Brannon Springer Ian Wilson Neil Jain

Hydroboration-Oxidation of (1R)-(+)--Pinene
Abstract:
The objective of this experiment was to perform a hydroboration-oxidation reaction on an alkene, (1R)-(+)--pinene, and form an alcohol product. After drying all glassware, we began the hydroboration by reacting the alkene with THF and heating the mixture. We then cooled the solution in an ice bath and performed the oxidation reaction by adding petroleum ether, HCl and finally water in fractions to the solution. Each time the aqueous layer was removed and the organic layer was saved. Finally we sublimed the organic layer in an attempt to purify our product by using a cold finger and vacuum. Unfortunately, we formed no product in this experiment and could not perform the other tests or even identify our end result. This error was most likely a human error as we possibly purified the wrong layer of solution from the oxidation reactions. .

Introduction:
In this experiment we investigated conversion of alkenes to alcohols via an antiMarkovnikov addition mechanism. We performed a reaction that exhibits both regioselectivity and stereoselectivity. The solutions that we worked with were air sensitive solutions so the addition of our compounds was crucial. We learned to use IR spectroscopy to confirm the conversion of a functional group (alkene) into another functional group (alcohol). Hydroboration of an alkene is the addition of borane across the double bond. This oxidation gives an oragnoborane intermediate, which upon alkaline hydrogen peroxide oxidation gives the corresponding anitMarkovnikov hydration product (alcohol). During the reaction boron adds at the less substituted carbon due to hydrogen having a larger electronegativity. The reaction of hydrogen peroxide with NaOH produces a hydroperoxide anion. This removes the boron atom to form a boron hydroperoxide. The alkyl group moves to the oxygen, while the hydroxide anion takes place simultaneously. This hydroxide anion forms another hydroperoxide anion. This process is repeated until all of the CB bonds are converted to C-O bonds. Hydrolysis then provides the product alcohol.

Experimental (Materials +Methods):

We started with the hydroboration process. We dried all glassware that was going to be used in the experiment and then proceeded to heat the glassware to remove all moisture. This is necessary because our reaction is very sensitive to air and unknown moistures. We placed them in a dessicator until cooled. We added .150 grams of (1R)-(+)--pinene to a dry 5 mL conical vial with a magnetic stirrer

and a Claisen head fitted with a CaCl2 drying tube, and a rubber septum. We used a dry syringe to add 600 uL (.600 mmol) of 1.0 M BH3-THF to the vial through the rubber septum. While the reaction was stirring we heated the reaction to 50C for 8 minutes. We then cooled the reaction in an ice bath, removed the rubber septum, and added a single drop of H20 while stirring. We then proceeded to the oxidation by cooling the reaction in and ice bath and transferring the aqueous product to a 3 mL conical vial with a pasteur pipet. We saved the organic layer in the reaction vial. We extracted the aqueous layer with 1.5 mL of petroleum ether and discarded the aqueous layer while transferring the petroleum ether extract to the first vial containing the organic layer. We then extracted the organic mix with 2.0 mL of .20 M HCl followed by 1.0 mL of water twice. Next we dried the organic layer. We the transferred the organic layer to a dry 125 mL filter flask and removed the solvent by evaporation in the hood under a slow stream of nitrogen. After oxidation we purified the product by sublimating it. We applied a vacuum using an aspirator. We then added ice to our cold finger. Once the apparatus was evacuated we used heat to sublime our product onto the cold finger and once no more product sublimed we let the cold finger warm to room temperature.

Results:
We did not get the results we were looking for. Our IR was very hard to produce because our product was in such a small amount. When we took the IR it told us that the bonds were too weak. Our peaks could not be labeled because the peaks were too weak. Overall our experiment reaction did not proceed as planned. The Melting point and Ceric Nitrate test were not done since there was no product formed. The IR spectroscopy revealed no significant peaks in the reading.

Discussion:
There could be many reasons why our experiment did proceed as planned. We added the correct amounts in the correct orders. The first possible problem could have occurred during the heating process. During this process hydroboration should have occurred but possibly this reaction never took place so then the oxidation couldnt take place and a chain reaction of non-occurring reaction would proceed. This is possible, but I do not believe this was the main problem because when we extracted the aqueous layer with petroleum the layers separated telling us that the polarities and solubilities were not the same. This showed that we had an aqueous polar layer and a non-polar organic layer. When we did the first extraction we extracted the wrong layer which could have been the cause of error, but we kept both layers and later put the other layer back in and redid our extractions to take out the petroleum ether layer and the organic layer and left behind the aqueous layer. After removing the solvent and subliming we had very little product so we only took and IR and didnt have enough product to even do that because the IR said bonds too weak.

Conclusion:

The purpose of this experiment was to investigate the conversion of alkenes to alcohols via an antiMarkovnikov addition mechanism. The reaction exhibited both regio- and stereoselectivity. 600 micro litres of BH3-THF is added to 150 milligrams of IR-+--pinene via a syringe and heated. After 2 drops of DI water 375 micro litres of 3 Molar NaOH and 375 micro litres of H2O2 are added. The aqueous layer is extracted with ether and then dried over anhydrous sodium suphate. The resulting products were put under a sublimation process but there was no product on the cold finger. Since the purification did not yield a visual sublime product the cold finger was washed with ether and the sample was collected in a vial for IR spectroscopy. The IR spectroscopy revealed no significant peaks even with 25 scans instead of the customary 4. Thus concluding that the product was not formed during the course of the reaction. Due to no product, the melting point analysis and Ceric nitrate test were not possible.

Post Lab Questions:

1) We could not take our melting point so this would be very hard to compare and contrast with other compounds. 2) Our IR spectrum had very few peaks. It had a relatively small peak at about 2900 cm-1 which might suggest that it had some (+)--pinene in it, but the peaks are so undistinguishable due to no formation of product that we can not truly compare any results. 3) Another chemical test that could have been performed was the boiling point of both the starting material and the final product. Since our final product was an alcohol, its boiling point would have been over 200C while (1R)-(+)--pinene only has a boiling point of 155-156C. 4) 6-88) a) In a Lewis sense, BH3 acts as a Lewis acid because it accepts the pair of electrons given to it by the oxygen on THF. This is also show by the negative charge on boron after the reaction. b)

6-89) a) BH3 reacts with the -bonds of the alkene because it is a sp2 hybridized molecule without a full octet. Therefore, its unfilled p orbital is looking to accept electrons and adds to the less substituted carbon. b) Diborane reacts slowly with the carbon-carbon double bond because diborane has a complete octet on both boron atoms and is not actively seeking electron pairs.

Also borane has not yet been reacted with hydrogen peroxide and has no oxygen atoms and a fairly low electronegativity. Once bonded with the carbon atoms however it does react with the hydrogen peroxide and undergoes a hydration react to form the product alcohol. 6-90) Boron will bond with the second carbon in the double bond because it is only bonded with a methyl group and hydrogen plus the CH group from the double bond. On the other hand, the first carbon in the double bond is bonded with two methyl groups and the CH2 group from the double bond. Almost every time, bonding to the second carbon is more stable and is the product most likely formed in this reaction. 6-91) Chlorine is highly electronegative compared with boron and will act differently in carbon bonding. Boron forms a anti-Markovnikov product in hydroboration while chlorine form both Markovnikov and anti-Markovnikov products. Chlorine is highly reactive as it attempts to form an octet with whatever carbon in the chain, and being the most wanted atom for its electrons, it usually gets its wish.

References:
http://guides.lib.purdue.edu/chemlabs Mayo, Dana; Pike, Ronald; Forbes, David. Microscale Organic Laboratory with Multistep and Multiscale Syntheses; John Wiley & Sons: United States, 2010. (Pg. 232 Mayo Pike, Micro Organic Laboratory)