugate base. Therefore, the statement "x is more acidic than y" is INCORRECT. (4) Being highly aromatic compounds, both burn with a sooty flame. (True)

Pattern Recognition

The reaction sequence Phenol + CO₂/NaOH arrow Salicylic acid is a staple (Kolbe's Reaction). Always test functional group properties: Phenols dissolve in NaOH but not NaHCO₃, while Carboxylic acids dissolve in both.

Chapter Mix

Class 12 Chemistry: Alcohols Phenols and Ethers Class 11 Chemistry: Organic Chemistry Some Basic Principles and Techniques

Q jee_main_2025_07_april_morning Acidity of Phenols
Which of the following compounds is least likely to give effervescence of CO₂ in presence of aq. NaHCO₃ ?
  • A.
  • B.
  • C. Ph - NH₃(+) Cl(-)
  • D.

Solution

Core Logic

For a compound to release CO₂ upon reaction with aqueous NaHCO₃, its acidity must be strictly greater than that of carbonic acid (H₂CO₃).

Let's evaluate the acidity of the options:

  • Picric Acid (2,4,6-trinitrophenol - Option A): Extremely acidic (pKₐ ≈ 0.38) due to three strong electron-withdrawing nitro groups. Reacts with NaHCO₃ easily.
  • 4-Nitrobenzoic Acid (Option B): Carboxylic acids generally have pKₐ ≈ 4--5. More acidic than carbonic acid (pKₐ ≈ 6.3). Reacts with NaHCO₃.
  • Anilinium Chloride (Option 3): A salt of a strong acid and weak base. The anilinium ion is quite acidic (pKₐ ≈ 4.6) and easily decomposes NaHCO₃.
  • 4-Nitrophenol (Option D): Only one nitro group is present. Its acidity (pKₐ ≈ 7.15) is weaker than carbonic acid. Hence, it does not react with sodium bicarbonate to yield effervescence of CO₂.
Pattern Recognition

Acid-bicarbonate test shortcut:

  • All carboxylic acids and picric acid give a positive bicarbonate test.
  • Normal phenols and mono/di-nitrophenols are too weak to decompose bicarbonate.
Chapter Mix

Class 12 Chemistry: Alcohols, Phenols and Ethers Class 12 Chemistry: Carboxylic Acids

Q31 jee_main_2025_07_april_morning Physical Properties of Ethers
Given below are two statements: Statement I: Dimethyl ether is completely soluble in water. However, diethyl ether is soluble in water to a very small extent. Statement II: Sodium metal can be used to dry diethyl ether and not ethyl alcohol. In the light of given statements, choose the correct answer from the options given below:
  • A. Statement I is false but Statement II is true
  • B. Both Statement I and Statement II are false
  • C. Statement I is true but Statement II is false
  • D. Both Statement I and Statement II are true

Solution

Core Logic

Statement I: Dimethyl ether (CH₃OCH₃) is highly soluble in water because its smaller alkyl chain allows substantial hydrogen bonding with water molecules. In contrast, diethyl ether has a larger hydrophobic ethyl group which drastically reduces its water solubility (to about 7.5 g per 100 mL). Thus, Statement I is true.

Statement II: Sodium metal (Na) reacts violently with alcohols like ethyl alcohol to release hydrogen gas:

2C₂H₅OH + 2Na arrow 2C₂H₅ONa + H₂

Since diethyl ether has no active acidic hydrogen, it does not react with sodium metal. Hence, sodium can dry diethyl ether but cannot be used for ethyl alcohol. Statement II is true.

Pattern Recognition

Ethers are miscible with water primarily when the non-polar alkyl parts are very small. Active hydrogen presence (-OH group in alcohols) prevents the use of alkali metals like sodium for moisture removal.

Chapter Mix

Class 12 Chemistry: Alcohols, Phenols and Ethers

Q jee_main_2025_08_april_evening Williamson Ether Synthesis
Which one of the following reactions will not lead to the desired ether formation in major proportion? (Given labels: iso-Bu ⇒ isobutyl, sec-Bu ⇒ sec-butyl, n-Pr ⇒ n-propyl, ^tBu ⇒ tert-butyl, Et ⇒ ethyl)
  • A. ^tBuO^-Na^+ + EtBr ^tBu-O-Et
  • B. PhO^-Na^+ + CH₃Br Ph-O-CH₃
  • C. PhO^-Na^+ + n-PrBr n-Pr-O-Ph
  • D. iso-BuO^-Na^+ + sec-BuBr sec-Bu-O-iso-Bu

Solution

Core Logic

Williamson Ether Synthesis operates strictly via an SN2 mechanism. To optimize ether formation yields, the alkyl halide component MUST be primary (1^°) or methyl to evade spatial shielding restrictions.

Let us review the alkyl halide across the options:

  • Option 1: Ethyl bromide (EtBr) is 1^° arrow Excellent ether yield via substitution.
  • Option 2: Methyl bromide (CH₃Br) is a unhindered methyl halide arrow High substitution efficiency.
  • Option 3: n-Propyl bromide (n-PrBr) is 1^° arrow Clean substitution pathway.
  • Option 4: sec-Butyl bromide (sec-BuBr) is a secondary (2^°) alkyl halide. When a sterically hindered 2^° halide is treated with a strongly basic alkoxide reagent like isobutoxide, alkene elimination (E2) competes aggressively and dominates as the major pathway over nucleophilic substitution (SN2).
    Competing elimination reaction mechanism layout for Q37
    Competing elimination reaction mechanism layout for Q37
Pattern Recognition

Williamson Synthesis Rule: Alkoxide can be as massive and complex as desired (3^° or branched), but the Alkyl Halide MUST be unhindered (1^° or methyl). If the halide is 2^° or 3^°, elimination wins, forming an alkene instead of an ether.

Chapter Mix

Class 12 Chemistry: Alcohols, Phenols and Ethers

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JEE Physics: Waves (+15.5%) | Electrostatics: Concentric Shells (-29.7%) | Modern Physics: Photoelectric Clones (+34.2%) | Mathematics: Definite Integrals (+18.1%) | Chemistry: Coordination Splitting (-11.4%) | JEE Physics: Waves (+15.5%) | Electrostatics: Concentric Shells (-29.7%) | Modern Physics: Photoelectric Clones (+34.2%) | Mathematics: Definite Integrals (+18.1%) | Chemistry: Coordination Splitting (-11.4%)