CHAPTER 8: Question 8

 

Simple Answers

At room temperature, the two chair conformations (A and B) of chlorocyclohexane are in rapid equilibrium, thus only a spectrum corresponding to the average of the two conformations is observed. This results in four lines in the spectrum corresponding to C1, C2 (=C6), C3 (=C5) and C4 as shown in the diagram below.

At -150oC however, the equilibrium between the two conformations is extremely slow, so now signals are seen for each of the two conformations, giving eight lines in total as shown in the diagram. The two conformations A and B are diastereomers of one another and so have different physical properties including solubility. Thus one of the two conformations (B) is less soluble in the NMR solvent than the other conformation, and crystalizes out. This leaves just the other conformation (A) in the solution, so only the four lines corresponding to this conformation are observed. If the crystals of conformation B are redissolved, then a spectrum corresponding to just the four lines of conformation B will be observed. If the solution of either conformation A or conformation B is allowed to warm to room temperature, then the rate at which the two conformations interchange will increase as the temperature is raised, and by the time the solution reaches room temperature the equilibrium between A and B will have been reestablished and the original four line, average spectrum will be observed.
 

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