Experimental Chemistry II, CH 463 & 463H Poster Abstracts for 2010
Department of Chemistry ~ Oregon State University
June 2, 2010 ~ 1:30 – 3:30
Gilbert Addition 313
1. CHARACTERIZATION OF 4-BROMO-4’-CHLOROBENZOPHENONE. Alia H. Beyer. Department of Chemistry, Oregon State University-Corvallis, Oregon 97331.
Synthesis of 4-Bromo-4’-chlorobenzophenone (BCBP) was attempted to yield a compound with potential photochemical reactivity and photophysical properties. In order to determine that the goal of the synthesis was met, the product of the reaction and subsequent recrystallization was characterized by various spectral analyses including mass spectrometry, infrared spectroscopy, and nuclear magnetic resonance spectroscopy.
2. CHARACTERIZATION OF 4-CHLORO-4'-ETHOXYBENZOPHENONE BY NMR, IR AND MASS SPECTROMETRY. C.T. Burns, Department of Chemistry, Oregon State University, Corvallis, Oregon 97331.
The benzophenone compound was synthesized by Friedel Crafts acylation and analyzed for its purity by NMR, IR and Mass spectrometry experiments. The IR stretching regions characteristic of the compound will be presented as well as the major splitting peaks in mass spectrometry. There were 1D and 2D H NMR experiments conducted, and they will both be presented along with a labeled drawing of the compound with all H's and C's identified, verifying the structure of the compound.
3. CHARACTERIZATION AND PHOTOCHEMICAL REDUCTION OF 4-CHLORO-4’-METHYLBENZOPHENONE. Gabriel J. Carrick, Oregon State University, Department of Chemistry, Gilbert Addition 309, Corvallis, OR 97331-4003.
A benzophenone with substituted chloro and methyl groups was synthesized and characterized using IR, NMR and mass spectroscopies. The benzophenone was bombarded with UV light in a solution of isopropanol, acetonitrile and glacial acetic acid catalyst in order to make a benzopinacol, however there was no evidence of benzopinacol formation.
4. PHOTOCHEMICAL CHARACTERISTICS AND TRANSITION STATE COMPARISONS OF 4-FLUORO-4'-METHOXYBENZOPHENONE USING POLAR AND NON-POLAR SOLVENT STUDIES. S.F. Christy, Department of Chemistry, Oregon State University, Corvallis, OR 97331.
The interactions of 4-fluoro-4'-methoxybenzophenone in a polar solvent EPA and non-polar solvent methyl cyclohexane were studied using UV absorption spectroscopy. It was determined that a normal n-pi* state is displayed in the presence of the non-polar solvent, however, in the polar solvent there is an observed elimination of the n-pi* transition, due to a charge transfer of one of the lone pairs on the methoxy substituent.
5. 4-BROMO-4'-METHYL BENZOPHENONE QUANTITATIVE UV. Yun-Soo Chung, Department of Chemistry, Oregon State University, Corvallis OR 97330.
4-bromo-4'-methyl benzophenone was prepared from toluene and 4-bromobenzoyl chloride by using AlCl3 catalyst. Product was used to study photophysics: "quantitative UV." Two solvents: EPA and methylcyclohexane (MCH) were used. Collected spectra were analyzed by GRAMSAI to construct Jablonski Energy Diagrams. Due to the different polarity for the two solvents and symmetry and spin changes, a shift in wavelength and oscillator strength (f) were observed. For the npi* transition, a blue shift was observed by changing solvent from MCH to EPA. On the other hand, in pipi* transition, a red shift was observed by changing solvent from MCH to EPA.
6. PHOTOPHYSICAL STUDY OF 4-CHLORO-4'-ETHYLBENZOPHENONE. D.M. Flanigan, Department of Chemistry, Oregon State University-Corvallis, Oregon 97330
Several absorption and excited state spectroscopic experiments were conducted on
4-chloro-4’-ethylbenzophenone. These experiments show the vibrational fine
structure for the n-pi* and pi-pi* transitions. The S0→S1 transition gave
ε
max = 140.08 M-1 cm-1 and
λ
max = 331.36 nm, while the S0←T1
gave and λ
max = 445 nm. The S0→S2, 3, 4 transition were also observed and gave
λ
max = 263.79, 216.62, and 202.29 nm, and
ε
max = 2.2042 x 104, 1.4565 x 104, and 2.9141 x 104
M-1 cm-1, respectively. In addition to this, the
phosphorescence in ethanol at 77 K was compared with a sample in poly(methyl
methacrylate) at room temperature.
7. Kristy Frakes: TBA
8. SYNTHESIS, CHARACTERIZATION, AND THEORETICAL INVESTIGATION OF 4-BROMO-4’-PROPYLBENZOPHENONE. Matthew W. Frogner, Department of Chemistry, Oregon State University, Corvallis 97331.
The synthesis of 4-bromo-4’-propylbenzophenone was achieved via a Friedel-Crafts acylation reaction involving 4-bromobenzoyl chloride, n-propylbenzene, and aluminum chloride. Compound was recovered with a 60.7% yield following recrystallization in hexane. The product was characterized through NMR, mass spectrometry, and melting point. These techniques confirmed the compound obtained was both pure and the desired benzophenone. In addition, quantum mechanical calculations (optimization and frequency) were carried out on different conformers of the benzophenone to determine its stable three dimensional structure.
9. PHOTOPHYSICAL PROPERTIES OF 4-BROMOBENZOPHENONE: A SOLVENT STUDY. Matthew C. Lewis, Department of Chemistry, Oregon State University, Corvallis, OR 97331
Polar and non-polar solutions of 4-bromobenzophenone were made up and used to experimentally determine several photophysical properties. UV absorption and low temperature excitation and emission spectrophotometry were used to measure and compare transitions. The nπ* transitions for both polar and non polar have transitions that are weakly allowed, indicating stabilization effects from the polar solvent.
10. PHOTOCHEMICAL SYNTHESIS AND CHARACTERIZATION OF 4-FLUORO-4’-METHYLBENZOPINACOL. Jason S. Lusk, Department of Chemistry, Oregon State University, Corvallis 97331.
Photochemical reduction is employed in the synthesis of 4-fluoro-4’-methylbenzopinacol from 4-fluoro-4-methylbenzophenone. A solution of benzophenone (992 mg) in isopropyl alcohol (16 mL) is treated with acetic acid catalyst (~8 drops) and irradiated at λ = 350 nm. After 2 days, thin-layer chromatography (25% acetone/hexane) confirms the disappearance of benzopnenone in place of a single UV-active product. The product is characterized via GC/MS, IR spectroscopy, and a variety of NMR experiments, including 1H NMR, 13 CNMR, COSY, HSQC, and HMBC. The IR spectrum confirms the loss of the carbonyl group (no peak at 1648 cm-1) and the appearance of an O-H group (broad peak at 3561 cm-1). The NMR experiments confirm the identity of the product as 4-fluoro-4’-methylbenzopinacol. Most of the 1H NMR and 13C NMR peaks appear as doublets or of higher multiplicity, indicating analogous protons and carbons in slightly different environments. The 2-D NMR experiments are used to assign proton and carbon NMR peaks to the pinacol structure.
11. SOLVENT FREE SYNTHESIS AND CHARACTERIZATION OF 4-METHOXYBENZOPHENONE. Paul V Munson. Oregon State Department of Chemistry, 153 Gilbert Hall Corvallis, Oregon 97331-4003.
4-methoxybenzophenone was produced via a Friedel Crafts acylation. Here we describe the solvent free synthesis using a ZnO catalyst. Anisole was added via the dropping funne to a mixture of ZnO and benzoyl chloride. The product was isolated by simple extraction of the solid mass with ethanol and followed by the usual work up. The pure product, 4-methoxybenzophenone, was obtained in a 30.1% yield.
12. UV ABSORPTION AND PHOSPHORESCENCE OF 4-CHLORO-4’-FLUOROBENZOPHENONE IN ETHANOL AND HEXANE. Nicole R Newcomb, Department of Chemistry, Oregon State University, Corvallis, OR 97331.
A solvent study was performed using concentrated and dilute solutions of 4-chloro-4’-fluorobenzophenone dissolved in both polar ethanol and non-polar hexane. A UV absorption spectra was obtained and the results were processed in GRAMSAI to achieve ideal curve fitting. These results were used to determine the
λ max, ε max, and IAC, which was then used for further calculations. A luminescence spectrometer was also used on solutions of concentrated ethanol and methyl cyclohexane (in place of hexane). Excitation, emission, and lifetime data was gathered on both solutions.
13. PHOTOCHEMICAL STUDIES OF 4,4'-DIFLUOROBENZOPHENONE. A.J. Perry, Department of Chemistry, Oregon State University - Corvallis, Oregon 97330
Benzophenones are fascinating molecules with unique electronic properties. Their ability to form radicals in the presence of ultraviolet radiation gives rise to some interesting photochemistry which transforms them into benzopinacols. The photochemical behavior of 4,4'-difluorobenzophenone along with the determination of its reduction efficiency will be outlined.
14. 4,4'-DICHLOROBENZOPHENONE SOLVENT STUDY. Nick Rosson, Department of Chemistry, Oregon State University, Corvallis, OR 97331.
A solvent study was conducted by dissolving 4,4'-dichlorobenzophenone in a polar solution of EPA and a non-polar solution of methylcyclohexane (MCH). UV spectroscopy and phosphorescence data was collected regarding n-pi* and pi-pi* electronic transitions at room temperature and 77 K. The data was fitted in GRAMS AI to determine the vibrational fine structure allowing for the calculation of numerous physical quantities.
15. PHOTO CHEMISTRY OF 4-METHYLBENZOPHENONE. Jacquelyn F. Seslar, Oregon State University, 97331.
By irradiating 4-methylbenzopeone a triplet state can be achieved. This Ketyl radical can bond with itself to form a reduction product of a benzopinacol. The reduction efficiency was calculated to be 41.3% by exposing four samples of constant molarity to the photon emitter for changing durations of time (10min, 20min, 30min, 40min). Those samples were then run through an IR and compared to varying concentrations of stock solution (100%, 75%, 50%, 25%) run on the same IR. The reduction efficiency was found by making a plot of the photons emitted vs. the moles of 4-methylbenzophenone lost.
16. SYNTHESIS, PURIFICATION AND CHARACTERIZATION OF 4-FLUOROBENZOPHENONE VIA FRIEDEL-CRAFTS ACYLATION. Todd M Stuhr, Department of Chemistry, Oregon State University, Corvallis, Oregon 97331.
Synthesis of 4-fluorobenzophenone was carried out neat with 17.5 ml (0.151 mol) benzoyl chloride, 43.1 ml (0.459 mol) fluorobenzene and 23.55g (0.0177 mol) aluminum chloride as a catalyst (1). The use of TLC was incrementally implemented where Rf values were compared to insure the reaction had gone to completion. Upon completion the crude product was purified yielding a total of 10.9549g (0.0548 mol) of pure product, for a percent theoretical yield of 54.77%. The characterization included the use of melting point determination where the product was shown to have a melting point of 46-470C which is consistent with literature values for 4-fluorobenzophenone (2). GCMS was used as well as IR, H-NMR, C-NMR plus 2D NMR (HSQC, HMBC and COSY) spectroscopy techniques in order to confirm and characterize the produced compound as 4-fluorobenzophenone.
17. EXCITED STATE STUDY OF 4-CHLORO-4’-NPROPYLBENZOPHENONE IN ETHANOL AND METHYLCYCLOHEXANE. Evan D. Styduhar, Department of Chemistry, Oregon State University, Corvallis, OR 97331
Investigation of excited state transitions of 4-chloro-4’-propylbenzophenone reveals relative changes in λ max in ethanol and methylcyclohexane (MCH). Absorption and emission spectra were taken on the HP Diode Array and AMINCO Bowman luminescence spectrometer. The n-pi* transitions are noticeably blue-shifted in ethanol, relative to MCH, due to hydrogen bonding, which effectively stabilizes the ground state. The pi-pi* transitions are seen to be red-shifted in ethanol, relative to MCH, resulting from stabilization of the pi* excited state.
18. SYNTHESIS AND CHARACTERIZATION OF 4,4'-DIBROMOBENZOPHENONE
Brianna Wang, Oregon State University, Corvallis, Oregon, 97330.
A di-substituted benzophenone, 4,4’dibromobenzophenone, was synthesized by Friedel-Crafts Acylation. The starting materials consisted of 4-bromobenzoyl chloride and bromobenzene, with aluminum chloride as a catalyst. A steam distillation, work-up, and recrystallization took place to obtain a purified product. The percent yield of the final product was 9.4975% and the thin layer chromatography revealed an Rf value of 0.7260. A series of characterization tests were performed, which included melting point, mass spectrometry, IR, HNMR, CNMR, HSQC, and HMBC.
19. CHARACTERIZATION OF 4-BROMO-4’-ETHOXYBENZPHENONE USING GCMS, 1HNMR, 13CNMR AND 2D-NMR ANALYSES. Jeffrey E. Wyant, Department of Chemistry, Oregon State University-Corvallis, OR 97331
The title compound was characterized using various analyses. GCMS was used to determine the molecular weight of a synthesized compound, which was compared to the molecular weight of 4-bromo-4’-ethoxybenzopheone (BEBP). The parent ion peak for the Mass Spectrum was at 304 amu, with a peak of equal intensity at M+2, indicating the presence of a Bromine on a molecule of the same molecular weight as BEBP. This data was used in addition to several 1D- and 2D-NMR spectra, including: 1HNMR, 13CNMR, COSY, HSQC and HMBC data, all of which indicate that BEBP was successfully synthesized.
20. IDENTIFICATION AND CHARACTERIZATION OF 4-BROMO-4-FLUOROBENZOPHENONE.
Matthew Yong, CH 463: Integrated Lab, Spring 2010, Department of Chemistry, Oregon State University, Corvallis, Oregon 97331.
A sample of crystals obtained from a Friedel-Crafts Acylation synthesis of Fluorobenzene and 4-Bromobenzoyl chloride with Anhydrous Aluminum chloride were characterized and analyzed with Melting Point determination, Infrared Spectroscopy, Mass Spectrometry, and Nuclear Magnetic Resonance Spectroscopy for confirmation of expected product, 4-Bromo-4-Fluorobenzophenone. Experiment melting point was to determine to be 109.5-110 °C. Prominent peak at 1648.11 cm-1 is evident of a carbonyl, notable peaks at 1601.32 cm-1 and 1584.28 cm-1 is evident of benzophenone, and significant peaks at 846.94 cm-1 and 755.58 cm-1 is evident of halogen in the infrared spectra. In the mass spectra, equal intensity peaks at 279 and 281 is characteristic of brominated compounds. The base peak of 123 m/z is fluorobenzene with carbonyl. 1H-NMR, 13C-NMR, and 2-D NMR are used to determine orientation.