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문제 19
Draw the important resonance contributors for both resonance-stabilized cations (in brackets) in the mechanism for acid-catalyzed hydrolysis of an amide.
문제 20.21
Show how the following ketones might be synthesized from the indicated acids, using any necessary reagents.
(a) propiophenone from propionic acid (using Friedel–Crafts acylation)
문제 20a
Propose a mechanism for the hydrolysis of N,N-dimethylacetamide
(a) under basic conditions.
문제 20b
Propose a mechanism for the hydrolysis of N,N-dimethylacetamide
(b) under acidic conditions.
문제 22
Propose a mechanism for the basic hydrolysis of benzonitrile to the benzoate ion and ammonia.
문제 23
The mechanism for acidic hydrolysis of a nitrile resembles the basic hydrolysis, except that the nitrile is first protonated, activating it toward attack by a weak nucleophile (water). Under acidic conditions, the proton transfer (tautomerism) involves protonation on nitrogen followed by deprotonation on oxygen. Propose a mechanism for the acid-catalyzed hydrolysis of benzonitrile to benzamide.
문제 24a
In which step(s) of the hydride reduction of an ester does the compound undergo reduction? (Hint: Count the bonds to oxygen.)
문제 24b
Propose a mechanism for the reduction of octanoyl chloride by lithium aluminum hydride.
문제 26
Draw a mechanism for the acidic hydrolysis of the magnesium salt shown below to acetophenone.
문제 27
Draw a mechanism for the reaction of propanoyl chloride with 2 moles of phenylmagnesium bromide.
문제 28a
Show how you would add a Grignard reagent to an ester or a nitrile to synthesize
(a) 4-phenylheptan-4-ol.
문제 28b
Show how you would add a Grignard reagent to an ester or a nitrile to synthesize
(b) heptan-4-ol.
문제 28c
Show how you would add a Grignard reagent to an ester or a nitrile to synthesize
(c) pentan-2-one.
문제 30a
Show how Friedel–Crafts acylation might be used to synthesize the following compounds.
a. acetophenone
문제 30b
Show how Friedel–Crafts acylation might be used to synthesize the following compounds.
b. benzophenone
문제 30c
Show how Friedel–Crafts acylation might be used to synthesize the following compounds.
c. n-butylbenzene
문제 32a,b
Show how you would use anhydrides to synthesize the following compounds. In each case, explain why an anhydride might be preferable to an acid chloride.
(a) n-octyl formate
(b) n-octyl acetate
문제 32c,d
Show how you would use anhydrides to synthesize the following compounds. In each case, explain why an anhydride might be preferable to an acid chloride.
(c) phthalic acid monoamide
(d) succinic acid monomethyl ester
문제 34a
Suggest the most appropriate reagent for each synthesis, and explain your choice.
(a)
문제 34b
Suggest the most appropriate reagent for each synthesis, and explain your choice.
(b)
문제 34c
Suggest the most appropriate reagent for each synthesis, and explain your choice.
(c)
문제 34d
Suggest the most appropriate reagent for each synthesis, and explain your choice.
(d)
문제 35a,b,c
Show how you would synthesize each compound, starting with an ester containing no more than eight carbon atoms. Any other necessary reagents may be used.
(a) Ph3C–OH
(b) (PhCH2)2CHOH
(c) PhCONHCH2CH3
문제 35d,e,f
Show how you would synthesize each compound, starting with an ester containing no more than eight carbon atoms. Any other necessary reagents may be used.
(d) Ph2CHOH
(e) PhCH2OH
(f) PhCOOH
문제 35i
Show how you would synthesize each compound, starting with an ester containing no more than eight carbon atoms. Any other necessary reagents may be used.
(i) HO–(CH2)8–OH
문제 36a,b
Show how you would accomplish the following synthetic transformations. You may use any necessary reagents.
(a) N-ethylbenzamide → benzylethylamine
(b) ethyl benzoate → N-ethylbenzamide
문제 36c,d
Show how you would accomplish the following synthetic transformations. You may use any necessary reagents.
(c) pyrrolidine → N-acetylpyrrolidine
(d) γ-aminobutyric acid → pyrrolidine
문제 37
Show how you would accomplish the following syntheses using amides as intermediates. You may use any necessary reagents.
(a) benzoic acid → benzyldimethylamine
(b) pyrrolidine → N-ethylpyrrolidine
(c) cyclopentanecarboxylic acid → cyclopentanecarbonitrile
문제 38a
Show how you would convert the following starting materials to the indicated nitriles:
(a) phenylacetic acid → phenylacetonitrile
문제 38b
Show how you would convert the following starting materials to the indicated nitriles:
(b) phenylacetic acid → 3-phenylpropionitrile
