Chapter 14: Q 42P (page 748)
Question. Give the structures of intermediates A through H in the following synthesis of trans-1-cyclohexyl-2-methoxycyclohexane.

Short Answer

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Chapter 14: Q 42P (page 748)
Question. Give the structures of intermediates A through H in the following synthesis of trans-1-cyclohexyl-2-methoxycyclohexane.


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(a) When ethylene oxide is treated with anhydrous HBr gas, the major product is 1,2-dibromoethane. When ethylene oxide is treated with concentrated aqueous HBr, the major product is ethylene glycol. Use mechanisms to explain these results.
(b) Under base-catalyzed conditions, several molecules of propylene oxide can react to give short polymers. Propose a mechanism for the base-catalyzed formation of the following trimer.

Propylene oxide is a chiral molecule. Hydrolysis of propylene oxide gives propylene glycol, another chiral molecule.
(a) Draw the enantiomers of propylene oxide.
(b) Propose a mechanism for the acid-catalyzed hydrolysis of pure .
(c) Propose a mechanism for the base-catalyzed hydrolysis of pure .
(d) Explain why the acid-catalyzed hydrolysis of optically active propylene oxide gives a product with lower enantiomeric excess and a rotation opposite that of the product of the base- catalyzed hydrolysis.
Question. Show how you would make the following ethers, using only simple alcohols and any needed reagents as your starting materials.
(a)1-methoxypropane
(b) 2-ethoxy-2-methylbutane
(c) 4-methylbenzyl cyclopentyl ether
(d) Trans-2-ethoxycyclohexanol
(e) The TIPS ether of (d)
(f) 4-methylcyclohexyl cyclopentyl ether
Question. (A true story.) An inexperienced graduate student moved into a laboratory and began work. He needed some diethyl ether for a reaction, so he opened an old, rusty 1-gallon can marked 鈥渆thyl ether鈥 and found there was half a gallon left. To purify the ether, the student set up a distillation apparatus, started a careful distillation, and went to the stockroom for the other reagents he needed. While he was at the stockroom, the student heard a muffled 鈥渂oom鈥. He quickly returned to his lab to find a worker from another laboratory putting out a fire. Most of the distillation apparatus was embedded in the ceiling.
(a) Explain what probably happened.
(b) Explain how this near disaster might have been prevented.
Question. The 2001 Nobel Prize in Chemistry was awarded to three organic chemists who have developed methods for catalytic asymmetric synthesis. An asymmetric (or enantioselective) synthesis is one that converts an achiral starting material into mostly one enantiomer of a chiral product. K. Barry Sharpless (The Scripps Research Institute) developed an asymmetric epoxidation of allylic alcohols that gives excellent chemical yields and greater than 90% enantiomeric excess.
The Sharpless epoxidation uses tert-butyl hydroperoxide, titanium(IV) isopropoxide, and a dialkyl tartarate ester as the reagents. The following epoxidation of geraniol is typical.

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