Jennifer Herrera Experiment Date: 3/12/2012 Photochemistry: Photoreduction of benzophenone and rearrangement to benzpinacolone

Abstract:
In this experiment Benzpinacolone was synthesized in a process that contained two steps. First the photoreduction of benzophenone in 2-propanol, which was done by placing the flask under sunlightfor the absorption of the UV rays to carry out the reaction. Then the second part was the dehydration of benzpinacol to benzpinacolone, where the benzpinacol product was converted to a ketone by the acid catalyzed rearrangement of the benzpinacol to the benzpinacolone; this was done by adding iodine and acetic acid to benzpinacol. The reaction was then refluxed, cooled in an ice bath, filtered and washed with ethanol. After allowing the benzpinacolone to dry, we found that our percent yield was 71% .Even though the yield was good, considering that the photoreduction period took a couple extra days due to lack of sunlight, loss of product can be attributed to this since we only could get 2.11g/3.0g of benzpinacol from the start of the lab. And since benzpinacol was the limiting reagent, before starting part 2 of the lab this already set us up for some loss in % yield. Also when we transferred our product from the filtration funnel to the watch glass there was product loss because many of the crystals were stuck in the flask and could not be removed to get an accurate weight. The observed melting point of the product was 164-165C which is a little lower than the theoretical mp value; this can be attributed to impurities in our product. An IR spectrum was given and analyzed for benzophenone. 1H NMR, 13C NMR, and IR spectrums were also given for benzpinacol and benzpinacolone and the peaks were analyzed for the purpose of recognizing functional groups and noting any similarities and differences between the compounds that were made.

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1.Introduction: Use ultraviolet light to carry out the photoreduction of benzophenone and use carbocation reaction conditions to effect the benzpinacol rearrangement. The absorption of the UV light creates electronically excited states in organic compounds, making the compounds to be in a higher energy state that will allow the compound to many reactions that normally do not happen when it is in the ground more stable state. In this experiment, the reduction of a ketone, benzophenone will be done in Part 1. Benzophenone absorbs ultraviolet radiation and uses the energy obtained as the driving force for its reduction by 2-propanol (isopropyl alcohol). The product, benzpinacol subsequently reacts with iodine in acetic acid to give the rearrangement product, benzpinacolone. Balanced Equation: IPA=isopropyl alcohol

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Mechanism: Part 1-Photoreduction of Benzophenone

Benzophenone to benzopinacol: Step 1: hydrogen abstraction from 2-propanol

Step 2: hydrogen abstraction from 2-propanol radical

Step 3: dimerization (Combine the 2 benzhydrol radicals)

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Mechanism: Part 2-Rearrangement to Benzpinacolone

Benzopinacol to benzopinacolone:

Diagrams:

Figure 3.1: Conversion of Benzophenone to the Diradical Species

Figure 3.2: Reflux Set-up

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2. Procedure: Part 1:Photoreduction of Benzophenone This experiment requires all irradiation period of at least 24 hr. 1. In a 125-mL E. flask, dissolve 6.0 g of benzophenone in 30 mL of 2-propanol (isopropyl alcohol). Warming on a steam bath may be necessary. 2. Add a dropper of glacial acetic acid to ensure that no alkali is present. 3. Label the flask, stopper it tightly with a cork, and give it to your instructor to be irradiated for a day or two. 4. After the irradiation, cool the test tube in an ice-bath for 10 min. and collect the solid by vacuum filtration. 5. Allow the solid to air dry. Determine its weight and melting point. Compare MP with book value. Part 2:Dehydration of Benzpinacol to benzpinacolone. 1. In a 50-mL RBF provided with a reflux condenser, place 0.05g of iodine (2-3 sm. crystals) and 15 mL of glacial acetic acid. Add 3.0g of benzpinacol and heat the soln slowly until it boils gently. 2. Reflux the rd soln 5-7 min. Cool the rxn flask in an ice-water bath, benzpinacolone will precipitate as fine needles. 3. Thin the pasty product with a few mLs of cold ethanol before collecting the crystals by vac. filtration. Wash the crystals until it is free of iodine color. 4. Dry the benzpinacolone, calculate % yield and determine its MP. 5. Obtain the NMR spectrum and the IR spectrum and analyze peaks.

Observations: Part1: Step#5: 2.11g of benzpinacol was obtained; MP 180C Part 2: -Step#2: benzpinacolone precipitate (fine needles) was observed

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3.Flow Chart: In a 125-mL E. flask, dissolve 6.0 g of benzophenone in 30 mL of 2-propanol (isopropyl alcohol). Warming on a steam bath may be necessary.

Part 1:Photoreduction of Benzophenone Add a dropper of glacial acetic acid. Label flask, stopper a cork instructor to be irradiated for 1-2 days. Next day; test tube in an ice-bath for 10 mincollect the solid by vac. filtration. Weight and MP. Compare w/ book value.

Part 2:Dehydration of Benzpinacol to benzpinacolone. Get 50-mL RBF w/ reflux condenser: + 0.05g of iodine (2-3 sm. crystals) + 15 mL acetic acid. + 3.0g of benzpinacol and heat slowly =>boils gently. Reflux the rd soln 5-7 min. Cool flask. Add few mLs of cold ethanol vac. filtrationWash crystals with cold ethanol. Weight, calc. % yield, and determine its MP. NMR spectrum + IR spectrum => analyze peaks.

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4. Table of Reagents: Compound Name

Benzophenone

Molecular weight (g/mol)

182

Density (g/mL)
1.11 g/mL

M.P. (C)
49

B.P. (C)
305

Concentration (for soln.)

-----------------

2-propanol 60.1 0.79 g/mL -89 83 -----------------

Glacial Acetic acid

60.1

1.05 g/mL

16-17

118-119

-----------------

Benzpinacol 366 1.24 g/mL 188 508 -------------------

Iodine

I2

127

4.93g/mL

114

184

---------------

Ethanol

46.1

0.79g/mL

-114

78

----------------

Benzpinacolone

348

N/A

179

N/A

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5. Results:(Data/Calculations included)
Part 1: Photoreduction of Benzophenone Mass of Benzpinacol: 2.11g MP of Benzpinacol: 179-180C Theoretical MP Benzpinacol: 188C Part 2: Mass of benzpinacolon used: 2.11g Mass of product (benzpinacolone): 1.42g Theoretical Yield of product: 2.01 g Experimental (observed) melting point: 164-165C Calculations: Part 2: Finding Limiting Reagent Benzpinacol= (BPNCol) Product= Benzpinacolone (BPNColone) (348 g product) (1 mol product) = 2.006 g product Percent Yield: 70.6% = 71% Theoretical MP: 179C

(2.11g BPNCol) x (1 mol BPNCol) x (1 mol product) x (366 g BPNCol) (1 mol BPNCol) Glacial Acetic acid (AA)

(15.0 mL AA) x (1.05 g AA) x (1 mol AA) x (1 mol product) x (348 g product) (1 mL AA) (60.1g AA) (1 molAA) (1 mol product) = 91.20 g product The limiting reagent is Benzpinacol. Theoretical Yield Benzpinacolone (2.11g BPNCol) x (1 mol BPNCol) x (1 mol product) x (366 g BPNCol) (1 mol BPNCol) Percent Yield For recrystallized product: (mass of recrystallized product) x 100% (theoretical yield) = (1.42 g) (2.01 g) x 100% = 70.65% =71% (348 g product) (1 mol product) = 2.006 g product Benzpinacolone

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5. Results (cont) Benzpinacolone was obtained in a 71% yield from the reaction of the limiting reagent benzpinacol and glacial acetic acid. A melting point was taken and resulted in 164 -165C which was fairly close to the theoretical mp, which indicated that our sample had a small amount of impurities and therefore concluding that our photoreduction and dehydration reaction was a success. - Since IR spectrum was given by Prof. Chanmugathas, the major peaks will be discussed in the discussion portion. -Physical properties of Product: Color- clear/colorless Crystal size- fine needles Smell- N/A -NMRs of benzpinacol and benzpinacolone are in the following pages

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6. Discussion: In this two part experiment, bezophenone first reacted with 2-propanol and sunlight (UV light) to form benzpinacol, then benzpinacol mad in part 1 was use to synthesize benzpinacolone by reacting it with 2 iodine crystals and acetic acid. The percent yield of the product was 71%. This was a very good yield due to the fact that we did not start with the required 3g for the reaction to give us a good yield in part 2, this was due to the rainy weather we were having and since the reaction required a substantial amount of light, possibly the solution did not receive the amount of UV light needed.. Another possible error that contributed to loss was that the mixture was in the reflux apparatus for 10-12 min, and since the iodine would not wash off the crystals, we added maybe more ethanol than was needed. Lastly another possible error was during filtration, since some crystals were stuck in the Buchner funnel and it was hard to scrape off without scrapping some of the filter paper as well. The observed melting point of the product was 164-165C which is fairly close to the theoretical melting point value of 179C. The observed melting point tells us that we have a good sample because the observed value is close to the book value, giving us a product with a low amount of impurities. The change of melting point could have been due to there still being some ethanol present in the product that didnt evaporate as well as some filter paper stuck to the crystals. An IR spectrum of benzophenone and IR and NMR spectrums of benzpinacol and benzpinacolone were given by our instructor. Upon analysis, the IR of benzophenone shows 3 peaks; a stretch C-H (sp2) peak at approx. 3020 cm-1, a stretch C=O peak at 1750 cm-1, and a stretch Aromatic C=C at 1600cm-1. The IR of benzpinacol shows 4 peaks; a stretch O-H peak at 3551cm-1, a stretch C-O at 1050cm-1, a stretch Aromatic C=C at aprox. 1500cm-1, and a stretch aromatic C-H peak at C-H (sp2) at approx. 3022cm-1.The IR of benzpinacolone shows 4 peaks; a stretch C=O at 1676cm-1, a stretch C-C at 1217cm-1, a aromatic stretch C=C at 1494cm-1, and an aromatic stretch at C-H (sp2) at 3083cm-1. The 1HNMR and 13C NMR peaks are in the results section. From the IR spectra, we can
look at what the characteristic for each peak to identify which functional groups are present and therefore identifying what type of molecule we have. The differences between benzpinacol and benzpinacolone is the CHOH group has changed into a C=O. That's going to change a lot of things in the spectra. In the benzpinacolone IR, an OH is gone, and a C=O has been formed, so a broad (and very obvious) -OH peak in the 3200-3400 range disappears, and is replaced by a strong and sharp C=O peak in the 1720+ range. In the proton NMR for benzpinacolone, you'll have fewer signals,no O-H signal, and no signal for the CH-OH proton on the carbon. The splitting pattern will get simpler, too. In the C NMR, the most obvious thing that will happen is the appearance of a C=O carbon signal in about the 200 ppm range.

My lab partner and I tried with the best of our abilities to follow every step of the experiment within an acceptable time frame and always double checking every step before performing the following step. Something that could have possibly given us that small amount of error was the that we could have lost some of our product while transferring to the Buchner funnel for filtration and possibly the addition of too much ethanol during washing. In conclusion, this photoreduction of benzophenone and dehydration of benzpinacol to benzpinacolone worked and was successful producing a yield of over 71%. Since the final product was a solid white fine needle size crystals, our % yield was good, and our products melting point was within a reasonable range, we can say that our experiment was a success in giving us our desired product

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7.References: Lab Handout: Nitration of Methyl Benzoate for Chemistry 212 WLAC Spring 2012, Dr. Chanmugathas