10. Addition Reactions

What stereoisomers are obtained from the reaction of the alkenes in [PROBLEM 10-32] with a peroxyacid ­followed by reaction with hydroxide ion?

c. cis-2-pentene

d. trans-2-pentene

Predict the products of the following reactions.

(g) trans-2,3-epoxyoctane + H⁺, H₂O

(h) propylene oxide + methylamine (CH₃NH₂)

Predict the products of the following reactions.

(m)

(n)

The existence of the NIH shift was established by determining the major product obtained from rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.

a. What would be the major product if the NIH shift occurs? (Hint: A C—H bond is easier to break than a C—D bond.)

Cellosolve® is the trade name for 2-ethoxyethanol, a common industrial solvent. This compound is produced in chemical plants that use ethylene as their only organic feedstock. Show how you would accomplish this industrial process.

Propose a mechanism for each of the following reactions:

a.

Predict the product of the following epoxide addition reactions.

(a)

The existence of the NIH shift was established by determining the major product obtained from rearrangement of the following arene oxide, in which a hydrogen has been replaced by a deuterium.

b. What would be the major product if the carbocation forms phenol by losing H⁺ or D⁺, rather than by going through the NIH shift?

Predict the major product when each reagent reacts with ethylene oxide.

(d) PhNH₂ (aniline)

(e) KCN (potassium cyanide)

(f) NaN₃ (sodium azide)

Triethylene glycol is one of the products obtained from the reaction of excess ethylene oxide and hydroxide ion. Propose a mechanism for its formation.

Three arene oxides can be obtained from phenanthrene.

c. If a phenanthrene oxide can lead to the formation of more than one phenol, which phenol will be obtained in greater yield?

Predict the major products of the following reactions, including stereochemistry where appropriate.

(c) (2S,3R)-2-ethyl-2,3-dimethyloxirane + CH₃O^– / CH₃OH

(d) (2S,3R)-2-ethyl-2,3-dimethyloxirane + H⁺ / CH₃OH

In Chapter 13, we discuss the ring-opening reactions of epoxides, such as the one shown here.

(a) Based on the bonds formed and the bonds broken, calculate ∆H°.

Propose a mechanism for the following reaction.