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Experiment #5: An Unexpected
Reaction of 2,3-dimethyl-2,3-butanediol
Author:
TAs: Lab Section:
AB1
Date:
10/11/2022
Objective:
Purify via fractional distillation and determine the identity of the unexpected product of the
acid-catalyzed reaction of 2,3-methyl-2,3-butanediol via IR, NMR, and boiling point analyses.
Introduction:
The pinacol rearrangement reaction was discovered in 1860, but despite being around for so
long, it still continues to be applied to various industries and cutting-edge research now, in the
21st century. The pinacol rearrangement reaction is important for synthesizing certain fertilizers,
fungicides, and pesticides. It’s also used to make pharmaceutical drugs such as pinacidil and
Stiripentol, which is used to . A study published in the European Journal of Medicinal Chemistry
detailed the use of pinacol rearrangement in finding other anticonvulsant drugs as an alternative
to Stiripentol.
https://doi.org/10.1016/j.ejmech.2011.11.004
Balanced Equation for Formation of Diene:
H
2
SO
4
C
6
H
14
O
2
--------------->
C
6
H
10
+ 2 H
2
O
Mechanism of Formation of Diene:
Balanced Equation for Formation of Unexpected Product:
H
2
SO
4
C
6
H
14
O
2
------------> C
6
H
12
O + H
2
O
Mechanism of formation of unexpected product:
Table of Reagents:
Name
Molecular
weight
(g/mol)
Melting
pt (c)
Boiling
pt (c)
Density
(g/cm³)
Hazards
2,3-dimethyl-2,3-butanediol
118.174
40- 41
157-159
0.967
irritant
2,3-dimethyl-2,3-butanediol
diene
82.143
----
approx
70
----
Sulfuric acid
98.079
10
337
1.83
Corrosive,
irritant
Dimethylformamide (DMF)
73.09
-61
153
0.948
Skin irritant
NaCl
58.44
801
1465
2.16
----
C6H12O (unknown)
100.16
---
---
---
----
Written Procedure / Observations:
Procedure Summary
Observations
●
Put 3.6g of
2,3,dimethyl-2,3-butanediol, 10mL
H2SO4 (3M), and stir bar in 25 mL
round bottom flask.
●
3.604 g pinacol used
●
Approx 11 mL H2SO4
●
Set up simple distillation and put
receiving (25 mL round bottom) flask
in ice water bath. Heat solution until
receiving flask is half full.
●
Heat set at 155C initially
●
H2SO4 fizzled slightly when stir bar
placed in → was it contaminated?
●
Heat eventually turned up to 505C →
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hot plate not heating correctly
●
Transfer distillate to separatory funnel
and rinse receiving flask with little bit
of water, add water to funnel, then
drain aqueous layer.
●
Distillate clear
●
Solution being heated was murky
white at first but turned dark brown by
the end of the distillation
●
Reaction flask was approx. ½ full
●
Add 6 mL NaCl to funnel and swirl,
stopper, shake it. Let stand for several
mins. If no clear layer separation ask
TA before adding 10 mL DCM.
Separate organic layer.
●
No DMF was added
●
Distillate is clear
●
Transfer organic layer to erlenmeyer
flask, add MgSO4, while swirling,
until doesn’t clump. Wet filter paper
with DMF, filter into round bottom
flask, wash product with 3 mL DMF.
●
Purify product by fractional
distillation -- cover with aluminum
foil up to thermometer. Can be 2+
fractions (two in 70-75C boiling point
range, one unknown). Record boiling
point range for all and collect in
pre-weighed flasks.
●
F1: 32.908 g
●
F2: 22.401 g
●
F3 38.054 g
●
Heat set at 220C
●
Started rising rapidly at 28.1, dropped
at 50.2
●
Rose rapidly to 83.3, dropped to 66.9
●
Rose to 94.5, dropped to 86.6 → F1
collected
●
Then rose to 90.7, dropped to 84.4 →
F2 collected
●
Rose rapidly from 94.7 to 120.3,
dropped → F3 collected
●
Rest rose past 130C
●
Obtain IR for each fraction.
●
Make NMR sample of fraction that
has carbonyl IR peak (aka the
unknown).
●
Measure mass of unknown.
●
Carbonyl peak on 2nd fraction, used
that for NMR
●
F1: 63.434
●
F2 : 52.541
●
F3: 68.570
Formal Report Procedure:
To a 25 mL round-bottom flask, 3.604 g of 2,3,dimethyl-2,3-butanediol and approx. 11 mL
H
2
SO
4
(3M) was added. Using this, a simple fractional distillation was set up and allowed to run
until the receiving flask was half full. The distillate was then put in a separatory funnel and
rinsed with water and 6 mL NaCl, then dried with MgSO
4
. The organic product was filtered into
a round bottom flask and washed with 3 mL DMF. It was then purified by fractional distillation,
and 3 fractions were collected. The boiling point for all fractions was noted. An IR spectra of all
fractions was obtained, and an NMR sample of the second fraction was made, since it had a
carbonyl peak in its IR. The weight of the third fraction, i.e, the unknown, was recorded (1.709g,
56.01% yield). The weights of the first two fractions, i.e, the diene, were also noted (1.179g and
68.71% yield for first fraction; 1.333g and 53.28% yield for second fraction).
Theoretical Yields:
3.6g C6H14O2 * (1 mol/118.174g) * (1 mol diene / 1 mol C6H14O2) * (82.143g / 1 mol diene)
= 2.502g diene
3.6g C6H14O2 * (1 mol / 118.174g) * (1 mol unknown / 1 mol C6H14O2) * (100.16g / 1 mol
unknown)
= 3.051g unknown
Summary Table of Products:
Weight of flask + cork for each fraction:
Fraction 1: 32.908 + 28.807 = 61.715 g
Fraction 2: 22.401 + 28.807 = 51.208 g
Fraction 3: 38.054 + 28.807 = 66.861 g
Product
Experimental Yield
Percent Yield
Boiling Point (°C)
Fraction 1 (diene)*
63.434 - 61.715 =
1.719 g
(1.719 / 2.502) * 100
= 68.71%
86.8 – 94.5
Fraction 2 (diene)*
52.541 - 51.208 =
1.333 g
(1.333 / 2.502) * 100
= 53.28%
84.4 – 90.7
Fraction 3 (unknown)
68.570 - 66.861 =
1.709 g
(1.709 / 3.051) * 100
= 56.01%
94.7 – 120.3
*The combined weight of the two diene fractions exceeds the theoretical diene yield, suggesting
experimental error.
Summary Table for IR Spectral Data:
Wavenumber (cm
-1
)
Intensity (s, m, w)
Functional Group
2873.83 - 2970.58
s
Alkane C-H
1707.91
s
Acyclic Ketone
The IR data has two strong peaks in the 2800-3000 cm
-1
region; this strongly suggests the
presence of an alkane C-H in the structure of the molecule. There is also a strong peak at
approximately 1700 cm
-1
, suggesting the presence of an acyclic ketone.
Summary Table for NMR Spectrum Data (include original printout with report)
Labeled protons on unknown product corresponding to the NMR spectrum
Assignment
Chemical
Shift (ppm)
Splitting
pattern
Coupling
Constant
(Hz)
Integration
Comments
A
2.24
singlet
----
N/A
Unknown
impurity
B
2.13
singlet
----
N/A
Unknown
impurity
C
1.38
singlet
----
3
product
D
0.39
singlet
----
9
product
Discussion:
The formation of the unknown product is well-supported by the NMR and IR data; the NMR
spectra has two singlet peaks, suggesting two unique hydrogens in the unknown product. The IR
spectra contain peaks that correspond to alkane C-H and acyclic ketones; both of these outcomes
are clearly supported by the chemical formula of the unknown product, C6H12O. The unknown
was in the third fraction collected via distillation, and has a boiling point (94.7 – 120.3°C) that is
significantly higher than the known diene collected in the two fractions before it.
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Overall, the experiment was rather unsuccessful, with significant errors being made during its
execution that contributed greatly to data flaws such as inconsistent experimental yield and
chemical impurities. The experimental yields of the first two fractions collected (which should
have been dienes) should ideally have added up to 2.502g, the predicted theoretical diene yield.
However, adding these two values exceeds the theoretical yield, suggesting that there was
cross-contamination between the diene and the unknown product. Because of likely
contamination, the yields are not a good gauge of experimental success. This is further
supported by the fact that the second fraction, not the third, had a prominent acyclic ketone peak
in its IR spectra, even though the second fraction should’ve been pure diene, and the third
fraction should have been the unknown. In the NMR spectra, singlets A and B, at 2.24 and 2.13
ppm respectively, are not part of the unknown’s proton peaks; rather, they also indicate
contamination. The experimentally-determined boiling point of the diene (ranges from 84.4 -
94.4°C) was notably higher than the expected boiling point of around 70°C; this is yet another
indication of contamination.
Because of this widespread impurity, likely caused by errors collecting fractions during the
distillation, the unknown could not be successfully isolated and measured in the third fraction.
When collecting the fractions, the temperature changes were not closely monitored, and fractions
were allowed to undergo several significant temperature changes before they were collected.
This experiment should be repeated and improved upon by more closely monitoring fluctuations
in temperature during fractional distillation, so that the fractions are collected at the right time.
Conclusion:
The objective of this experiment was to isolate and identify the unknown in a pinacol
rearrangement of 2,3,dimethyl-2,3-butanediol. 56.01% of the unknown was ultimately
recovered. Although the product was formed (as indicated by the IR and NMR), severe
contamination/impurities were present, which is indicated by the higher-than-expected boiling
points, inconsistent percent yields, and extraneous NMR peaks.
Post Lab Questions:
1.
A
B
C
D
2.
Diene:
●
In a CNMR, I’d expect to see 3 signals, since there are 3 unique carbons present
in the molecule.
●
In an HNMR, there are 2 unique protons (2 signals expected)
○
Proton A: integration = 2, multiplicity = 1, chemical shift =
○
Proton B: integration = 3, multiplicity = 1, chemical shift =
Unknown:
●
In a CNMR, I’d expect to see 4 signals, since there are 4 unique carbons present
in the molecule.
●
In an HNMR, there are 2 unique protons (2 signals observed)
○
Proton A: integration = 9, multiplicity = 1, chemical shift = 0.39
○
Proton B: integration = 3, multiplicity = 1, chemical shift = 1.38
3.
(1) HCl is very volatile and would’ve gotten rid of all the acid, leading the reaction to not
proceed.
(2) Moreover, H2SO4 is hydroscopic; it removes water from the reaction, further driving
the reaction forward.
(3) Acid is used because it helps make alcohol a better leaving group.
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NMR Spectra:
Assignment
Chemical
Shift (ppm)
Splitting
pattern
Coupling
Constant
(Hz)
Integration
Comments
A
2.24
singlet
----
N/A
Unknown
impurity
B
2.13
singlet
----
N/A
Unknown
impurity
C
1.38
singlet
----
3
product
D
0.39
singlet
----
9
product
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Author:William L. Masterton, Cecile N. Hurley
Publisher:Cengage Learning

Elementary Principles of Chemical Processes, Bind...
Chemistry
ISBN:9781118431221
Author:Richard M. Felder, Ronald W. Rousseau, Lisa G. Bullard
Publisher:WILEY