Chem 112A Fall 2012 Homework E Cycloalkane nomenclature and conformational analysis (lectures 9/18) From the Loudon

don textbook: Read pages 268-285 and 288- 290 (skip the discussion about enantiomers on pages 285-288). Solve problems: 7.1, 7.5, 7.6, , 7.7, 7.10 (a and b only), 7.11, 7.15, 7.36, 7.37, 7.38

Conformational analysis of Menthol Menthol (shown below) is a major component of peppermint oil, and is responsible for the cooling sensation felt upon contact with skin.
Change in free energy for select cyclohexane substituents upon chair-flip conformational change (kcal/mol): H 0 Me 1.70 Et 1.75 iPr 2.20 tBu 5 OH 0.94

menthol

A. Complete the chair conformation drawings of menthol below (center of page) by adding the alkyl substituents at the appropriate positions. B. Using the values provided above, calculate G for this equilibrium. Clearly show your work in the appropriately labeled box. Place your answer in the box labeled G = . C. Based on your calculated G, use arrows to express which side the equilibrium (K) would favor.

D. Estimate the equilibrium ratio (major:minor) that the G that you calculated above would correspond to at room temperature. Fill in the blanks below to indicate the order of magnitude. Between ____________:1 and _______________:1 E. If the temperature of the sample was increased, how would the equilibrium ratio (major:minor) be affected? Explain your answer in 15 words or less.

F. What extra interaction(s) between substituents does your calculation neglect? Predict the effect on G (increase or decrease) of each additional interaction(s).

G. Isomenthol (shown to the right) is a diasteromer of menthol. Would you expect the magnitude of G for ring-flipping in isomenthol to be larger, smaller, or about the same as the value you calculated for menthol above? Explain your answer in 20 words or less (with or without a picture). Circle one: Explain: Larger Smaller About the Same

HO isomenthol