Introduction The Grignard reaction is one of the most versatile methods of forming carbon-carbon bonds, in that a Grignard

reagent can be made from virtually anything. Tertiary, vinylic, and benzoic halides can all be turned into Grignard reagents, which work by making carbon nucleophilic via a strong negative charge placed on it when magnesium metal is added to the halide. The purpose of this experiment was to explore the reaction of phenylmagnesium bromide with benzaldehyde, to verify that benzhydrol, the expected product, would be made by the following reaction:

The reaction follows this mechanism:

Calculations and Data Table
Limiting Reagent and Theoretical Yield: Given the following reactions:

PhBr+Mg0 Et2O PhMgBr PhMgBr+PhCHO →Ph2CHOH
And assuming that all the bromobenzene becomes phenylmagnesium bromide, and that the second reaction goes entirely to completion, the limiting reagent will be given by whichever reagent yields the least amount of product. Because

3.2 g PhMgBr x 1 mol PhMgBr181.12 g PhMgBr x 1 mol benzhydrol1 mol PhMgBr=0.018 mol benzhydrol
and

2.2 g PhCHO x 1 mol PhCHO106.12 g PhCHO x 1 mol benzhydrol1 mol PhCHO=0.021 mol benzhydrol
Therefore, the phenymagnesium bromide will be the limiting reagent in this reaction, and the theoretical yield will be given as follows:

3.2 g PhMgBr x 1 mol PhMgBr181.12 g PhMgBr x 1 mol benzhydrol1 mol PhMgBrx 184.23 g benzhydrol1 mol benzhydrol=3.25 g benzhydrol
Percent Yield:

0.81 g crude product3.25g benzhydrolx 100%=24.9%
Percent Recovery:

0.045 g recrystallized product0.37 g crude product used x 100%=12.2%

Table 1. Various data concerning the crude and recrystallized product in the synthesis of benzhydrol.

Benzhydrol Synthesis Data
Crude Product Mass of bromobenzene Mass of benzaldehyde Mass of product Percent Yield Observed Melting Point Literature Reported Melting Point 3.2 g 2.2g 0.81 g 24.9% 58-65 °C 65-67 °C Recrystallized Product Mass of crude product 0.37 g Mass of product 0.045 g Percent Recovery 12.2% 64-65.6 °C 65-67 °C

Discussion The first step in the formation of benzhydrol was the actual synthesis of the Grignard reagent, phenylmagnesium bromide. A reflux apparatus with a water-cooled condenser and addition funnel were set up to create this reagent. The addition funnel served two purposes; it prevented oxygen from reacting with the magnesium metal to form magnesium oxide, and prevented moisture from entering the system. The latter of which would kill the reaction entirely, since the Grignard reagent is highly reactive with any electrophile. The apparatus was also flame-dried to reduce moisture. Approximately 3.2 g of bromobenzene, along with 0.61 g of magnesium were added and allowed to reflux for 20 minutes under heat; this produced a dark brown solution. The magnesium was in excess so that enough pure metal would be present to react with the bromobenzene, and an iodine chip was also added to clean the magnesium surface, which again helped combat air-oxidation of the magnesium. Following this, 2.1 mL of benzaldehyde was dissolved in approximately 15 mL of anhydrous ether and added to the addition funnel. Again, the ether had to be anhydrous, as any water present in the system would stunt the reaction. However, the benzaldehyde added was contaminated; it was almost black, when it should have been clear. Luckily, only a few drops were added to the flask containing the Grignard reagent before this was noticed and rectified by cleaning out the addition funnel and adding a fresh 2.1 mL of benzaldehyde in anhydrous ether. The impurity of the reagents was noticed; however, in that the solution immediately turned green upon addition of the contaminated benzaldehyde. Following the reflux of 15 minutes, the solution was now light brown – almost tan – with a green layer above it, stuck to the flask. In order to recover the neutral benzhydrol created, the solution in the flask was added to cold, dilute sulfuric acid. This served to neutralize the benzhydrol, so that it could be extracted using standard techniques. The extraction involved three main steps; the initial separation of the aqueous solution with ether to bring the benzhydrol into the organic layer, a washing with sodium bicarbonate to remove any excess strong acid present, and a final wash with water to remove any other water-soluble impurities. After the final extraction, the organic layer was a pale yellow, a clear sign of impurities. The solution was dried with magnesium sulfate to remove excess water and then gravity filtered to separate out the dry ether. The gravity filtration left the saturated magnesium sulfate behind while leaving only the benzhydrol dissolved in now anhydrous ether. The ether was evaporated under reduced pressure to produce a crude product of approximately 0.81 g. The product was then collected via vacuum filtration, using cold ligroin as a wash. This was effective in removing biphenyl and benzene, two common byproducts, which are soluble in cold ligroin, while benzhydrol is not. However, the impurities present were obvious; the crystals collected were yellow and brown in color, and the observed melting point, 58-65 °C was well below the reported range. Because of the impurities, only half the crude product (0.368 g) was recrystallized so that a comparison of the two could be made to determine if the crystal purity increased. The recrystallization was carried out using 95% ethanol as the solvent, which was a good choice of solvent, because it would remove any polar impurities present within the crystals. Initially, a bit too much ethanol was used, so some had to be evaporated before the crystals crashed out of the solution. The recrystallized product was whiter in color, and given the melting point of 64-65.6 °C, was much purer. However, the recrystallization afforded a low percent recovery, which is likely due to the excess of ethanol added, as well as the sheer amount of impurities present in the crude product.

Overall, this reaction was not very successful in the formation of benzhydrol; percent yield was very low (24.9%) and percent recovery was lower still (12%). The cause of this was more than likely moisture in the air that day, which is deadly to the Grignard reaction. Because it was raining on the day of this experiment, there was an obvious increase in moisture in the air, and this is likely the best explanation for the poor results. The equipment was flame dried; however, it is possible that despite this, the humidity in the lab added an excess amount of moisture that essentially killed the reaction. Furthermore, the contaminated benzaldehyde likely produced side reactions with the Grignard reagent that used it up, leaving little to create the benzhydrol once the pure benzaldehyde was added. This is evident from the green color the solution turned when the impure benzaldehyde was added. Therefore, with better conditions, the reaction would be expected to go much more smoothly with higher yields. Conclusion While the procedure definitely generated some benzhydrol, it was in very low yields, as only 0.81 g crude product was obtained, which corresponded to a 24.9% yield. However, the recrystallization afforded a higher quality product, which could clearly be seen when comparing the two directly; the recrystallized benzhydrol was much whiter, and more regular in shape. Further, it had a melting point of 64-65.6 °C, which was very close to the reported value, and much better than the 58-65 °C melting point of the crude product; hence, a purer product was obtained.