26. Amines

Predict the product of the following reaction sequences.

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Give the expected products of lithium aluminum hydride reduction of the following compounds (followed by hydrolysis).

(a) butyronitrile

(b) N-cyclohexylacetamide

(c) e-caprolactam

Predict the products of the following reactions.

(e) <IMAGE>

(f) <IMAGE>

Show how each transformation may be accomplished by using a nitrile as an intermediate. You may use any necessary reagents.

(a) hexan-1-ol --> heptan-1-amine

Show how to prepare the following aromatic amines by aromatic nitration, followed by reduction. You may use benzene and toluene as your aromatic starting materials.

(d) m-aminobenzoic acid

Show how you can synthesize the following compounds starting with benzene, toluene, and alcohols containing no more than four carbon atoms as your organic starting materials. Assume that para is the major product (and separable from ortho) in ortho, para mixtures.

(g) <IMAGE>

Using any necessary reagents, show how you can accomplish the following multistep syntheses.

(b) <IMAGE of reaction>

Show how you would accomplish the following

synthetic conversions.

(a) benzyl bromide → benzylamine

Several additional amine syntheses are effectively limited

to making primary amines. The reduction of azides

and nitro compounds and the Gabriel synthesis leave

the carbon chain unchanged. Formation and reduction

of a nitrile adds one carbon atom. Show how these

amine syntheses can be used for the following conversions.

(c) 1-bromo-3-phenylheptane → 3-phenylheptan-1-amine

Reductive amination of aldehydes and ketones is a versatile method for attaching alkyl groups to amines, but the alkyl group is restricted to a 1° or 2° carbon by this method. Prof. Phil Baran of Scripps Research Institute has reported (Science, 2015, 348 (6237), 886–891) a novel way to reduce an aromatic nitro group and add the resulting amine to an alkene so that the aromatic amine is bonded to a 3° carbon—all in a continuous sequence of reactions.

For example:

<IMAGE of reaction>

Predict the products using these starting materials, all of which are reported in this paper.

(c) <IMAGE>

(d) <IMAGE>

Predict the products of the following reactions:

(d) <IMAGE of reaction>

Show how you can synthesize the following compounds starting with benzene, toluene, and alcohols containing no more than four carbon atoms as your organic starting materials. Assume that para is the major product (and separable from ortho) in ortho, para mixtures.

(b) N-methylbutan-1-amine

Show how you can synthesize the following compounds starting with benzene, toluene, and alcohols containing no more than four carbon atoms as your organic starting materials. Assume that para is the major product (and separable from ortho) in ortho, para mixtures.

(a) pentan-1-amine

Using any necessary reagents, show how you can accomplish the following multistep syntheses.

(c) <IMAGE of reaction>