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Exercises · 8.17

Q.Complete each synthesis by giving missing starting material, reagent or products

Exercise 8.17 (i): structure(s) drawn as printed in the NCERT textbook, with the labels
Figure
Exercise 8.17 (ii): structure(s) drawn as printed in the NCERT textbook, with the labels
Figure
(iii) C6H5CHO→H2NCONHNH2\mathrm{C_6H_5CHO} \xrightarrow{\mathrm{H_2NCONHNH_2}}
Exercise 8.17 (iv): structure(s) drawn as printed in the NCERT textbook, with the labels O, C
Figure
Exercise 8.17 (v): structure(s) drawn as printed in the NCERT textbook, with the labels O, CHO
Figure
Exercise 8.17 (vi): structure(s) drawn as printed in the NCERT textbook, with the labels
Figure
(vii) C6H5CHO+CH3CH2CHO→Δdil.NaOH\begin{array}{c}\mathrm{C_6H_5CHO}\\ +\\ \mathrm{CH_3CH_2CHO}\end{array} \xrightarrow[\Delta]{\mathrm{dil.NaOH}}
(viii) CH3COCH2COOC2H5→(ii) H+(i) NaBH4\mathrm{CH_3COCH_2COOC_2H_5} \xrightarrow[\text{(ii) } \mathrm{H^+}]{\text{(i) } \mathrm{NaBH_4}}
Exercise 8.17 (ix): structure(s) drawn as printed in the NCERT textbook, with the labels OH
Figure
Exercise 8.17 (x): structure(s) drawn as printed in the NCERT textbook, with the labels CH2, CHO
Figure
Exercise 8.17 (xi): structure(s) drawn as printed in the NCERT textbook, with the labels 2, O
Figure
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Each step is a single named transformation. Watch which group actually reacts: alkaline KMnO4 oxidises benzylic side chains; SOCl2 makes acid chlorides; Tollens' and NaBH4 are selective (aldehyde-oxidation and carbonyl-reduction respectively); dilute NaOH drives an aldol condensation; O3/Zn-H2O cleaves C=C.

Step-by-step

(i) Ethylbenzene with hot KMnO4/KOH undergoes benzylic side-chain oxidation; the whole side chain becomes -COOH. Product: benzoic acid (C6H5COOH) (as potassium benzoate in base).

(ii) SOCl2 converts each -COOH into -COCl. Benzene-1,2-dicarboxylic acid therefore gives benzene-1,2-dicarbonyl dichloride (phthaloyl chloride), the ortho-C6H4(COCl)2.

(iii) Benzaldehyde + semicarbazide is a nucleophilic addition-elimination of the -NH2 of the =N-NH2 end onto the carbonyl, losing water. Product: benzaldehyde semicarbazone, C6H5-CH=N-NH-CO-NH2.

(iv) To put a C6H5-CO- group onto benzene you acylate it: the missing reagent is benzoyl chloride (C6H5COCl) with anhydrous AlCl3 (Friedel-Crafts acylation), giving benzophenone.

(v) Tollens' reagent oxidises only the aldehyde group (a mild oxidant); the ring ketone is untouched. The -CHO becomes -COOH. Product: 4-oxocyclohexane-1-carboxylic acid (the cyclohexane ring keeps its C=O and gains a para -COOH).

(vi) NaCN/HCl adds to the aldehyde carbonyl to form a cyanohydrin (the ketone-free -CHO is the reactive site). The -CHO becomes -CH(OH)CN. Product: 2-[cyano(hydroxy)methyl]benzoic acid, i.e. ortho-HOOC-C6H4-CH(OH)-CN.

(vii) Benzaldehyde has no alpha-hydrogen, so it acts only as the electrophile; propanal supplies the alpha-carbanion. A crossed aldol addition followed by dehydration (dilute NaOH, heat) gives the alpha,beta-unsaturated aldehyde C6H5-CH=C(CH3)-CHO (alpha-methylcinnamaldehyde, 2-methyl-3-phenylprop-2-enal).

(viii) NaBH4 reduces the ketone carbonyl but leaves the ester intact. Ethyl 3-oxobutanoate therefore gives, after acid work-up, ethyl 3-hydroxybutanoate, CH3-CH(OH)-CH2-COOC2H5.

(ix) CrO3 oxidises the secondary alcohol cyclohexanol to the ketone. Product: cyclohexanone. …

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