ACID-CATALYZED DEHYDRATION OF 2-METHYLCYCLOHEXANOL

Douglas G. Balmer

(T.A. Mike Hall)

Dr. Dailey

Submitted 8 August 2007

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Introduction: The purpose of this experiment is to acid-catalyze the dehydration of 2-methyl

cyclohexanol. The product mixture will contain 1-methylcyclohexene and 3-methylcyclohexene.

A 2:1 ratio in favor of 3-methylcyclohexene would be statistically expected based on the number

of β hydrogens (Fig. 1). The actual ratio of products will be measured using gas-liquid

chromatography, G.C.

Russian scientist, Alexander Saytzeff, came to the conclusion that the most highly

substituted alkene usually predominates in addition reactions. Since 1-methylcyclohexene has

three substituents on the double bond and 3-methylcyclohexene only has two substituents,

Saytzeff’s rule predicts that 1-methylcyclohexene will predominate (Fig. 2).

Removal of this H would lead to 1-methylcyclohexene.

Removal of one of these H's would lead to

H H
3-methylcyclohexene.
H

FIGURE 1 Statistically, 3-methylcycloexene has twice the probability of forming as

1-methylcyclohexene.

1-methylcyclohexene 3-methylcyclohexene
3o 2o

FIGURE 2 Saytzeff’s rule predicts that 1-methylcyclohexene will predominate because it is

more highly substituted.
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Main Reaction and Mechanism: The first step of the mechanism involves the hydronium ion.

The hydronium ion is produced when sulfuric acid deprotonates in water. The alcohol’s oxygen

acts as a Lewis base and donates electrons to a hydrogen on the hydronium ion. This forms an

oxonium ion. The oxonium ion cleaves from the cyclohexane ring, forming a 2o carbocation.

The water acts as a Lewis base as electrons are donated to a β-hydrogen. The β-hydrogen

transfers its electrons to the ring forming a methylcyclohexene. Sayzteff’s rule predicts that 1-

methylcyclohexene will predominate.

H H
H
O oxonium ion
O

O
O
+ + H H
H H
H

H H
O

O
+ H H

H
H O H
O
+ +
H H H H
H

AND (major product)

H
H O H
O
+ H H +
H H
H

(minor product)
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FIGURE 3 The acid-catalyzed dehydration mechanism of 1-methylcyclohexanol. The major

product is 1-methylcyclohexene and the minor product is 3-methylcyclohexene.

Table of Reactants:

Mol. Vol. Stoich.

Reactant Structure Wt. Mass Required Properties
(amu) Moles (mol)
OH
5.0mL
ρ = 0.93g/mL
cis and trans
m.p. = -38˚C
2-methylcyclohexanol 114.187 4.65g 1
f.p. = 58˚C
C7H14O
b.p. = 163-166˚C
40.7mmol
9M ρ = 1.84g/mL
sulfuric acid m.p.=3oC
H2SO4 --- 98.0734
3.5mL
catalyst
b.p.=280oC
ρ vap= 3.4

Table of Products:

Mol.
Stoich.
Product Structure Wt. Theor. Yield Properties
Required
(amu)
ρ = 0.811g/mL
1 m.p. = -120˚C
1-methylcyclohexene (40.7mmol)
96.1718 3 1 f.p. = -3˚C
C7H12
= 13.6mmol b.p. = 110˚C

ρ = 0.801g/mL
2 m.p. = -124˚C
3-methylcyclohexene (40.7mmol)
96.1718 3 1 f.p. = -3˚C
C7H12
= 27.1mmol b.p. = 104˚C

Yield Data: A volume of 5.0mL corresponds to 40.7mmol. The mass of the methylcyclohexene

isomers produced should be 3.91g (Eq.1). The actual amount of product obtained was 1.86g.

The percent yield for the reaction was 47.6%.

1 96.1718g
40.7mmol alcohol x molar ratio x = 3.91g alkene (1)
1 1mol
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Experimental Procedure: A reflux apparatus was assembled with a 25mL round-bottom flask

and magnetic stirbar (Fig.4). 2-methylcyclohexanol (5.0mL) and 9M sulfuric acid (3.5mL) were

added to the reaction flask. The Thermowell heater was adjusted to 70V for a reflux rate of 1

drop every 1-2 seconds. A 10mL graduated cylinder, cooled in an ice bath, was used to collect

the distillate. The distillate’s volume and temperature were recorded (Tbl. 1, Fig. 5). It took

approximately 60 minutes for the reflux to complete.

FIGURE 4 Reflux apparatus with a 10mL graduated cylinder cooled in an ice bath for
collection.

Distillate Volume (mL) Head Temperature (oC)

0.0 78.8
0.5 79.0
1.0 79.1
1.5 79.1
2.0 79.1
2.5 75.0
3.0 75.9
3.78 88.0

TABLE 1 Volume and head temperature data for the distillate.

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Head Temperature Vs. Distillate Volume

90
88

Head Temperature (oC)

86
84
82
80
78
76
74
0 0.5 1 1.5 2 2.5 3 3.5 4
Distillate Volume (mL)

FIGURE 5 Head temperature vs. distillate volume graph.

The distillate was transferred to a separatory funnel and washed with 10mL of water.

The bottom aqueous layer was clear, and the top organic layer was cloudy-white. Lots of the

organic layer formed droplets on the walls of the separatory funnel. The aqueous layer was

acidic, because it turned blue litmus red. The aqueous layer was separated, and the organic layer

was washed with 10mL of 3N NaOH. The bottom aqueous layer was a little cloudy, and the top

organic layer was relatively clear. No organic droplets formed on the walls of the separatory

funnel. The acid was neutralized, because the aqueous layer turned red litmus blue. The

aqueous layer was separated, and the organic layer was washed with 10mL of brine solution.

Both of the layers were very clear, and there was a nice separation between the two. The

aqueous layer was separated and the organic layer was drained into a 25mL Erlenmeyer flask.

Several spatula scoops of calcium chloride were placed in the corked Erlenmeyer flask to dry the

organic layer. The dry, organic layer was transferred by pipette to a tared vial. The mass of the

methylcylcohexene isomers was 1.86g.

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A bromine unsaturation test was performed on the product, cyclohexane, and

cyclohexene. Two drops of each sample and ten drops of methylene chloride were transferred to

separate test tubes. A 0.1M solution of bromine in methylene chloride was added dropwise until

a light orange persisted. A positive test was indicated by the rapid disappearance of the orange

color. The results of the bromine unsaturation tests are shown in Table 2.

Sample Result of adding bromine solution

methylcyclohexene isomers rapidly cleared; positive for unsaturation
cyclohexane stayed orange; negative for unsaturation
cyclohexene rapidly cleared; positive for unsaturation

TABLE 2 Bromine unsaturation test results.

A Baeyer unsaturation test was performed on the product, cyclohexane, and cyclohexane.

Two drops of each sample and 2mL of 95% ethanol were transferred to separate test tubes.

Several drops of purple 0.1M KMnO4 were added to each test tube. A positive test was indicated

by the formation of a brown precipitate, MnO2. The results of the Baeyer unsaturation tests are

shown in Table 3.

Sample Result of adding bromine solution

methylcyclohexene isomers turned brown and cloudy; positive for
unsaturation
cyclohexane stayed purple and transparent; negative
for unsaturation
cyclohexene turned brown and cloudy; positive for
unsaturation

TABLE 3 Baeyer unsaturation test results.

The products were analyzed using GC #7. A 2.5µL sample was injected into column A

which was set at the following conditions: + polarity, 100mA current, 77oC column temperature,

125oC detector temperature, and 125oC injector temperature.

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Properties of Products:

A 1.86g sample of methycyclohexene isomers was collected. The sample consisted of

67.712% 1-methylcyclohexene and 32.288% 3-methylcyclohexene (Fig. 6).

Bromine Baeyer
Product Mass (g) Appearance
Test Test
methylcyclohexene
1.86 positive Positive clear liquid
isomers

FIGURE 6 GC trace of the methylcyclohexene sample. 3-methylcyclohexene had the shortest

retention time (top) and 1-methylcyclohexene had the longest retention time (bottom).
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Significant Side Reactions: The methylcyclohexene isomers were distilled for two reasons.

First, by removing the product, the equilibrium between the alcohol and alkene was shifted

toward the alkene. Secondly, the alkene could react with the carbocation to form a polymer (Fig.

7).

+ n

FIGURE 7 Polymerization of 1-methylcyclohexene with the 2o carbocation.

The possibility for a third alkene does exist. If the 2o carbocation shifted a hydride ion

from the 3o location, a 3o carbocation could form. If this carbocation became an alkene, it could

form 1-methylcyclohexene and methylene cyclohexane (Fig. 8). It would be hard to distinguish

between 3-methylcyclohexene and methylenecyclohexane since their boiling points are 104oC

and 103oC, respectively.

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H
H

H O
O
+
+ H H
H H H

(major product)

H
H C H

O
O +
+ H H
H H H

(alternate product)

FIGURE 8 Hydride shift to form a 3o carbocation. The 3o carbocation can form 1-

methylcyclohexene and

Method of Purification: The products were purified according to Figure 9. The distilled

methylcyclohexene isomers were washed with water to absorb any sulfuric acid. The sodium

hydroxide wash was used to neutralize any remaining surfuric acid left in the organic layer. The

brine wash was used to help separate remaining water from the organic layer. Finally, calcium

chloride was used to dry the organic layer.

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distilled alkene isomers, sulfuric acid

water wash

water, sulfuric acid alkene isomers

NaOH

water, netralized sulfuric acid alkene isomers

brine wash

water alkene isomers

CaCl2

dry alkene isomers

FIGURE 9 Purification of methylcyclohexene isomers.

Conclusions: The results support that the acid-catalyzed dehydration of 2-methycyclohexanol

was successful. The GC percentages support Sayzteff’s rule; the more highly substituted alkene

was the major product. 1-Methycyclohexene formed 67.712% of the product mixture and 3-

methylcyclohexene formed 32.288% of the product mixture. Both the bromine and the Baeyer

unsaturation tests were positive for unsaturation. The product ratio was relatively close to the

75%, 25% ratio predicted using thermodynamic stability and the free energy equation,

∆G = RT ln K.
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Answers to Assigned Questions: Page 289-291 (1,21)

1) Why is the boiling point of the parent alcohol higher than that of the product alkene?

The 2-methylcyclohexanol has the higher boiling point because it has more

intermolecular forces. It has the ability to hydrogen bond, whereas the methylcyclohexene

isomers are nonpolar and only have London dispersion forces.

21) Provide a detailed mechanism for the acid-catalyzed dehydration of cyclohexanol.

H H
H
O
O

O
O
+
+ H H
H H
H

H H
O

O
+ H H

H
H O O
+ +
H H H H
H
 Balmer 12

Additional Question) What is the predicted product ration between 1-methylcyclohexene and 3-
methylcyclohexene using Chem3D?

Keq

Torsion: -0.4902kcal/mol Torsion: 0.3631kcal/mol

Non-1,4 VDW: -0.9801kcal/mol Non-1,4 VDW: -1.1340kcal/mol
1,4 VDW: 4.4087kcal/mol 1,4 VDW: 4.8038kcal/mol
Dipole/Dipole: 0.1869kcal/mol Dipole/Dipole: 0.1099kcal/mol
Total: 3.9936kcal/mol Total: 5.0287kcal/mol

5.0287kcal/mol – 3.9936kcal/mol = 1.0351kcal/mol = 4330.8J/mol

[3 - methylcyclohexene]
Keq =
[1 - methylcyclohexene]

∆G = RT ln K

4330.8J/mol = 8.3145J/molK * 373K x ln (K)

Ln (K) = -1.40

K = 0.25

Based on thermodynamics, the product ratio should be 75% 1-methylcyclohexene and

25% 3-methylcyclohexene. The actual product ratio was relatively close. It has a ratio of

67.712% 1-methylcyclohexene and 32.288% 3-methylcyclohexene.