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Q.(a)

(i) Write the mechanism of the following reaction : (2 + 1) 2CH3CH2OH→H+, 413 KCH3−CH2−O−CH2−CH3+H2O2CH_3CH_2OH \xrightarrow{H^+,\ 413\ K} CH_3-CH_2-O-CH_2-CH_3 + H_2O
(ii) Why ortho-nitrophenol is steam volatile while para-nitrophenol is not ?
(OR)
(b) What happens when (3 × 1)
(i) Anisole is treated with CH3ClCH_3Cl/anhydrous AlCl3AlCl_3 ?
(ii) Phenol is oxidised with Na2Cr2O7/H+Na_2Cr_2O_7/H^+ ?
(iii) (CH3)3C−OH(CH_3)_3C-OH is heated with Cu/573 K ? Write chemical equation in support of your answer.
CBSECBSE Class XII Board 2023Subjective· 3mImportance★★★★★
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Part (a): Acid protonates ethanol; a second ethanol displaces water (SN2S_N2, 413 K) and loses H+H^+ to give diethyl ether. o-Nitrophenol is steam volatile (intramolecular H-bond); p-nitrophenol is not (intermolecular H-bond).

Part (b): Anisole →\rightarrow o-/p-methylanisole (Friedel–Crafts); phenol →\rightarrow benzoquinone; (CH3)3C(CH_3)_3C-OH over Cu/573 K dehydrates to 2-methylprop-1-ene.

Part (a)

(i) Mechanism — acid-catalysed condensation of ethanol to diethyl ether (413 K). At 413 K the reaction follows an SN2S_N2 path (bimolecular):

  1. Protonation of ethanol by H+H^+ converts –OH into a good leaving group (–O+H2–\overset{+}{O}H_2):

CH3CH2OH+H+⇌CH3CH2O+H2CH_3CH_2OH + H^+ \rightleftharpoons CH_3CH_2\overset{+}{O}H_2

  1. Nucleophilic attack — the oxygen of a second ethanol molecule attacks the carbon bearing O+H2\overset{+}{O}H_2, displacing a water molecule in one step:

CH3CH2OH+CH3CH2O+H2→CH3CH2O+(H)CH2CH3+H2OCH_3CH_2OH + CH_3CH_2\overset{+}{O}H_2 \rightarrow CH_3CH_2\overset{+}{O}(H)CH_2CH_3 + H_2O

  1. Deprotonation of the protonated ether gives the product:

CH3CH2O+(H)CH2CH3→CH3CH2-O-CH2CH3+H+CH_3CH_2\overset{+}{O}(H)CH_2CH_3 \rightarrow CH_3CH_2\text{-}O\text{-}CH_2CH_3 + H^+

(At the higher temperature ~443 K, dehydration to ethene competes.) …

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