Conclusions Experiment 3 Steric Effects of Reactants on Elimination Reactions In this experiment we performed an E2 reaction between 2-bromoheptane and a sodium

m methoxide in methanol nucleophile. The expected observed products were 1heptene (minor), trans-2-heptene (major) and cis-2-heptene (minor). The purpose of the reaction was to observe the effects of bulky side-chain nucleophiles such as sodium tertbutoxide on the reaction mechanism and the products obtained, as opposed to non-bulky side-chain nucleophiles such as sodium methoxide. The class was divided into four groups of students, each performing a reaction between 1-bromoheptane and 2-bromoheptane with sodium tert-butoxide in t-butanol and sodium methoxide in methanol as the nucleophiles. The main characteristics of the reagents and expected products needed for the analysis of the success and yield of this reaction were the boiling points, which were used for the gas chromatogram interpretation. The boiling points of all reactants, expected products, and solvents of my reaction were: pentane (solvent): 36C, methanol (solvent): 65C, 2bromoheptane (reactant): 64-66C, 1-heptane (product): 94C, trans-2-heptane (product): 98C, cis-2-heptane (product): 99C, 2-methoxyheptane (possible side product): boiling point could not be found in literature, 1-methoxyheptane (not a possible side product, but boiling point taken here as an approximation of the boiling point of 1-methoxyheptane): 131.7C. The reaction was performed under reflux. The procedure consisted of preparing a sand heat bath at 75C. I filled a 5-mL conical vial with 1.6 mL of 25% sodium methoxide in it. After the sand bath had reached 75C, I added 0.3 mL methanol, placed the vial in the sand bath, setting up the reflux system and stirring the reaction mixture on top of a stir plate using a magnetic stir vane. The mixture was left to react at 75C for 30 minutes. After that I dismantled the reflux system and left the conical vial to cool at room temperature. I then added one pipette-full of pentane and one pipette full of DI water. Prior to the addition of water there was a white solid on the bottom of the vial, after the addition of the water this solid, which was most likely sodium bromide salt, dissolved completely in water. The presence of sodium bromide salt indicated that bromide ion had been released during the E2 reaction and was free to react with the sodium ions from the sodium methoxide nucleophile, forming a salt precipitate in the organic solvent, as an indicator of a successful reaction. When water was added this salt dissolved. The aqueous phase was removed by pipetting. The washing of the organic layer with water was repeated three times. The organic phase appeared on top, whereas the aqueous phase appeared on bottom of the vial, due to density differences (water is denser). Once the organic phase had been washed, I added a very small amount of anhydrous sodium sulfate to remove any remaining water in the vial. I then transferred 1 mL of the organic phase to the GC (gas chromatography) vial. The GC chromatogram produced 6 peaks. The first peak, which had the largest area of 377582[pA*s], was pentane, with retention time of 3.2 minutes. The last peak, with retention time of 11.65 min, had the second largest area of 5033, and this peak was most likely representative of the major product. The peak that eluted second had a retention time of 4.3 minutes, and an area of 230. The third peak eluted with retention time of 4.6 min, and area of 659. The fourth peak eluted after 4.8 min, with an area of 180, and the fifth peak eluted after 9 min, with area 432. GC separated based on both boiling point and polarity. Since 1-heptene and trans-2-heptene have similar polarities, their polarities play a major role in determining which one is to be expected to elute first. Since 1-heptene has lower boiling point, it is expected to elute first, trans-2-heptane is expected to elute second, and cis-2-

heptane is expected to elute last. More polar compounds elute with higher retention times than less polar compounds. Methoxyheptane has both a very high boiling point, much higher than all the rest of solvents, products and reactants, and it also has a very high polarity, so it would had been expected to elute last. It is additionally a side-product, so it is expected to have a very small area as a result of small concentrations in solution. My GC chromatogram displayed no peaks with higher retention time than peak 6, which had the second largest area indicative of a major product, so I conclude that no methoxyheptane was present in the reaction mixture sample being tested. Even though trans-2-heptane is less polar than cis-2-heptane, they have very similar boiling points, and I would had expected them to elute together as a single peak, the peak with area 5033. 1-heptene has a lower polarity than 2-heptene, and it also has a lower boiling point, so I expect it to have a much lower retention time, probably the peak at 9 min with area 432. This is the fourth largest area. The third larges area, 659, is most likely methanol, one of the solvents. The areas that surround that peak are expected to correspond to the starting material, which have boiling points ranging below and above the boiling point of methanol, so they can elute before and after methanol. Therefore, the peaks with areas 230 and 178 correspond to 2-bromoheptane. If the reaction was performed with t-buthoxide instead of methoxide, I would had expected to see 1-heptene as the major product. The bulky side-chain of t-butoxide would had prevented the nucleophile from reaching an internal hydrogen, and would had been more likely to abstract a hydrogen from the first carbon in the chain, which is less hindered. Therefore 1-heptene would had been the more likely product in such a reaction.

Anastazija Ristovska September 27, 2012