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Question. Give the structures of intermediates A through H in the following synthesis of trans-1-cyclohexyl-2-methoxycyclohexane.

Short Answer

Expert verified

Cyclohexanol on reaction with sulphuric acid followed by heating undergoes dehydration, and forms alkene which is product A. Product A undergoes epoxidation and forms product F which on reaction with product E undergoes coupling, and forms product G. Product A on alkoxymercuration-demercuration leads to the formation of product B in which methoxy group is attached.

Product B on reaction with hydrogen bromide followed by heating undergoes elimination and methoxy group acts as a good leaving group, and bromide ion adds to the alkene carbon which forms bromocyclohexane which is product D. Side product formed is methylbromide which is product C.

Formation of products A, B, C, D, E, F and G

Step by step solution

01

Step-1. Formation of products A, B, C, D, E, F, G:

Cyclohexanol on reaction with sulphuric acid followed by heating undergoes dehydration, and forms alkene which is product A. Product A undergoes epoxidation and forms product F which on reaction with product E undergoes coupling, and forms product G. Product A on alkoxymercuration-demercuration leads to the formation of product B in which methoxy group is attached.

Product B on reaction with hydrogen bromide followed by heating undergoes elimination and methoxy group acts as a good leaving group, and bromide ion adds to the alkene carbon which forms bromocyclohexane which is product D. Side product formed is methylbromide which is product C.

Formation of products A, B, C, D, E, F and G

02

Step-2. Formation of product H:

Product G undergoes reduction reaction with sodium and forms product H in which oxygen of hydroxyl group has negative charge and acts as a good nucleophile and further on reaction with methylbromide, the oxygen anion attacks at methyl and substitution reaction takes place which forms final product.

Formation of product H

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Most popular questions from this chapter

(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 (R)-propyleneoxide.

(c) Propose a mechanism for the base-catalyzed hydrolysis of pure (R)-propyleneoxide.

(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.

  1. Which of these reagents is most likely to be the actual oxidizing agent? That is, which reagent is reduced in the reaction? What is the likely function of the other reagents?
  2. When achiral reagents react to give a chiral product, that product is normally formed as a racemic mixture of enantiomers. How can the Sharpless epoxidation give just one nearly pure enantiomer of the product?
  3. Draw the other enantiomer of the product. What reagents would you use if you wanted to epoxidize geraniol to give this other enantiomer?
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