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Q.

Given below are two statements. One is labelled as Assertion (A) and the other is labelled as reason (R). 

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a

Both (A) and (R) are true but (R) is not the correct explanation of (A)

b

Both (A) and (R) are true and (R) is the correct explanation of (A)

c

Both (A) and (R) are false

d

(A) is true but (R) is false

answer is D.

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Detailed Solution

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Vinylic halides are not reactive towards nucleophilic substitution reactions because

  • Resonance effect: In vinylic halides, the electron pairs on halogen atom are in conjugation with p-electrons of the ring and the following resonating structures are possible. C—Cl bond acquires a partial double bond character due to resonance. As a result, the bond cleavage in vinylic halide is difficult than haloalkane and therefore, they are less reactive towards nucleophilic substitution reaction.
  • Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the carbon atom attached to halogen is sp3 hybridised while in case of vinylic halide, the carbon atom attached to halogen is sp2 hybridised. The sp2 hybridised carbon with a greater s-character is more electronegative and can hold the electron pair of C—X bond more tightly than sp3 -hybridised carbon in haloalkane with less s-chararcter. Thus, C—Cl bond length in haloalkane is 177pm while in vinylic halide is 169 pm. Since it is difficult to break a shorter bond than a longer bond, therefore, vinylic halides are less reactive than haloalkanes towards nucleophilic substitution reaction. 
  • Instability of vinyl cation: In case of vinylic halides, the phenyl cation formed as a result of self-ionization will not be stabilized by resonance and therefore, SN1 mechanism is ruled out.
  • Because of the possible repulsion, it is less likely for the electron rich nucleophile to approach electron rich arenes. 
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