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Compounds Containing Nitrogen question

2024 · 31 Jan · Shift 2 · Q19
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Compounds Containing Nitrogen question

2024 · 31 Jan · Shift 2 · Q19

JEE MainChemistryCompounds Containing NitrogenMCQ+4 / −1
Given below are two statements : Statement I : Aniline reacts with con. H2SO4\mathrm{H}_2 \mathrm{SO}_4H2​SO4​, followed by heating at 453−473 K453-473 \mathrm{~K}453−473 K gives p\mathrm{p}p-aminobenzene sulphonic acid, which gives blood red colour in the 'Lassaigne's test'. Statement II : In Friedel - Craft's alkylation and acylation reactions, aniline forms salt with the AlCl3\mathrm{AlCl}_3AlCl3​ catalyst. Due to this, nitrogen of aniline aquires a positive charge and acts as deactivating group. In the light of the above statements, choose the correct answer from the options given below :
  1. A
    Both statement I and statement II are true
  2. B
    Statement I is true but statement II is false
  3. C
    Statement I is false but statement II is true
  4. D
    Both statement I and statement II are false
View written solutionFree

Correct answer: A

  1. Check Statement I

    Aniline reacts with concentrated sulfuric acid first to form anilinium hydrogen sulfate, and on heating at about 453−473 K453-473\,\text{K}453−473K, rearrangement/sulfonation gives ppp-aminobenzene sulfonic acid (sulphanilic acid).

    \ceC6H5NH2−>[conc. H2SO4][453−473 K]H2N−C6H4−SO3H\ce{C6H5NH2 ->[conc.\ H2SO4][453-473\ K] H2N-C6H4-SO3H}\ceC6H5NH2−>[conc. H2SO4][453−473 K]H2N−C6H4−SO3H

    Now, in Lassaigne's test for sulfur, sodium fusion converts sulfur into sodium sulfide, which with sodium nitroprusside gives a violet/purple color. However, compounds containing both nitrogen and sulfur on fusion can form sodium thiocyanate, and with ferric ion this gives a blood red color due to ferric thiocyanate.

    Since sulphanilic acid contains both NNN and SSS, it gives blood red color in Lassaigne's test.

    Therefore, Statement I is true.

  2. Check Statement II

    In Friedel-Crafts alkylation/acylation, aniline does not undergo the reaction normally because the lone pair on nitrogen coordinates with the Lewis acid catalyst \ceAlCl3\ce{AlCl3}\ceAlCl3 to form a salt/complex.

    \ceC6H5NH2+AlCl3−>C6H5NH2.AlCl3\ce{C6H5NH2 + AlCl3 -> C6H5NH2.AlCl3}\ceC6H5NH2+AlCl3−>C6H5NH2.AlCl3

    This interaction makes nitrogen positively polarized/effectively positively charged, reducing electron density on the benzene ring. Hence, the −\ceNH2-\ce{NH2}−\ceNH2 group loses its activating effect and behaves as a deactivating group.

    Therefore, Statement II is true.

  3. Conclusion

    Both Statement I and Statement II are true.

    So the correct option is:

    A\boxed{\text{A}}A​

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