1

2 Abstract The intent of this experiment was two-fold, with the first part comprised of the preparation of the Grignard reagent, i.e. phenylmagnesium bromide. This Grignard reagent was then used in part 2 of the experiment to form triphenylmethanol upon addition of benzophenone in ether, and addition of water following. Success of part 2 (and overall experimental success) was contingent upon proper synthesis of the Grignard reagent. Both extraction and crystallization techniques were used to arrive at crude and then pure triphenylmethanol. To determine if the product was made and the purity thereof, the melting point was found and infrared spectrum taken, respectively. Based on the hydroxyl group peak present in the final IR spectrum (and comparative absence in the initial) the experiment was successful and triphenylmenthanol was produced. Comparison of the experimental melting point with the literature value points to a less successful completion of the purification technique.

3 Introduction A Grignard reagent can be reductively referred to as an organomagnesium halide with its composition explicitly laid-out in said reduced term. An alkyl halide and magnesium metal are brought together in a system containing anhydrous ether to yield the Grignard reagent. The magnesium will insert between the alkyl group and the halide and the ether will aid in stabilizing the reagent. In this experiment, a bromobenzene (bromine being the halide of choice) is introduced to magnesium in the presence of ether, effecting phenylmagnesium bromide, as laid out in the reaction and mechanism following:

Br
bromobenzene

Mg

ether

MgBr
phenylmagensium bromide

Br

Mg
ether

MgBr
ether

MgBr

bromobenzene

phenylmagensium bromide

Subsequent to synthesis of the Grignard reagent, in part 2 of the experiment, triphenylmethanol will be produced through the introduction of benzophenone and the conversion of phenylmagnesium bromide to a tertiary alcohol. Here lies the reaction and mechanism:

phenylmagensium bromide

MgBr

+
O ether O Mg+Br
-

H3O+ OH

MgBr(OH)

benzophenone

triphenylmethanol

H O H
+

MgBr

MgBr

MgBr
OH

O phenylmagensium bromide
+

triphenylmethanol benzophenone

In elaboration, the means for this mechanism is first the nucleophilic addition in the reaction of the Grignard reagent and the bromobenzene. In the first mentioned reaction, an unequal sharing of electrons between the carbon and magnesium produces a persisting positively polarized magnesium. Thus, the alkyl component of the Grignard manifests properties of a carbanion. This negative charge will seek the positive charge on the carbon in the benzophenones carbonoxygen double-bond (the positive charge here being the result of resonance). In the last part, hydrolysis occurs with the addition of hydrochloric acid. From a Grignard reagent, a ketone is made a tertiary alcohol. Inherent characteristics of the Grignard reagent make this experiment quite sensitive, one such characteristic being the high-energy intermediate of the carbanion. If any water is present,

5 rather than acting as a nucleophile, the Grignard reagent will act as a base and conduct an acid/base reaction. This effectively deactivates the reagent. To prevent this, all glassware is dried in an oven prior to the experiment. Also, the biphenyl byproduct destroys the Grignard reagent. Bromobenzene radicals, if left to their own devices in large quantities, will bond with one another, forming biphenyl. This is avoided by adding the bromobenzene into the system slowly. At the end of the experiment, recrystallization allows the crude product to be purified, and if all precautions are taken, the formation of the triphenylmethanol should be evident from the IR Spectra: the alcohol displays a broad peak around 3600-3200 cm-1 Procedures: Glassware used in the experiment was dried in an oven for one hour. A drying tube with anhydrous calcium chloride was prepared. Approximately 0.15g of magnesium turnings were scrubbed until shiny with steel wool and put into a 20-mL round bottom flask with a magnetic stir vain. 0.7mL bromobenzine was combined with 4mL anhydrous diethyl ether and put into a pre-weighed conical vial. The weight was taken again and the weight of the mixture was determined. The apparatus was placed in a warm sand bath on top of the hot plate and the stir was set on a low level. A syringe containing .8mL of the bromobenzine solution was inserted into the rubber septum of the apparatus and was added to the flask containing the magnesium turnings at the rate of about 6 drops every 30 seconds. The rest of the bromobenzine was added in the same manor. 2 mL of anhydrous ether was placed into the vial originally containing the bromobenzine solution and was added using the syringe to the reaction mixture. The magnesium turnings were dissolved and the mixture was cooled to room temperature. 1.09g benzophenone was combined with 2mL anhydrous ether and was rapidly injected into the reaction mixture using a syringe. The mixture was cooled to room temperature. 1mL anhydrous

6 ether was put in and the vial that contained the benzophenone solution and was added to the reaction mixture. The mixture solidified. 6mL of hydrochloric acid was added to the reaction mixture drop wise until the mixture dissolved into a liquid and 2 distinct layers formed. The top layer was extracted and put into a 10mL beaker. The aqueous layer was re-extracted with 5mL anhydrous ether 2 times. The top layers were combined into the beaker and dried with anhydrous sodium sulfate and rinsed with diethyl ether. The water was evaporated using air drying technique. Vacuum filtration was used to collect the triphenylmethanol. The crude produce was weighed. The product was recrystallized. The pure product was weighed. A melting point was obtained. An IR spectroscopy was performed. Results: Synthesis of Grignard Molecular weight of bromobenzene: 157.01g Initial mass of bromobenzene: 1.07g Molecular weight of magnesium: 24.31g Initial mass of magnesium: 0.162g Limiting Reagent calculation (synthesis of Grignard): 1.07g bromobenzene * 1 mol * 1 mol phenylmagnesium bromide = 0.00681 mol product 157.01g 1 mol bromobenzene

0.162g magnesium

* 1 mol * 1 mol phenylmagnesium bromide = 0.00666 mol prodcut 24.31g 1 mol magnesium

Magnesium is the limiting reagent

Formation of Triphenylmethanol Molecular weight of phenylmagnesium bromide: 157.01g Mass of phenylmagnesium bromide (Grignard): 1.209g Molecular weight of benzophenone: 182.22g Mass of benzophenone: 1.095g

7 Limiting Reagent calculation (formation of triphenylmethanol): 1.209g Grignard * 1 mol * 1 mol triphenylmethanol = 0.00666 mol triphenylmethanol 157.01g 1 mol Grignard 1.095g benzophenone * 1 mol * 1 mol triphenylmethanol = 0.00601 mol triphenylmethanol 182.22g 1 mol benzophenone

Benzophenone is the limiting reagent

Literature Melting point of triphenylmethanol: 162C Percent Yield calculation: Molecular weight of triphenylmethanol: 260.313 Mass of crude triphenylmethanol (crude product): 0.663g

1.095g benzophenone

* 1 mol * 1 mol triphenylmethanol * 260.33g = 1.564 g 182.22g 1 mol benzophenone 1 mol

0.663g * 100% = 42.4 % 1.564g Mass of purified triphenylmethanol (pure product): 0.440g Percent Recovery Calculation: 0.440g * 100% = 66.37 % 0.663g

See IR Spectrum attached: Discussion: As aforementioned, this experiment was intricate, in part due to the temperamental nature of the Grignard reagent. Because utmost care was taken and the system meticulously withheld from water, the resulting IR Spectrum did show a broad peak corresponding to the hydroxyl group in the desired product at 3472 cm-1. Had the triphenylmethanol not been synthesized, there would be no such peak. In the initial IR Spectrum of the ketone, there would be only the following peaks on display: aromatic peak at 1600 cm-1, peak at 1680 cm-1 for the carbon-

8 oxygen double-bond, as connected to the phenols, and slight peaks above 3000 cm-1 for the sp2 hydrogen-carbon bonding. Again, the hydroxyl group peak affirmed triphenylmethanol was produced. One point of concern in the data was the discrepancy between the experimental melting point and the literature, 140-156C and 162C, respectively, which indicates there were still impurities present in the pure product. The percentage yield was also low. The variance in melting point and the low percentage yield vis--vis the IR spectrum necessitates improvements in extraction and crystallization in future experiments. One such improvement in extraction would be a more controlled and careful conduction of the procedure. Extraction of the ether layer with the Pasteur pipette was a source of some difficulty, and that, combined with an insufficient amount of extractions could have affected the percent yield and even, indirectly, hampered the accuracy of the melting point. Also, of note, is that the synthesis of the Grignard reagent is a step perpetually riddled with room for improvement. There are slight observations that can be made during the synthesis and following tertiary alcohol formation (e.g. such as color, quantity of solid), but overall, it was hard to measure each individual step for success. Thus, if triphenylmethanol was formed, reflection of each step in the reaction for means of betterment proves difficult.