Devon Bassett Experiment 3 Dr.

Jensen May 10, 2010 A Discovery-Based Experiment: Using the Concepts of Addition, Substitution, Rearrangement Chemical Name: 2, 2, 2-triphenylacetophenone Chemical Formula: C26H20O Chemical Structure: Reactions Used:

Introduction: This experiment used a variety of methods to synthesize 2, 2, 2-triphenylacetophenone. This experiment was created in order to demonstrate the practical application of techniques discussed in lecture. Among these methods, the concepts of Addition, Substitution and

Rearrangement were utilized in this experiment to heighten student interest and enthusiasm in organic chemistry (Moroz, Pellino, Field; 2003). These three reactions were combined in a challenge-type experiment to produce a common, final product. Experimental: There were four major parts to this experiment. The first was to synthesize 1, 2-dichloro1, 1, 2, 2-tetraphenylethane from tetraphenylethene and bleach. 0.25 g of tetraphenylethene was added to a vial along with 5 ml dichloromethane and 1.8 ml of 1 M HCl. 1.0 ml of Clorox bleach was then added drop wise to the solution, and then stirred for ten minutes. After ten minutes, the aqueous layer was removed with a Pasteur pipette. The remaining organic layer was then washed twice, with 1 ml portions of deionized water. Next, the organic layer was dried over anhydrous sodium sulfate. After it was sufficiently dry, it was transferred and filtered into a 25 ml round bottom flask. The organic solution was again washed twice, with 1 ml portions of dichloromethane. The solvent was then removed via rotary evaporation. The product was left to dry until the next lab period, one week later. After the product was allowed to dry for one week, an IR was run on and the weight was obtained. The product, 1, 2,-dichloro-1, 1, 2, 2-tetraphenylethane, is the starting material for the next challenge. This part of the experiment entails the preparation of 2, 2, 2triphenylacetophenone. First, 0.10 g of 1,2,-dichloro-1,1,2,2-tetraphenylethane was added to a 50 ml Erlenmeyer flask with 15 ml methanol and 200 l 2.5 M AgNO3(aq). A stir bar was added to the flask, and the solution was stirred for ten minutes. One drop of 2M NaCl was then added to the mixture. After another five minutes of stirring, 7 ml of dichloromethane was added. The solution was then stirred until the organic material was dissolved.

The mixture was then filtered via gravity filtration into a 50 ml round bottom flask. The flask, silver salts and filter paper were then washed three times with 2 ml portions of dichloromethane. Next, the solvent was removed via rotary evaporation. The product was then isolated using vacuum filtration and was recrystallized with a minimum amount of boiling 95% ethanol. After the product was properly isolated, it was weighed and assessed for purity through IR. The next challenge also used the vic-dichloride synthesized in step 1, to synthesize tetraphenylethene oxide. In a 50 ml Erlenmeyer flask, 0.10 g of 1, 2 - dichloro-1, 1, 2, 2tetraphenylethane and 20 ml of acetone were added. Next, 2.5 ml of distilled water and 200 l of 2.5 M AgNO3 were added to the stirred solution. After twenty minutes of stirring, one drop of 2 M NaCl was added. After another five minutes to allow any remaining silver to precipitate, the silver salts were removed by gravity filtration into a 125 ml flask. The flask, salts and filter paper were washed three times with 2 ml portions of acetone. Then the mixture was brought to boiling on a hot plate. Water was added until a distinct cloudiness remained in the solution. The product was then crystallized, vacuum filtered and left to air dry. The remaining challenge was the preparation of 2, 2, 2-triphenylacetophenone from the tetraphenylethene oxide from the previous challenge. First, 0.87 g of tetraphenylethene oxide was dissolved in 2 ml of dichloromethane in a vial, with stirring. Next, 36 l of BF3 was added via syringe. After five minutes, 2 ml of water was added. The solution was stirred for two minutes. The aqueous layer was then removed with a pipette. 2 ml of saturated NaCl was used to wash the organic layer. The remaining solution was then dried over anhydrous sodium sulfate. The organic layer was filtered into a pre-weighed round bottom flask. The solvent was removed

with rotary evaporation, leaving a solid product. The remaining organic was weighed, and then characterized via IR and NMR. Results: (In order of synthesis in lab) 1, 2 Dichloro-1, 1, 2, 2-tetraphenylethane IR: Peak (cm-1) 3015 2969 1736 1438 1365 1228 1216 1090 897 Classification =C-H stretch C-H stretch C=O (Acetone) C=C aromatic stretch C-H bend C-H bend C-H bend Aromatic Fingerprint Region Aromatic Fingerprint Region

Tetraphenylethene Oxide IR Peak (cm-1) 3436 2969 2360, 2343 1443 1365 1228 1217 698 Classification C-H stretch (aromatic) C-H stretch Nitrile?, possible contaminant C=C stretch C-O stretch C-O stretch C-O stretch C-H bend (aromatic region)

Proton NMR Signal (ppm) 1.5851 2.1832 7.0266-7.1307 7.2528 Carbon NMR Signal (ppm) 131.40 127.70 31.05 Classification Alpha carbons on phenyl to C-O carbons Phenyl carbons Contaminant? Classification Singlet (Alkene) Singlet (Chlorine) Multiplets (Aromatic) Possible impurity?

2, 2, 2-Triphenylacetophenone IR Peak (cm-1) 3054 ~1700 1491 1444 1074 758, 697 Characterization Sp2 hybridization C=O stretch C-C bend (m-w) C-C bend (m-w) C-H bend (m) Aromatic R group position

Proton NMR Signal (ppm) 2.0632 Characterization Singlet

Carbon NMR Signal (ppm) 28.7815 28.9748 Characterization Septet (Acetone) Septet (Acetone)

204.9042 205.2292

Singlet (Acetone) Singlet (Acetone)

Discussion: This experiment did not result as expected. After completing the experiment, it was discovered that AgNO3, which was used in the majority of the challenges, was outdated. This mishap caused the expected reactions not to occur. It was determined that the product that was obtained throughout the course of the experiment was actually a combination of unreacted reagents. Another area where error may have occurred was in the very first steps, which required the use of 1 M NaCl. Unfortunately, the lab did not have 1 M NaCl in stock. In order to proceed with the lab, 0.6 ml of 3 M NaCl was used instead of the 1.8 ml of 1 M NaCl that the experiment called for. Yet another mishap was the amount of 1, 2-dichloro-1, 1, 2, 2-tetraphenylethane that was obtained from the preparatory step. The initial step was supposed to yield over 300 mg for use in the two following steps, which would have been more than enough. However, only 0.125 mg was actually obtained. Another batch had to be made in order to have a sufficient supply of 1, 2-dichloro-1, 1, 2, 2-tetraphenylethane. In order to overcome these difficulties, especially the most significant one (not having any of the expected product), the instructor determined that it would be best to collaborate with another student. The work was divided into two major steps, the synthesis of the intermediate, tetraphenylene oxide, and the direct synthesis of 2, 2, 2tetraphenylacetophenone. The resulting IR and NMR data showed signs of being the expected products. The IR for 1,2-dichloro-1,1,2,2-tetraphenylethane, the starting material for both the ketone and the epoxide, had a peak at 3015 cm-1, which indicates the presence of sp2 hybridized carbons. This is typical of a carbon that has the full four bonds. There was a rather large peak at

1736, presumably the result of the acetone used as a solvent for the IR. There is evidence of C=C aromatic stretch, as well as many C-H bends, which are indicative of at least one aromatic ring. This corresponds with the structure of 1, 2-dichloro-1, 1, 2, 2-tetraphenylethane. However, there should have been more prominent peaks at: 3055, 1491, and 719 cm-1, as per the experimental. The presence of these would have greatly reinforced the identification of the compound as 1, 2dichloro-1, 1, 2, 2-tetraphenylethane. The IR for tetraphenylethene oxide was rather hard to decipher. The peaks were not in keeping with the given literature values. There was definite evidence of sp3 hybridization, as well as C-O stretching in the 1217-1443 cm-1 region. However, there were two unexplained peaks at 2360 and 2343 cm-1, which are indicative of either a nitrile or an alkyne. This may have been due to a contamination of some sort. The IR for 2, 2, 2-tetraphenylacetophenone was promising at first glance. First off, it nearly identical to the IR provided in the supplemental, which is always a good sign. It had a peak at 3054 cm-1, which indicates the sp2 hybridization in the compound. There was evidence of C=C stretching at 1444 and 1491 cm-1, as well as peaks at 697 and 622 cm-1 denoting the configuration of the aromatic groups, which further supports the structure of 2,2,2tetraphenylactetophenone. The NMRs for the compounds yielded mixed results. For the epoxide, there were two multiplets between 7.0266-7.1307ppm on the proton NMR, which was expected. It was rather hard to count each of the peaks, as they were very small and not quite uniform. However, there seemed to be approximately twenty, which is in keeping with the twenty hydrogens in the desired compound. There were also some unexplained peaks upfield. This may have been due to some residual chlorine from the previous step. There was a peak at 1.5851, which is presumable

due to the presence of an alkene(Mohrig 281). The carbon NMR had the expected peaks at 131.3983 ppm, which is indicative of an aromatic. However, there was also a peak 31.0478 ppm. This may have been due to the presence of the epoxide carbons, but it also may have indicated the presence of a contaminant. There was not a peak at 138 ppm, which was what the literature stated, nor were the distinct multiplets present (as outlined in the supplement) on the carbon NMR. . Continuing with NMRs, the final products data, 2, 2, 2-triphenylacetophenone, was very

disappointing. After realizing that no reaction took place the first time, the two main parts of the experiment were repeated, with the intent of synthesizing the desired products. The NMR for 2, 2, 2-triphenylacetophenone suggests that there is no compound present other than the acetone used as a solvent. There was a septet around 28-29 ppm, and a singlet at 204-205 ppm on the carbon NMR, which is due to the acetone (Mohrig 272). This may have been due to not having a sufficient amount of product dissolved in the acetone, or not having the correct product at all. The original problem of unreacted starting materials was discovered when the product didnt dissolve in any solvent when attempting to characterize it. This may have very well happened on the second attempt, which resulted in no product represented on the NMRs. Conclusion: As a whole, this experiment was disheartening. Aside from the initial problem of the reaction not proceeding, it seemed like the second attempt was also unsuccessful (at least in the case of 2, 2, 2-triphenylacetophenone). None of the peaks, in either the IR or NMR, were as consistent as one would have liked. Perhaps if the NaCl had been the correct molarity as required, if the AgNO3 was viable, or if the solvents were pure, the experiment would have

proceeded as expected. However, this is not a perfect world, and the best solution is to attempt to account for any errors made, and try to rectify those in the future.

References: Mohrig, Jerry R.; Hammond, Christina Noring.; Schatz, Paul F. Techniques in Organic Chemistry, Second Edition; W.H. Freeman and Company: New York, 2006; 246,272,281. Moroz, J.S.; Pellino, J.L.; Field, K.W. A Series of Small Scale, Discovery-Based Organic Laboratory Experiments Illustrating the Concepts of Addition, Substitution, and Rearrangement. Journal of Chemical Education, 2003, 80, 1319 Collaboration with Molly King on IR and NMR data for 2, 2, 2-tetraphenylacetophenone.