26. Amines

What products are obtained when the following tertiary amines react with hydrogen peroxide followed by heat?

c.

Give the products expected when the following tertiary amines are treated with a peroxyacid and heated.

(b) N,N-diethylhexan-2-amine

Give the products expected when the following tertiary amines are treated with a peroxyacid and heated.

(c) cyclohexyldimethylamine

Predict the products from the reactions of the following amines with sodium nitrite in dilute HCl.

(b) N-ethylhexan-2-amine 

What products are obtained when the following tertiary amines react with hydrogen peroxide followed by heat?

d.

Give the products expected when the following tertiary amines are treated with a peroxyacid and heated.

(a) N,N-dimethylhexan-2-amine

Predict the products of the following reactions:

(i)

When the (R,R) isomer of the amine shown is treated with an excess of methyl iodide, then silver oxide, then heated, the major product is the Hofmann product.

(b) Some Zaitsev product is also formed. It has the (E) configuration. When the same amine is treated with mCPBA and heated, the Zaitsev product has the (Z) configuration. Use stereochemical drawings of the transition states to explain these observations.

Predict the products of the following reactions:

(i) <IMAGE of reaction>

Give the products expected when the following tertiary amines are treated with a peroxyacid and heated.

(d) N-ethylpiperidine

Predict the products of the following reactions:

(c)

(d)

In Section 21-16, we saw that Sevin insecticide is made by the reaction of 1-naphthol with methyl isocyanate. A Union Carbide plant in Bhopal, India, once used this process to make Sevin for use as an agricultural insecticide. On December 3,1984, either by accident or by sabotage, a valve was opened that admitted water to a large tank of methyl isocyanate. The pressure and temperature within the tank rose dramatically, and pressure-relief valves opened to keep the tank from bursting. A large quantity of methyl isocyanate rushed out through the pressure-relief valves, and the vapors flowed with the breeze into populated areas, killing about 2500 people and injuring many more.

(a) Write an equation for the reaction that took place in the tank. Explain why the pressure and temperature rose dramatically.

(b) Propose a mechanism for the reaction you wrote in part (a).

Predict the products of the following reactions:

(g)

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

(e)

(f)