Hydration of a Terminal Alkyne.

Preparation of 3-Methyl-3-Hydroxy-2-Butanone
Riyushi Mahadik
4/10/2014
Introduction
The objective of this lab is to prepare 3-methyl-3-hydroxy-2-butanone by hydration of 2-methyl3-butyn-2-ol. The preparation process includes the usage of techniques such as heating under
reflux, steam distillation, rotary evaporation, vacuum filtration, and recrystallization. Moreover,
the final product will also be analyzed by IR spectroscopy, semicarbazone derivativatization, and
melting point determination.
When a Lewis base interacts with electrophilic reagents such as Lewis acids, an Electrophilic
addition reaction produces both alkenes and alkynes. The reagents E-Nu are added to the carboncarbon multiple bonds in the process alkynes undergo an electrophilic addition reaction which is
termed as hydration of the carbon-carbon triple bond. In the presence of mercuric ion and
sulfuric acid, the alkyne is transformed into a ketone and the mercuric ion is converted into a
cyclic mercurinium ion which facilitates the attack of water to the more substituted carbon. As
shown in Figure 1, the hydration of alkynes results leaving mercuric ion forming vinyl alcohol
which is very unstable and quickly tautomerizes to give the ketone.

Figure 1
The hydration of alkynes requires both sulfuric acid (H2SO4) and mercuric oxide (HgO). The H+
and Hg2+ acts like catalyst so the addition of Hg2+ forms much more stable and also low in
energy mercurinium intermediate. If only H2SO4 was present, then very unstable 1 vinylic
carbocation would form that is too high in energy. Thus, the water molecule (nucleophile) would
not attack an unstable carbocation that is produced in absence of Hg2+and ketone formation
would not occur. As shown in Figure 2. , hydration of an alkyne is regioselective, that is the
reaction prefers one site of a functional group over other sites that could undergo the same
reaction. This reaction follows the Markovnikov rule to form the final product. Based on
Markovnikov Rule, a proton is added to the least substituted carbon (more hydrogen) atom to
form a stable carbocation intermediate.

Figure 2
In order to perform the hydration of alkynes, different techniques are needed. For example, in
this lab many techniques such as heating under reflux, steam distillation, extraction of organic
solution from aqueous solution, and recrystallization are used to produce alkynes. The
importance of heating mixture under reflux is to heat reaction at its boiling point for long period
of time. Thus, creating a very high temperature allows the mixture to proceed for Markovnikov
addition over anti-Markovnikov addition to form the ketone. The purpose of steam distillation is
to separate the organic product from excess mercuric oxide. The volatile product would be codistilled with water vapor.
In order to separate excess CH2Cl2 from the product, rotatory evaporation was performed. In
rotary evaporator, solvents are evaporated under reduced pressure without bumping. The solution
is under vacuum, lowering the pressure above the liquid decreases its boiling point which results
in faster evaporation. The hot water bath heats the liquid bringing it closer to the boiling point. In
rotatory evaporation methylene chloride was removed from the product. The surface area for
evaporation for of the solution increases because of centrifugal and frictional forces produced.
The rate of evaporation in a rotatory evaporator can be controlled by adjusting the vacuum, the
temperature of the water bath, and the rate of rotation of the flask.
A ketone or aldehyde functional group solutions are converted to semicarbazones that are highly
crystalline solids. In this lab, semicarbazone derivatization was performed to verify the product
of hydration. Semicarbazide undergoes a condensation reaction with ketones and aldehydes. The
mechanism of semicarbazone formation is shown in Figure 3, so only the beta-nitrogen atom
which is the second atom adjacent to the carbonyl carbon of semicarbazide undergoes addition to
the aldehyde or ketone and it is the most nucleophilic. The electron pairs on the alpha nitrogen
atoms that is the first atom adjacent to the carbonyl carbon are delocalized through resonance.
Therefore, they are less available for bonding to other atoms, which makes the nitrogen atom less
nucleophilic.

Figure 3
The last step of the experiment is to perform melting point of the substance to verify the purity of
the product of hydration. Pure solids melt over a narrow range-usually 1C or less whereas an
impure sample will have a broadened melting point range and a overall decrease in the melting
point. The reason for not performing boiling point is because it is less accurate and less precise
when using a simple distillation setup with an uncalibrated thermometer. In contrast, melting
point analysis only requires a small amount of the product. Along with that, melting points of
many semicarbazones are reported in the chemical literature, a comparison with the experimental
values can help identify or verify the product of the reaction. As shown in Figure 3, through
Markovnikov addition, the 3-hydroxy-3-methyl-2-butanone will form a semicarbazone with a
melting point from 162-163C and through anti-Markovnikov addition, the 3-hydroxy-3-methylbutanal will form a semicarbazone with a melting point of 222-223C. Recrystallization of the
semicarbazone product was performed to determine the percent yield of the hydration product.
And IR was performed to analyze the structure of the product. The IR graph of 2-methyl-3butyn-2-ol will not have a peak for the carbon-carbon triple bond because dipole moment
between them is very small. The structure of -hydroxy-3-methyl-2-butanone has a ketone and so
there will be a peak between 1705-1725 cm-1 region. The hydration product also has a hydroxyl
group showing the peak between 3200-3650 cm-1.
Procedure:
Part I. Preparation of 3-Hydroxy-3-methyl-2-butanone
In a 250 round bottom flask, 20 mL of 3M sulfuric acid was added. Then, 0.22g of HgO and
swirled to dissolve.The flask was cooled to 50C. and it was equipped with reflux condenser
with water tubes allowing the water into the condenser. From the top of the condenser, 3.6 mL of
2-methyl-3-butyn-2-ol was added to the round bottom flask and swirled for few minutes. Two
water tubing were obtained and were hooked with the condenser. After the white precipitate is
seen, the mixture was then heated for 30 minutes, and allowed to cool to room temperature.
Part II. Steam Distillation

The steam distillation apparatus was assembled with the the reaction mixture heated in reflux
condensation of 250 ml bottom flask attached to claisen adapter, stillhead, west condenser (thin
column), bent vacuum adapter, separatory funnel, thermometer, and thermometer adapter. To
prevent vapor from escaping apparatus, the equipment were tightly clipped with keck clips. The
separatory funnel with warm water was placed at the open end of claisen adapter and stillhead
was placed through another open end. A thermometer was placed into stillhead with the support
of thermometer adapter. The thermometer was placed slightly below the entrance of condenser to
ensure the mercury bulb of thermometer is immersed thoroughly in the vapors. Then, two water
tubing were obtained and were hooked with west condenser. One of the water tubing allowed the
water into the condenser and the other was there to drain it. The distillate was collected upto 48
ml in a pre-weighed graduated flask.
Part III. Extraction
In a separatory funnel, 48 mL of distillate collected through steam distillation was transferred
and 2.5 g of potassium carbonate (K2CO3) was added to dissolve. Then, about enough NaCl was
added to make the solution saturated. The mixture was then sequentially extracted with three
portions of 10 mL of dichloromethane (CH2Cl2). The bottom layer was the organic layer. The
organic extracts were then combined. About 1-2 g of anhydrous sodium sulfate was added to
organic extractions to remove any suspended aqueous solution in the organic extract. Then, the
solution was decanted into a pre-weighed 50 mL round bottom flask. Finally, rotatory
evaporation was performed at 4 rotations in warm water to remove methylene chloride.
Part IV. Rotatory Evaporation

The flask was attached in such a way that the solution could be heated by the hot water bath. The
flask was rotated at 4 rotations per second which caused the solution to spread out over the flask.
Rotation helped prevent bumping. In order to avoid excessive bumping of solution, the pressure
was released frequently. The solution was under reduced pressure which resulted in lowering its
boiling point and thus increasing the rate of evaporation. The product was now weighed and
percent yield was calculated.
Part V. Derivatization
1.3 ml of final product, 3-hydroxy-3-methyl-2-butanone was added into a test tube with 1g of
semicarbazide hydrochloride and 1.6 g of sodium acetate dissolved in 5 mL of water. It was
shaken vigorously and the crude solids were collected by performing vacuum filtration using. A
piece of filter paper was placed in the funnel to cover the holes of the funnel. The liquid
impurities go down the filtration flask as the crystalline solid gets collected in the funnel.
Part VI. Recrystallization of Semicarbazone
About 0.5 g of crude solids were then added to 5 ml of hot 2-Propanol. The mixture was then
allowed to cool to room temperature and it was placed in ice bath for recrystallization. The final
crude solid was collected after performing vacuum filtration again. Then, the melting point of
solid without the recystrallization was taken in a melting point apparatus.
Melting Point and Spectroscopy
Due to some issues with the recrystallization, the product before the recrystallization was used to
determine the melting point using the Mel-temp apparatus. The sample was transferred into a
melting-point capillary tube which was placed into the melting point apparatus and the heat was
gradually turned higher while both solid compounds were observed through the lens. The
temperature interval at which solids melted was recorded. IR Spectroscopy test was performed of
3-hydroxy-3-methyl-2-butanone.
Data Acquisition/ Calculation:
The percent yield will help in determining the success of this experiment. The formula for
calculating the percent yield as follows,

Percent Yield = [(Actual Yield) / (Theoretical Yield)] x 100

Compound
Density
Molar Mass
2-methyl-3-butyn-2-ol (1)
0.8608 g/mL
84.118g/mol
3-hydroxy-3-methyl-20.971 g/mL
102.13 g/mol
butanone (3)
semicarbazide hydrochloride
111.53 g/mol
Semicarbozone (8)
155.19 g/mol
Reference from: http://www.chemsynthesis.com/base/chemical-structure-14072.html
Theoretical Yield:
3.6 ml 2-methyl-3-butyn-2-ol (0.8608 g/ml) (84.118g/mol) = 0.0368 mols of 2-methyl-3-butyn2-ol
0.0368 mols of 2-methyl-3-butyn-2-ol (1 mol of 2-methyl-3-butyn-2-ol/ 1 mol of 3-hydroxy-3methyl-2-butanone) (102.13 g/mol 3-hydroxy-3-methyl-2-butanone) = 3.76 g 3-hydroxy-3methyl-2-butanone
Actual Yield:
Mass of empty flask = 29.76 g
Mass of the flask + product = 31.25 g
Mass of the product (3-hydroxy-3-methyl-2-butanone) =
(Mass of the flask + product) (Mass of empty flask) = 31.25 g 29.76 g = 1.49 g 3-hydroxy-3methyl-2-butanone
Percent Yield: [(1.49g) / (3.76g)] x 100 = 39.6%
Semicarbazone derivative:
Semicarbazide + 3-hydroxy-3-methyl-2-butanone = semicarbazone (8)
Theoretical Yield:
(1g semicarbazide)( 111.53 g/mol)(1 mol carbazone/1mol carbazide) = 0.0089 mol
semicarbazone

(1.3 mL 3-hydroxy-3-methyl-2-butanone)( 0.971 g/mL)( 102.13 g/mol)(1 mol carbazone/1mol 3hydroxy)= 0.0123 mol semicarbazone

Limiting reactant is semicarbazide

(0.0089 mol semicarbazone) (155.19 g/mol) = 1.39 g semicarbazone

Actual Yield of semicarbazone: 0.01 g
Percent Yield: [(0.01 g) / (1.39 g)] x 100 = 0.72 %.
Melting Point
The melting point was obtained to confirm the purity of the collected crystal and if the
Markovnikov rule was carried out by hydration reaction.
Substance
Semicarbazone

True melting Point (C)

162 163 C

Experimental Melting Point (C)

155 160 C

Infrared Spectroscopy
The infrared spectroscopy was performed to determine the presence of functional groups in the
final product.
Frequency
3454.17 cm-1
2978.39 cm-1
1708.42 cm-1

Intensity
Broad, Short
Short
Strong, Sharp

Functional Group(s)
O-H (Alcohol)
Hybridized sp3 C-H bond
C=O (of Ketone group)

Conclusion:
The purpose of the lab is to prepare 3-methyl-3-hydroxy-2-butanone by hydration of 2-methyl-3butyn-2-ol. The preparation process includes the usage of techniques such as heating under
reflux, steam distillation, rotary evaporation, vacuum filtration, and recrystallization. Moreover,
the final product will also be analyzed by IR spectroscopy, semicarbazone derivativatization, and
melting point determination. All these methods were successful because the final product was
achieved at the end. Due to IR peaks, it was verified that the product resulted after hydration was
at the end was 3-methyl-3-hydroxy-2-butanone (3) showed three peaks: a short, broad O-H peak
at 3454.17cm-1, a short sp3 hybridized C-H bond peak at 2978.39 cm-1, and a strong, sharp
carbonyl peak of the ketone at 1708.42 cm-1.
Even the melting point determination further identified the isolated pure compound
semicarbazone by melting at 155 160 C. The produce was derived from 3-hydroxy-3-methyl2-butanone. The melting point range was close to the original melting point range. This confirms
that our derivatization of semicarbazone was successful through reaction based on Markonikov
rule. The other major identification was that if the reaction gone under anti-Markonikov rule
then, the melting point range for the semicarbazone would have been close to 222-223C.

Similarly, percent yield specifically examined the amount of product produced and how
efficiently. The percent yield was calculated twice; first percent yield was calculated after steam
distillation and rotatory evaporation were performed, and second percent yield was calculated
after derivatization of semicarbazone. The percent yield of 3-hydroxy-3-methyl-2-butanone was
39.6%. The reason why the entire formed product was not recovered could be that some of the
ketone could have been lost in the transformation as the experiment procedure involved several
steps or could have evaporated due to its high volatility. The percent yield of semicarbazone was
only 0.72%. Such low percent yield suggests that we might have made errors while performing
derivatization process. Also while performing vacuum filtration after derivatization, we didnt
obtain any of the crystalline product. Therefore, derivatization was performed twice followed by
vacuum filtration and this might have reduced the quantity of our product.
Despite having low percent yields of the final products, overall our experiment was successful
because our data for the IR and melting point range were mostly accurate. Therefore, hydration
of 2-methyl-3-butyn-2-ol to obtain 3-hydroxy-3-methyl-2-butanone was successfully performed
and the purity of our final product was verified by IR, derivatization, and melting point analysis.
Reference