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JEE Advanced 2017 Paper 1 · Chemistry · Hydrocarbons · easy

Aromatic substitution and its limitations are used in the following statements.

One or more options correct

Aromatic substitution and its limitations are used in the following statements. The CORRECT statement(s) is/are
  1. A. Friedel-Crafts alkylation of benzene with 11-chloropropane and anhydrous AlCl3\mathrm{AlCl_3} gives mainly isopropylbenzene, because the primary carbocation-like species rearranges by a hydride shift.
  2. B. Nitrobenzene undergoes Friedel-Crafts acylation with CH3COCl/AlCl3\mathrm{CH_3COCl}/\mathrm{AlCl_3} at the meta position in good yield.
  3. C. Acylation of benzene with propanoyl chloride/AlCl3\mathrm{AlCl_3} followed by Clemmensen reduction gives nn-propylbenzene free from isopropylbenzene.
  4. D. Nitration of chlorobenzene with HNO3/H2SO4\mathrm{HNO_3}/\mathrm{H_2SO_4} gives mainly 11-chloro-33-nitrobenzene, since −Cl-\mathrm{Cl} is an electron-withdrawing group.
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Answer: A, C

(A) With AlCl3\mathrm{AlCl_3} the incipient primary cation CH3CH2CH2+\mathrm{CH_3CH_2CH_2^+} undergoes a 1,2-hydride shift to the more stable secondary cation, which alkylates benzene, so isopropylbenzene (cumene) predominates: correct. (B) A nitro group strongly deactivates the ring (and complexes with AlCl3\mathrm{AlCl_3}), so nitrobenzene does not undergo Friedel-Crafts reactions at all: wrong. (C) The acylium ion CH3CH2CO+\mathrm{CH_3CH_2CO^+} does not rearrange; it gives propiophenone, PhCOCH2CH3\mathrm{PhCOCH_2CH_3}. Clemmensen reduction (Zn(Hg)/HCl\mathrm{Zn(Hg)/HCl}) converts C=O\mathrm{C=O} to CH2\mathrm{CH_2}, giving nn-propylbenzene with no isopropyl isomer: correct. (D) Chlorine withdraws electrons by the −I-I effect, which deactivates the ring, but its lone pairs donate by +M+M, which directs the incoming nitronium ion ortho and para. The major products are 11-chloro-44-nitro and 11-chloro-22-nitrobenzene: wrong.
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