DEHYDRATION OF

2-METHYLCYCLOHEXANOL AND
DISTILLATION OF METHYLCYCLOHEXENES
CHEM 203 Formal Lab Report
Chapter 9 Distillation: Dehydration of Alcohols

Name: Moyan Jia

ID: mkj5122 916970666
Section: 004
TA: Jason Marko
Date: 11/11/16

Dehydration of 2-Methylcyclohexanol and Distillation of Methylcyclohexenes

Introduction
Distillation is one of the isolation and purification techniques in organic
chemistry. The basic principle behind distillation is to separate liquid substances with
different boiling points in a mixture by turning each component into gas and condense.
When the mixture is heating, substance with low boiling point will primarily turn into
gas and condense into liquid for collection. There are several apparatuses among
distillation; i.e. simple distillation, steam distillation, fractional distillation, and vacuum
distillation, etc. Simple distillation, which was used in this experiment, is to separate
liquids whose boiling points difference is greater than 75. Miscible liquids can be
purified via simple distillation, and immiscible liquids can be isolated as well. Steam
distillation is to isolate essential oils from natural plants with water steam offering vapor
pressure. Fractional distillation is used when liquids boiling points are close, difference
less than 75, and this apparatus can isolate immiscible liquids and purify miscible
liquids. Fractional distillation is effective but time consuming. Vacuum distillation is
used for compounds with high boiling points and easy to decompose.1 Dry-distillation
should be avoided because heating dry glassware will crack the apparatus.
Distillation has great industrial significance. It is widely applied in alcohol
production and beverage purification. Pharmaceutical research also involves distillation
techniques.2
This reaction is appropriate for distillation is because both reactant and
products are liquids with distinct boiling points. The byproduct water is easy to separate
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from products. Additional solvent is not necessary in distillation, and so does this
reaction. In this experiment, the reactant 2-methylcyclohexanol and the product
methylcyclohexenes exist in the reaction mixture at equilibrium. Both are liquids but
immiscible. The former has boiling point at 163-166, and the latter have boiling
points around 102.3,4 Although the difference is not as great as 75, but simple
distillation is capable of separation. The condensation/vaporization theoretical plate is
large enough to separate compounds. This reaction is reversible, but simple distillation
separated methylcyclohexenes from the mixture, pushed the reaction to the right, and
prevented mechanism from reversing. Products include isomers and can be analyzed
further via GC and GC-MS.

Figure 1. Synthesis of methylcyclohexenes 2, 3, and 4 from 2-methylcyclohexanol 1.

At the beginning of this experiment, 2-methylcyclohexanol 1 was dehydrated
in phosphoric acid condition. The system was heated and the product
methylcyclohexenes were distilled and collected. Products contained 3 isomers,
methylenecyclohexene 2, 1-methylcyclohexene 3, and 3-methylcyclohexene 4 (Figure
1). Methylcyclohexenes are widely used as organic chemistry solvent in synthetic
laboratory.5

Scheme 1. Mechanism of dehydration of 2-methylcyclohexanol 1.

Within the mechanism, firstly, the lone pair electrons on the nucleophilic
alcohol attack the hydrogen from acid and form a water molecule attaching on the
hexane ring. This is protonation. Then, the single between the ring and the oxygen
breaks and provides electrons to the electrophilic oxygen atom. This step is single bond
breaking. Water is eliminated, and a carbocation intermediate forms. The lone pair
electrons on the oxygen of the conjugated base of phosphoric acid move to a hydrogen
on the ring. The hydrogen adjacent to the carbocation provides electrons to form a C-C
bond. If the adjacent hydrogen is on the same carbon with the methyl group, 1methylcyclohexene 3 forms; if the adjacent hydrogen away from the methyl group is
attacked, 3-methylcyclohexene 4 forms. If the carbocation intermediate runs a
whitmore shift, which allows the adjacent hydrogen shifts to the original carbocation,
a new carbocation forms with a methyl attached on it. While one hydrogen moves from
the methyl group to the conjugate base, a new bond and methylenecyclohexene 2
form. The step of electrophilic elimination finishes (Scheme 1). Product 3 and 4 are
kinetic control because their mechanisms do not include extra step of hydrogen shift as
2 does. Product 3 is the most thermodynamically stable because one carbon on the
double bond is secondary and have more substitutes. The predicated product ratio based
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on stability is and kinetics is 3>4>2. This mechanism is reversible, but distillation

pushes the reaction to the right.
Dehydration of alcohol is a common method to synthesize alkene. Since the
reaction includes carbocation formation from secondary or tertiary alcohol, multiple
products isomers form in the mixture. 1H NMR is inappropriate to analyze products
because the reactant and the products cannot be distinguished by unique hydrogens on
the spectrum. The hydrogen on alcohol group has a chemical shift at 7.0-12.0, which is
hard to detected or in the same range with hydrogen on the rings. Also, the products are
in mixture, methylene and methyl groups are difficult to justice belonging to which
compound. IR was used in this experiment, because it detects functional groups. The
product spectrum should display absence of C-O (1100 cm-1) and O-H stretch (36003200 cm-1), and presence of C=C-H (3300-3000 cm-1) stretch instead. Gas
chromatography (GC) was used to analyze the components of the mixture. The
compound with lower boiling point comes out from GC tube and displays a peak on the
spectrum primarily; and the one with hi1gher boiling point comes out later. The time
extension and the order of peaks are compared with gas chromatography mass
spectroscopy (GC-MS) data. GC-MS identifies compounds by time extensions and its
molar mass. The area of each peak on GC tells the percent product yield and product
ratio. GC/GC-MS is widely used in isomer identification.1
The experiment purpose was to apply simple distillation to isolate alkene
products. Once the products (methylenecyclohexene, 1-methylcyclohexene, and 3methylcyclohexene) were synthesized from 2-methylcyclohexanol dehydration,
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products were isolated via simple distillation. Then alkenes were extracted from
byproduct water. The alkenes were analyzed and identified via IR and GC/GC-MS. The
key stretches of IR were the absence of C-O (1100 cm-1) and O-H stretch (3600-3200
cm-1), and presence of C=C-H (3300-3000 cm-1) stretch. GC was supposed to
demonstrate 3 peaks for products and 1-methylcyclohexene was the major compound.
Experimental
2-methylcycloheanol (20 mL) and phosphoric acid (5.5 mL, 85%) were mixed
and stirred. The simple distillation apparatus was installed and heated.
Methylcyclohexenes (12.7349g, 81.32% crude yield) were condensed and collected in
a beaker containing water in ice bath. The reaction time, collecting situation, and
observed temperature of vapors were recorded (Table 1). Liquid-liquid extraction was
used to separate the top alkene layer from the water. After the alkene layer was washed
by sodium bicarbonate and sodium chloride, it was dried with anhydrous sodium sulfate.
The alkene mixture was transparent colorless liquid. The product (11.4616g, 90%
product yield) was identified via IR and GC/GC-MS.1 GC was run at the initial
temperature of 40 for 5 min; and then rate of heat was set 10/min; the final
temperature was 150.
Time (min)
0
15
30
45
60
70

Collecting
No
No
No
Yes
Yes
Yes

Observed Temperature
25
33
74
84
102
103

Table 1. Time and collection observation of distillation

Time (min)
1.408
1.493
3.457
3.847
4.232
9.235
9.393

Area
287
1689575
5125
987
27307
2893
826

Identification
Solvent dichloromethane
Solvent dichloromethane
Alene product
Alkene product
Alkene product
Alcohol starting material
Alcohol starting material

Product Ratio
N/A
N/A
15.33%
2.95%
81.71%
N/A
N/A

Table 2. GC data and product ratios.

Final
Mass

Theoretical
Yield

Crude %
Yield

% Product

12.7349g

15.66g

81.32%

Yield

Actual
Yield

% Yield Overall
Rxn

90%

11.4614g

73.19%

Table 3. Yield calculations based on GC data.

Frequency, cm-1
3353.51
2923.50
2857.16
1445.31

Functional Group
O-H Stretch
(C=) C-H Stretch, Ring
(C-) C-H Stretch, Ring
C-H, Methyl

Table 4. IR data of methcyclohexenes.

Results and Discussion
Once the products were distilled, identification of methylcyclohexenes via IR
and GC/GC-MS was discussed below.
The alkene products were collected in a beaker containing water. Initially, the
alkene liquid was cloudy, and after it was washed by brine it turned into transparent
colorless. At the very end of reaction, alcohol turned yellow and began to foam. Only
small amount of starting material was left in the reflux apparatus. According to the time
and collecting observation of distillation, vapor temperature between 74 and 84
triggered the distillation of alkenes. The process of distillation was time consuming,
and at 70 min the reaction was completed. After the vapor reached 103, the
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temperature decreased because alkenes were condensed into liquid and on longer at
vapor stage. The measured final mass of product was 12.7349 g, which is close to the
theoretical yield 15.66 g (Table 3). Dehydration of alcohol was successful since
appropriate amount of product was received and the refluxing was finished.
Refer to the IR spectrum (Figure 2), four distinct stretches were detected. A
large curve at 3353.51 cm-1 displays on the spectrum, which is the O-H stretch of
alcohol. Starting material alcohol was is the product mixture, and the quantity of alcohol
was also verified via GC. The reaction was not perfectly completed because of the
presence of alcohol. (C-) C-H stretch was detected at 2923.50 cm-1. This stands for the
hydrogen on the single-bonded carbon on the ring. Since both reactant and product
contain this stretch, it was not used for alkene identification. (C=) C-H stretch was at
28757.16 cm-1. This is the evidence of product presence because only alkene contains
double bond between two carbons. And last, methyl group was shown at 1445.31 cm-1.
Both reactant and product contain a methyl group. The C-O stretch of starting material
was not shown on the spectrum, which reveals the absence of alcohol. Above all, key
stretch C=C was detected and C-O was not detected, but O-H still existed in the product
mixture. Alkene product was formed, but the starting material alcohol was in the
mixture as well. The mount of alkene was analyzed further via GC.
Based on GC data (Figure 3), 3 alkenes were detected and so were solvent
dichloromethane and alcohol. In the first 2 min, dichloromethane came out. Around 9
min, alcohol starting material came out because 2-methylcyclohexanol has higher
boiling point than methylcyclohexenes.3 At 3.457 min, one product at the ration of
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15.33% came out; at 3.847 min, another product at the ratio of 2.95% came out; and at
4.232, product at the ratio of 81.71% came out (Table 2). Refer to the hypothesis, 15.33%
of

the

products

methylenecylohexene;

was

3-methylcyclohexene;

and

81.71%

was

2.95%

of

1-methylcyclohexene.

products
Because

was
1-

methylcycloexene has a secondary substituted alkene, which is thermodynamic favored

and kinetic controlled, it is the major product. It is the most stable one, so it has highest
boiling point and came out on the GC spectrum at last. Methylenecyclohexene has an
extra step of whitmore shift during the formation mechanism, it is the least favored
product. Also, it has a secondary carbocation intermediate whose stability was
relatively good, so it came out at the second on the GC spectrum. 3-methylcyclohexene
is kinetic controlled as well, so its ratio was in the middle; however, its stability was
poorest so it came out at first on the GC spectrum. The product ratios were compared
with a previous experiment that contained 80% 1-methylcyclohexene, 16% 3methylcyclohexene, and 4% methylenecyclohexene.6 These data were similar with
current results, so the experiment is reproducible and repeatable. As the final crude
mass was 12.7349 g, after calculation, the crude percent yield was 81.32%. Furthermore,
based on GC data, percent product yield was 90%, which means 90% of the mixture
was alkenes and the rest was alcohol. Thus, the actual yield of alkene was 11.4616 g,
and the percent yield for overall reaction was 73.19%. The yield situation was relatively
high. Possible loss was caused by incomplete dehydration and co-distill of small
amount of alcohol and alkenes.
According to the GC-MS data (Figure 4-1), the peaks representing alkenes can
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be correlated with GC spectrum.7 3-methylcyclohexene with the samll peak came out
at first; methylenecyclohexene with the smallest peak came out at second; and 1methylcycohexene with the largest peak came out at last. The order and the areas of
peaks are similar with GC data. The alcohol starting material alcohol was detected
around 9 min as well as GC. On the 3.74 min panel (Figure 4-2), 3-methylcyclohexene
was detected. Its molar mass is 96.17 g/mol, and the last peak on this panel is at 96.00
m/z. It has a difference of 15 m/z with a large peak on the left at 80.97 m/z. This
difference represents the loss of a methyl group. On the 4.16 min panel (Figure 4-3), a
peak at 96.05 m/z was shown. There is not distinct loss of any functional group, so this
methylenecyclohenxe with molar mass of 96.17 g/mol. On the 4.53 min panel (Figure
4-4), 1-methylenecyclohexene was detected. This peak at 95.99 m/z has a difference of
15 m/z with another peak on the left. The molar mass matches the peak, and the
difference represents the loss of a methyl group. Although the time retentions are not
exactly same as GC, their values are close. The identification of each alkene was
justified. The results are relevant with secondary alcohol dehydration and the
hypothesis.
The synthesis was not completely done because remaining starting material
was detected in the product mixture. During the distillation, temperature was decreased
around 30 min; it is because the reflexing apparatus was not perfectly insulated, and the
temperature decreased. Although insulation was enhanced, alcohol might be distilled
and condensed in this period.
A small amount of alcohol existed in the product mixture, but the alkene
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products were collected. At the end of reaction, the amount of staring mixture was in
small quantity and its color turned yellow. This was a signal of completion. Since the
dry-distillation was avoided, some starting material remaining was reasonable. The
presence of key (C=) C-H stretch and absence of C-O stretch was displayed on IR
spectrum. Also, the GC and GC/MS data identified the presence and ratio of 3 alkene
isomers and their ratios are relevant with mechanisms. Furthermore, the percent yield
of product and overall reaction were high. Above all, the dehydration and distillation
was successful. Analytic methods including IR, GC, and GC-MS were appropriated for
this experiment.
Conclusion
In conclusion, simple distillation and dehydration were successful. The
conetent of product was high (90% product yield). The product ratios of previous
experiment were similar with this experiment (1-methcyclohexene 81.71%, 3methylcyclohexne 15.33%, and methylenecyclohexene 2.95%). This experiment is
reproducible and repeatable. IR identified the products were alkenes (presence of (C=)
C-H at 2857.16 cm-1 and absence of C-O stretch). GC and GC/MS are correlative and
consistent with the reaction mechanisms. All analytic technique mentioned above are
effective and appropriate for this experiment. No unexpected result noticed in the
overall reaction. The insulation of distillation should be emphasized in the future
experiment otherwise the vapor temperature will decrease and affect the quality of
products. Simple distillation can be used to isolate another dehydrated alcohol, i.e. 4methylcyclohexanol, or other synthesis reaction like esterification.
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Reference
1). Bortiatynski, J.; Losey, D.; Lab Guide for Chemistry 203 A Life Science
Experience in The Organic Chemistry Laboratory.; Hayden-McNeil, 2016; pp
157-184.
2). Arifin, S.; Chien, I.; Design and control of an isopropyl alcohol dehydration
process via extractive distillation using dimethyl sulfoxide as an entrainer.
Industrial & Engineering Chemistry Research, [Online]2008, 47(3), 790-803.
3). 2-methylcyclohexanol; CAS-No. 583-59-5 [Online] Sigma-Aldrich: St. Louis,
MO, Mar 20, 2015.
http://www.sigmaaldrich.com/catalog/product/aldrich/397237?lang=en&region=U
S (accessed Nov 11, 2016)
4). Methylcyclohexenes; CAS-No. 591-47-9 [Online] Sigma-Aldrich: St. Louis, MO,
Mar 20, 2015.
http://www.sigmaaldrich.com/catalog/product/aldrich/m39008?lang=en&region=
US (accessed Nov 11, 2016)
5). Rissanen, P.; Kurtn, T.; Sipil, M.; et.al.; Effects of chemical complexity on the
autoxidation mechanisms of endocyclic alkene ozonolysis products: From
methylcyclohexenes toward understanding -pinene. The Journal of Physical
Chemistry. A, [Online]2015, 119(19), 4633.
6). Bortiatynski, J., A Life Science Experience in the Organic Chemistry Laboratory,
Lec19Fall2016PostLecture.ppt, The Pennsylvania State University.

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https://psu.instructure.com/courses/1798687/files/folder/Lectures%20Pre%20and
%20Post%20files?preview=79884454 (accessed Nov 11, 2016)
7). Methylcyclohexenes_gcms.pdf. The Pennsylvania State University.
https://psu.instructure.com/courses/1798687/files/folder/Chapter%209%20Dehydr
ation%20of%20Alcohol/Dehydration%20of%20Alcohols%20GC_MS%20data?pr
eview=79801887 (accessed Nov 11, 2016)
Supplemental Information
Figure 2. IR Spectrum for Methylcyclohexenes.
Figure 3. GC Spectrum for Methylcyclohexenes.
Figure 4-1. GC-MS Spectrum for Methylcyclohexenes.
Figure 4-2. GC-MS Spectrum for 3-Methylcyclohexene.
Figure 4-3. GC-MS Spectrum for Methylenecyclohexene.
Figure 4-4. GC-MS Spectrum for 1-Methylcyclohexene.

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