Name Desk# Date Class

Phase Transfer Catalysis: Addition of Dichlorocarbene to Cyclohexene

Objective: In this lab, a phase transfer catalytic reaction was performed to generate a carbene. We prepared 7,7-dichlorobicyclo[4.1.0]heptane, also known as 7,7-dichloronorcarane by the reaction:

Background: The formation of a halogenated carbene usually involves a twophase reaction. Because the base is insoluble in the organic solvent, a phase transfer catalyst is used to move the hydroxide ion from the aqueous layer into the organic layer. A common type of phase transfer catalyst is a quaternary ammonium salt. In our experiment we are using such a catalyst, namely benzyltriethylammonium chloride. As the chloride, benzyltriethylammonium chloride is insoluble in chloroform, but quite soluble in water. However, as the quaternary ammonium hydroxide, it is somewhat soluble in the organic solvent. So, it can transport the hydroxide ion from the aqueous layer to the organic layer where the hydroxide ion reacts. After reacting, the halide ion is transported back to the organic layer.

This is the mechanism of the carbene formation:

(Note: The SN2 reaction (also known as bimolecular nucleophilic substitution) is a type of nucleophilic substitution, where a lone pair from a nucleophile attacks an electron deficient electrophilic center and bonds to it, expelling another group called a leaving group.)

Procedure: 1. Added 0.40 ml cyclohexene, 1.0 ml 50% NaOH and 1.0 ml chloroform to vial with spin vane, sequentially. 2. To this mixture added 0.04 g phase transfer catalyst, benzyltriethylammonium chloride. Capped quickly. 3. Placed vial in 40C hot water bath and stirred rapidly for one hour. 4. Removed vial and allowed to cool to room temperature. 5. Mixture was pipetted to centrifuge tube and 1.5 ml water and 1.0 mL methylene chloride were added. This was capped and shaken gently for 30 seconds. 6. As layers separated, the lower organic layer was collected, along with a 1.0 mL methylene chloride addition for a 2nd collection. 7. This organic layer was added to a centrifuge tube along with 1.0 mL NaCl aqueous solution and shaken for 30 seconds. 8. Once again, the organic layer was removed to a dry vial and dried over anhydrous sodium sulfate. 9. Mixture was transferred to a clean, dry vial and evaporated in a warm water bath of 50C for approximately 30 minutes until condensation no longer formed or vapor was visible. Results:

Data Grams measured 0.43 1.23 Molecular Weight Grams/Mole 82.2 165 Moles Calculated 0.00523 0.0745 142.4%

Cyclohexene Limiting Reactant 7,7-dichloronorcarane Product Obtained Percent Yield

Clearly we did not produce product out of thin air, although that would have been a neat trick ;o) We lacked the apparatus to dry the solvent, methylene chloride, out of our mixture and so, consequently, must have had that weighing in with our final product. While we may have been able to continue to heat the mixture to continue evaporation, time did not permit.

Conclusions: Although we did not successfully isolate our product completely from the solvent, we probably did successfully perform the addition of dichlorocarbene to cyclohexene with the aid of a phase transfer catalyst. Id like to think so. We learned a lot anyway.

Discussion: This exercise showed how phase transfer catalysis can assist a reaction, saving time and cost. It was very interesting to learn that the catalyst functions like a detergent for solubilizing the salts into the organic phase. I also found it very interesting that a sodium chloride solution could be used to withdraw water from an organic solution, like we did before treating the solution with anhydrous sodium sulfate to further dry the mixture.