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Q.Complete the following chemical equations:

(i) R−CHO+…+3O‾H⟶RCOO‾+2Ag+2H2O+4NH3R-CHO + \ldots + 3\overline{O}H \longrightarrow RCO\overline{O} + 2Ag + 2H_2O + 4NH_3
(ii) Toluene (C6H5CH3)+CrO2Cl2→CS2…→H3O+(C_6H_5CH_3) + CrO_2Cl_2 \xrightarrow{CS_2} \ldots \xrightarrow{H_3O^+} Benzaldehyde (C6H5CHO)(C_6H_5CHO)
(iii) Benzene (C6H6)→Anhydrous AlCl3 / CuClCO, HCl…(C_6H_6) \xrightarrow[\text{Anhydrous } AlCl_3\,/\,CuCl]{CO,\ HCl} \ldots
(iv) …→Pd−BaSO4H2\ldots \xrightarrow[Pd-BaSO_4]{H_2} Benzaldehyde (C6H5CHO)(C_6H_5CHO)
(v) R−CN+SnCl2+HCl⟶…→H3O+RCHOR-CN + SnCl_2 + HCl \longrightarrow \ldots \xrightarrow{H_3O^+} RCHO OR Write notes on the following:
(i) Clemmensen Reduction
(ii) Wolff-Kishner Reduction
(iii) Aldol Condensation
(iv) Cannizzaro's Reaction
(v) Hell Volhard Zelinsky Reaction
Uttar Pradesh UpmspUP Board (UPMSP) Intermediate 2022Subjective· 5mImportance★★★★★
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Each blank is a named aldehyde synthesis/reaction: (i) Tollens' reagent oxidation, (ii) Etard reaction, (iii) Gattermann-Koch reaction, (iv) Rosenmund reduction, (v) Stephen reduction.

  1. Tollens' (silver-mirror) reaction. The missing reactant is Tollens' reagent, 2[Ag(NH3)2]+2[Ag(NH_3)_2]^+ (ammoniacal silver nitrate). It oxidises the aldehyde to the carboxylate and deposits metallic silver: R−CHO+2[Ag(NH3)2]++3 O‾H⟶RCOO‾+2Ag↓+2H2O+4NH3R{-}CHO + 2[Ag(NH_3)_2]^{+} + 3\,\overline{O}H \longrightarrow RCO\overline{O} + 2Ag\downarrow + 2H_2O + 4NH_3
  2. Etard reaction. Toluene is oxidised by chromyl chloride (CrO2Cl2CrO_2Cl_2) in CS2CS_2 to a brown chromium complex, which on acidic hydrolysis (H3O+H_3O^+) gives benzaldehyde: C6H5CH3→CrO2Cl2,  CS2C6H5CH(OCrOHCl2)2⏟chromium complex→H3O+C6H5CHOC_6H_5CH_3 \xrightarrow{CrO_2Cl_2,\;CS_2} \underbrace{C_6H_5CH(OCrOHCl_2)_2}_{\text{chromium complex}} \xrightarrow{H_3O^+} C_6H_5CHO
  3. Gattermann–Koch reaction. Benzene treated with carbon monoxide and HCl in presence of anhydrous AlCl3AlCl_3/CuClCuCl gives benzaldehyde directly: C6H6+CO+HCl→anhyd. AlCl3/CuClC6H5CHO+HClC_6H_6 + CO + HCl \xrightarrow{anhyd.\,AlCl_3/CuCl} C_6H_5CHO + HCl
  4. Rosenmund reduction. The missing reactant is an acyl chloride, C6H5COClC_6H_5COCl (benzoyl chloride). Hydrogenation over palladium poisoned with BaSO4BaSO_4 stops at the aldehyde: C6H5COCl→Pd-BaSO4H2C6H5CHO+HClC_6H_5COCl \xrightarrow[Pd\text{-}BaSO_4]{H_2} C_6H_5CHO + HCl …

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