Friedel Crafts

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Friedel Crafts Winona State University-Chemistry Department, Winona, MN 55997 CHEM 340-01, Dr. Kopitzke April 6, 2020
Introduction: Nuclear magnetic resonance, also known as NMR, is a spectroscopy technique primarily used for the analysis of organic compounds. 1 NMR functions based on magnetic fields and particle spins. The nucleus of an atom is positively charged and creates a magnetic field as it randomly spins. Once an external magnetic field is introduced on the sample by the spectrometer, the nuclei either spin with or in the opposite direction of the field. 2 The machine then generates a plot of signal frequency versus intensity depending on how the atoms interact with the current. This data allows researchers to identify the structure of the organic compound. In this experiment, a reaction of isobutyl benzene, acetyl chloride, aluminum trichloride, and dichloromethane was finalized, and the product was tested using nuclear magnetic resonance spectroscopy. Isobutyl benzene is an aromatic compound, meaning it has a cyclic structure along with special stability allowing it to be used as a solvent for nonpolar compounds. 3 The aromatic compound in this chemical process is responsible for the specific organic compound created by the reaction. The primary objective of this experiment was to employ IR and NMR spectroscopy to determine which isomer was composed by the successfully completed reaction. Experimental: All supplies were obtained for the experiment. 2mL of CH 2 Cl 2 and 0.8 g of AlCl 2 was added to a round bottom flask and a vent was created. 0.6 mL of acetyl chloride is slowly added to the round bottom flask over a period of 2 minutes. 0.5 mL of the given aromatic (isobutyl benzyne) was added into the reaction over 5 minutes. The transfer was completed by using a few extra milliliters of CH 2 Cl 2 . After the reaction was completed, 4 mL of ice cold water was added drop by drop into the solution. The solution separated into two layers, the organic bottom layer and the acid top layer. The organic layer was removed without disturbing the acid layer and added into a 5 mL conical vial. 1 mL of 5% sodium bicarbonate was added into the vial containing the
organic layer. Dry the substance with sodium sulfate and decolorize with a pipette column containing about 3 cm of Alumina. Substance was contained in a clean 50 mL flask and dried using N 2 . A final weight was taken and the product was sealed in a flask for use the following week. Infrared and NMR were both done. For IR, a drop of sample was put in between the AgCl plates and read by the computer. For NMR, 2 drops of sample as well as 2 inches of CHCl 2 was added to the NMR tube and read. Proper washing and storage of the glassware was done to finish the lab. Results: Table 1: Yield Final Mass 0.966 g % Yield of isobutyl acetophenone 175% Calculations: Isobutyl Benzene (Aromatic Substrate) = 0.5 mL * * = 3.13 * 10 -3 0.853 𝑔 1 ?𝐿 1 ?𝑜? 136.22 𝑔 mol Acetyl Chloride = 0.6 mL * * = 8.41 * 10 -3 mol 1.1 𝑔 1 ?𝐿 1 ?𝑜? 78.49 𝑔 Theoretical Yield = 3.13 * 10 -3 mol * = 0.552 g isobutyl acetophenone 176.25 𝑔 1 ?𝑜? % Yield = * 100 = * 100 = 175% 𝑎𝑐??𝑎? ?ℎ𝑒𝑜𝑟𝑒?𝑖𝑐𝑎? 0.966 𝑔 0.552 𝑔 Table 2: Infra- Red Data Wave number(s) Bond Type 2956.61 C - H (Sp 3 ) 1683.22 C = O 1606.05 C = C (Benzene) 1267.34 C - C
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Figure 1: IR Data Plot Table 3: 1 H-NMR Data δppm Int Splitting Assignment 7.86 1.93 (2) Doublet (2) A 7.22 2.18 (2) Doublet (2) B 2.58 2.82 (3) Singlet (1) C 2.52 1.85 (2) Doublet (2) D 1.89 1.00 (1) Multiplet (8) E 0.90 6.32 (6) Doublet (2) F
Figure 2: 1 H-NMR plot of product Figure 3: Structure of final product, with labeled hydrogen regions supported by table 3 Discussion: The theoretical yield of isobutyl benzene was calculated to be 0.552 g, however the actual yield of the product was 0.966 g, giving a 175% yield. The extra mass can be attributed to incomplete or improper abstraction of solvent from the product. The infrared data that was collected, seen in table 2, showed four distinct peaks that were identified to be C-H (sp 3 ) at 2956.61, a C=O bond at 1683.22 as a ketone, a
C=C at 1606.05 as a benzene, and 1267.34 as a C-C bond. In table 3, the 1 H-NMR data shows two peaks about the benzene, both depicted as a doublet and integrated values of ~2, are labeled as A and B with values of 7.86 ppm and 7.22 ppm, respectively. A peak at 2.58 ppm with an integrated value of ~3 shows a singlet and identified as region c in figure 3. The shift at 2.52 ppm had an integrated value of ~2 and split into a doublet, labeled as region D in figure 3. The shift at 1.89 ppm had an integrated value of ~1 and showed a multiplet, indicating to be region E. Lastly, the shift at 0.90 ppm with an integrated value of ~6 showed a doublet peak and labeled as region F. The 1 H-NMR data that was collected, alongside with the IR spectroscopy data supported the conclusion that the Friedel-Crafts alkylation proceeded to some extent, and that the major product was the para- substituted molecule rather than the ortho- substituted molecule. Conclusion: Throughout this experiment, the main objective was to determine which isomer was composed by the successfully completed reaction. After concluding the experiment it is known that the isomer formed was para-isobutyl benzene. If this experiment were to be done again, students should be sure to thoroughly dry the final product to ensure accurate infrared and NMR results. This, in turn, would create a more precise percent yield, resulting in more accurate data. References: 1. Reusch, W. (2013, May 5). Nuclear Magnetic Resonance Spectroscopy. Retrieved April 4, 2020, from https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/nmr1.ht m 2. PROTON NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (H-NMR). (n.d.). Retrieved April 4, 2020, from https://www.chem.ucla.edu/~harding/notes/notes_14C_nmr02.pdf 3. Libretexts. (2019, June 5). 13.8 Examples of Aromatic Compounds. Retrieved from https://chem.libretexts.org/Courses/University_of_Illinois,_Springfield/UIS:_CHE_
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267_-_Organic_Chemistry_I_(Morsch)/Chapters/Chapter_13:_Benzene_and_Aro matic_Compounds/13.08_Examples_of_Aromatic_Compounds