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Formal Lab Report for EXPERIMENT 2: Pinacol Rearrangement

Juei-Sheng (Joshua) Chiu, Experiment performed 2/5/15 and 2/12/15


Report submitted 2/19/15

Objective: The objective of this experiment was to react pinacol with sulfuric acid under heat, and after
rearrangement under those conditions, isolate pinacolone from water. Thereafter, we were to verify the product
through reaction with DNP, and run IR and NMR spectra on the product.
Synthetic equation for the reaction:

Figure 1. Reaction of Pinacol in an acidic solution with heat yielded Pinacolone and water.
Chemical Formula & Structure, Molar Mass, Density, Melting/Boiling Point & Hazards 1,2.
Pinacol (C6H14O2), melting pt. 40 C, mol. Mass 118.2 g/mol., Irritant, flammable.

Pinacolone (C6H12O), boiling pt. 103 C, mol. Mass 100.16 g/mol., density .8g/mL, flammable.

2,4-dinitrophenylhydrazine (C6H6N4O4), melting pt. 198 C, mol. Mass 198.1 g/mol., flammable.

2,4-dinitrophenylhydrazone (C12H16N4O4), melting pt. 125 C, mol. Mass 280.28 g/mol.

Sulfuric Acid (H2SO4), boiling pt. 337 C, mol. Mass 98.08 g/mol., density 1.84 g/mL, corrosive.

Sodium Chloride (NaCl), melting point 801 C, mol. Mass 54.44 g/mol., irritant.
Sodium Sulfate (Na2SO4), melting point 884 C, mol. Mass 142 g/mol., irritant.

Water (H2O), boiling pt. 100 C, mol. Mass 18.02 g/mol., density 1g/mL.
Procedure
3.0 g of pinacol and 30 mL of deionized water were added to a 50 mL round-bottom flask. The mixture
was then heated gently in a heating mantle until it dissolved. The flask and its contents were cooled to room
temperature by immersion in a tap water bath. The use of an ice bath was avoided. 1-2 boiling chips were added
and then 5.0 mL of concentrated sulfuric acid was carefully added, with swirling. It was exothermic reaction. If
Formal Lab Report for EXPERIMENT 2: Pinacol Rearrangement
Juei-Sheng (Joshua) Chiu, Experiment performed 2/5/15 and 2/12/15
Report submitted 2/19/15
the flask seemed to have become too hot, it was cooled in a tap water bath. The mixture was swirled for 10
minutes. The round bottom flask was connected to a simple distillation apparatus and distilled into a 25 mL
round bottom flask. The distillation was stopped when the vapor temperature reached 100 C. Then, 5 ml of
saturated NaCl solution was added to the distillate, and mixed well. The aqueous layer was removed using a
transfer pipet. Nothing was thrown out when IR spectra verified the product. The organic layer was dried over
anhydrous sodium sulfate and the dried liquid was decanted into a clean, dry, pre-weighed sample vial. The
liquid was weighed. The product was kept sealed until the following week when IR and NMR spectra were run.

Additionally, a 2,4-DNP test was performed on the product. 1mL of 2,4-DNP test reagent was added to a dry
test tube. 5 drops of the product were added and mixed with a stirring rod. The results were recorded.

Calculation of percent yield.


Reaction of 1 mole of pinacol will yield 1 mole pinacolone, under ideal conditions (this is the theoretical yield).
Therefore,
3g of pinacol * (1 mole pinacol/118.2 g pinacol) = .0254 moles pinacol reacted = .0254 moles pinacolone
produced, .0254 moles pinacolone * (100.16 g / 1 mole pinacolone) = 2.542 g pinacolone (theoretical)
Mass of product weighed was 1.15g.
% Yield = (experimental / theoretical) x 100 = (1.15g/2.542g) x 100 = 45.24%.
Results
The product of the reaction was decanted after drying over anhydrous sodium sulfate into a sample vial, with a
measured mass of 1.15g. This was a percent yield of 45.24%.
The result of the DNP test was that a yellow-orange precipitate was observed in the test tube.
IR spectra was performed on both the reactant, pinacol, and the product, pinacolone. Pinacol had IR peaks at
2941, 2978, and 3441 wavenumbers. Pinacolone had IR peaks at 1708, 2875 and 2975 wavenumbers. Both IR
spectra are attached.
NMR spectra was performed on both the reactant, pinacol, and the product, pinacolone. Pinacol had NMR
peaks at approximately 1 (height 12) and 2 (height 2) ppm, while pinacolone had NMR peaks/clusters at 1
(height 9), 2.1 (height 3) ppm. Both NMR spectra are attached.
Discussion
In this experiment, we used the full pinacol rearrangement mechanism to react a diol (pinacol) into a ketone
(pinacolone), using sulfuric acid as the catalyst (forming an acidic solution) and producing water as a
byproduct. The first step in the reaction is the protonation of one of the hydroxyl groups on the pinacol diol.
Dehydration then occurs when the protonated OH group leaves as water, forming a forming a tertiary
carbocation. A methyl shift (alkyl rearrangement) then occurs, gives a resonance-stabilized carbocation, which
is stabilized due to oxygen having two lone pairs. Two of the four unbonded electrons on the oxygen
spontaneously form a double bond with the carbocation. Once a double bond is formed, the oxygen is then
deprotonated, forming a ketone. See mechanisms on last page of report.
Formal Lab Report for EXPERIMENT 2: Pinacol Rearrangement
Juei-Sheng (Joshua) Chiu, Experiment performed 2/5/15 and 2/12/15
Report submitted 2/19/15
As the pinacol reacted to form pinacolone, the flask was kept heated and the product, pinacolone, was
continuously co-distilled with water from the reaction mixture, which drove the reaction equilibrium towards
the product side of the equation. Since water and pinacolone were immiscible, Raoult’s law applied, which
meant that the two liquids would co-distill at a lower temperature than either of their individual boiling points.
Therefore, when the temperature of the distillate reached 100 C, all of the pinacolone would have been distilled
– and that is when the distillation was stopped. Thereafter, the bottom layer in the receiving flask was identified
as water and removed, since water had a higher density than pinacolone (1 g/mL versus 0.81g/mL).

Pinacolone and 2,4-dinitrophenylhydrozine reacted in a test tube to form 2,4-dinitrophenylhydrozone derivative,


which is a yellow/orange/red precipitate. Since we observed a yellow-orange precipitate, the product was
probably pinacolone.

The IR spectrum of the reactant, pinacol, had a major peak at 3441 wavenumber. A peak at 3441 wavenumber
corresponds to a hydroxyl functional group, which was thicker in this case because of the presence of two
hydroxyl groups; this identifies the reactant as pinacol. The IR spectrum of the product had a peak at 1708
wavenumber, which corresponds to a carbonyl group. Since pinacolone has a internal carbonyl, a ketone, this
confirms that the product was pinacolone.

The NMR spectrum of the reactant, pinacol, had a peak at 1 ppm (height 12), which corresponds to the four
triplets of primary hydrogens (methyl groups); the peak is a singlet because the carbons the hydrogens were
attached to was attached to a tertiary carbon (which had a hydroxyl group occupying the fourth bond) – so there
were no adjacent carbons for any of the four triplets of primary hydrogens. The second peak in the pinacol
(reactant) NMR at 2 ppm corresponds to a hydrogen in a hydroxyl group; the peak was height 2 because there
were two hydroxyl groups, and the peak was a singlet because both hydroxyl groups were attached to tertiary
carbons (so no adjacent hydrogens were present).
The NMR spectrum of the product had a peak at 1 (height 9), which corresponded to the three triplets of
primary hydrogens (methyl groups); the peak is a singlet because the carbon the three triplets are attached to
was quaternary (so there were no adjacent hydrogens present) The NMR spectrum of the product had another
peak at 2.1 (height 3), which corresponds to a single triplet of primary hydrogens attached to a ketone carbon;
peak is a singlet because the adjacent carbon is a ketone and therefore contains no attached hydrogens. Since the
NMR spectrum of the product corresponds to the expected functional groups on pinacolone, the product was
confirmed to be pinacolone.
References
1. Aldritch, Sigma-. (No date). Sigma-Aldritch. Retrieved February 15, 2015, from
http://www.sigmaaldrich.com/united-states.html
2. Sneden, Albert T. (No date). EXPT. 2: Pinacol Rearrangement. Richmond, VA: VCU Department of
Chemistry.
Formal Lab Report for EXPERIMENT 2: Pinacol Rearrangement
Juei-Sheng (Joshua) Chiu, Experiment performed 2/5/15 and 2/12/15
Report submitted 2/19/15

Figure 2. Mechanism of Pinacol rearrangement.