Dehydration of Alcohols with an Introduction to HNMR Spectroscopy

One of the principle ways to form alkenes in organic synthesis is by dehydration of an alcohol precursor. The dehydration reaction proceeds under thermal conditions in refluxing acid through a carbocation intermediate. The carbocation is formed through an E1 mechanism as shown below.

Because the reaction occurs under thermal conditions (high temp, long reaction time) if multiple alkene products are possible, then the more stable Zaitsev Product should predominate. For example, in the next figure, multiple alpha hydrogens may eliminate to form the double bond. The Zaitsev Product contains the more substituted double bond and thus should predominate.

It is not known to what degree the Zaitsev Product will predominate in any given system (i.e. what the product percentage will be in the final product). In this experiment 3-methyl-3-pentanol will be dehydrated to form alkene products in some unknown ratio. Proton nuclear magnetic resonance (1H NMR) spectroscopy will be used to determine the ratio by looking at the relative proton integration. Safety Never heat a sealed apparatus. Phosphoric acid is very corrosive, thus goggles and gloves are a must. The starting material and products are flammable so avoid sources of ignition.

Procedure (Microscale Reflux) Obtain 2 g of 3-methyl-3-pentanol in a 5 mL conical vial. Add a spin vane and 0.25 mL of 85% phosphoric acid solution. Attach a Hickman still and condenser and begin water flow. Heat at ~40-50 % power until product alkenes begin to distill off and collect in the Hickman still. Weigh a small test tube or vial and transfer the product liquid into this vial as you distill. Once distillation ceases, obtain the weight of your product and the vial. Put your sample in an HNMR tube and bring to the instrument room for HNMR training. Using the integrated spectra of your product mixture, determine the product distribution (% of each product) in the final sample. Post Lab Questions 1. Does your proposed product distribution agree with Zaitsevs Rule? Explain. 2. What products do you suppose would result from the dehydration of 3-methyl-2-butanol? Draw a mechanism each proposed product.