For the following reactions, ks and ke are respectively, the rate constants for substitution and elimination reactions…
Haloalkanes & Haloarenes · Class 12 · JEE Main Previous Year Question
For the following reactions,
and are respectively, the rate constants for substitution and elimination reactions and , the correct option is:
- a
and (A) > (B)
- b
and (A) > (B)
- c✓
and (B) > (A)
- d
and (B) > (A)
and (B) > (A)
Step 1: Identify the bases
Base A: (ethoxide) - small base
Base B: (tert-butoxide) - bulky base
Step 2: Understand substitution vs elimination
Small base (ethoxide):
- Can approach carbon easily
- Favors substitution
- Some elimination also occurs
- is higher (more substitution)
Bulky base (tert-butoxide):
- Sterically hindered
- Cannot easily approach carbon for
- Acts as base instead → E2 elimination favored
- is lower (less substitution, more elimination)
Step 3: Compare μ values
- Higher μ: More substitution relative to elimination
- Lower μ: More elimination relative to substitution
Ethoxide (A): More substitution → is higher
tert-Butoxide (B): More elimination → is lower
Therefore: ✓
Step 4: Compare values
Elimination rate constant:
- Bulky bases are better at elimination
- tert-Butoxide is stronger base and bulkier
- (B) > (A) ✓
Answer: (c) and (B) > (A)
Key Principles:
Base size and selectivity:
| Base | Size | Favors | μ value | |------|------|--------|----------| | Small (OEt⁻, OH⁻) | Small | | High | | Bulky (t-BuO⁻, LDA) | Large | E2 | Low |
Competition between and E2:
- Same substrate can undergo both
- Base size determines selectivity
- Temperature also affects (heat favors elimination)
- Substrate structure matters (1° favors , 3° favors E2)
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