Experiment 10:

ACID-CATALYZED
DEHYDRATION
OF AN ALCOHOL
WITH REARRANGEMENT

Objectives

To perform a dehydration of 2methylcyclohexanol to form isomeric alkenes

under E1 conditions.

To purify the product using simple distillation.

To analyze the product using GC analysis in

order to identify and quantify products.

To characterize the reactant and products

using IR spectroscopy.

Before coming to lab

Please review:

Simple distillation

E1 elimination reactions

GC Analysis

CHEMICAL EQUATION
Three different ISOMERIC alkenes can be
produced.

Because this reaction is performed near

equilibrium conditions, the relative amount of
each product reflects its stability.

OH

CH3
H2SO4
heat

CH3

CH3

CH2

more substituted = lower energy = more stable = more

predominate!

RATE LIMITING STEP

C C
H OH
..

H OSO3H
Fast Reaction

C C
H
O+ H
H

HSO4-

Rate limiting step

C C

C C
+
H

C C

C C
H O+ H
H

+ HSO4-

+ H2O

+ H2SO4

Fast Reaction

The rate of elimination of water depends on the

stability of the carbocation formed.
Formation of the carbocation is the most
energetically unfavorable, and therefore the slowest,
step in dehydration reactions.

E1 Mechanism reaction
1. The hydroxyl
oxygen attacks
and removes a
proton from
sulfuric acid

2. which forms a
new O-H bond,
where oxygen
bears a positive
charge (oxonium
ion). Water is
eliminated-forms
2o carbocation.

OH
CH3
H

H
Products may
form from the 2o
carbocation, but it is
more likely that the
2o C+ will rearrange
to a 3o C+.

H
H

H
H

CH3

CH3

H + H2O + HSO4

secondary carbocation

+ HSO4a

2o

SO3H

H
b

CH3
H2O

c) Hydride Shift

Carbocation
rearrangement

H e
d
3o

C
H

a) -H3O+

1-methyl-1cyclohexene

CH3

b) -H3O+

d) -H3O+

CH3
3-methyl-1cyclohexene

1-methyl-1cyclohexene

4. At the
carbocation stage,
water will remove a
proton from the
carbon ADJACENT
to the carbocation.
The electrons form
the pi bond of the
alkene.

H
H

H 2O

e) -H3O+
CH2

CH3

methylenecyclohexane

THEORETICAL YIELD

The only reactant is 2-methylcyclohexanol.

The H2SO4 is simply a catalyst, since it is
regenerated in the end.

Theoretical yield is calculated assuming that

the major product formed is one that results
from the most stable carbocation
intermediate.

Theoretical yield (g) =

# g reactant
#g

Amount
you
started
with

1 mol of reactant
Molecular
weight of
reactant

1 mol reactant

1 mol product
1 mol product

Stoichiometric
ratio

Molecular
weight of
product

Always
end up in
units of
grams of
#g
product!!!

OVERVIEW

Set up and perform simple distillation to collect

products.
Obtain final product mass and calculate percent yield.
Prepare and submit GC sample for analysis.
Pick up GC results and record standard retention
times.
Identify components in sample chromatogram by
comparing to standard chromatogram.
Quantify alkenes by calculating adjusted area
percent.
Characterize reactant and products using provided IR
spectra.

EXPERIMENTAL
PROCEDURE:
(Simple distillation)
Clamp
flask to
ring
stand
here!

Place 2methylcyclohexanol,
sulfuric acid and boiling
chips in 50 mL round
bottom flask.

Blue Keck
clips
here!
water out
water in

Clamp
flask to
ring
stand
here!

50
mL
Heating Mantle

Clamp flask to ring stand.

Weigh 10 mL flask. Clamp

to other ring stand.

10
mL

Attach clear hoses to

condenser. Run water in at
the bottom, out at the top!

iron ring
to
voltage
regulator

Build rest of distillation

apparatus, using blue Keck
clips to secure top and
bottom joints around

EXPERIMENTAL
PROCEDURE:
(Simple distillation)
Begin water flow, and
apply heat (VR@30) to boil
solution.

Record temperature when

distillate begins to collect in
10 mL flask (Ti).

water out
water in

Keck
clips!
Heating Mantle

iron ring
to
voltage
regulator

Collect ~ 5 mL distillate.

Record temperature right

before you drop the heating
mantle (Tf).

Allow the solution to cool.

Reweigh 10 mL flask to
obtain actual product yield.

Prepare GC
sample and

Table 10.1:
Experimental Results
must calculate the amount of
product that can be formed based on
the amount of 2-methylcyclohexanol
used!

Theoretical Yield (g)

This mass will be obtained by

weighing the 10 mL round bottom
flask before and after the distillation.
The difference in the mass is the
actual product yield.

Actual Yield (g)

% yield

Product Appearance

Actual yield (g) X 100

Theoretical yield (g)

physical state and color of distillate.

Table 10.2:
GC Analysis Results
Compound

GC Retention time
(min)
Standar
d

Sample

Area
Percent

Adjusted
Area Percent

methanol

Never calculate
adjusted area % based
on the solvent!

2-methylcyclohexanol

No need to calculate
adjusted area % on the
reactant, either!

1-methyl-1cyclohexene

Area % THIS alkene

X 100
Sum area% all alkenes

3-methyl-1cyclohexene

Area % THIS alkene

X 100
Sum area% all alkenes

methylenecyclohexane

Area % THIS alkene

X 100
Sum area% all alkenes

Infrared Spectroscopy
(IR)

Q: What is it?

Vibrational energy of bonds

Certain types of polar bonds absorb IR

radiation and vibrate (excited state)

Q: Why is it useful?

Certain functional groups absorb at

characteristic frequencies.

By looking at what frequencies are

absorbed, we can identify the presence
or absence of certain types of bonds!

Infrared Spectroscopy
(IR)

Q: How does it work?

This molecule is represented with a
potential energy diagram.
Each horizontal line represents a
vibrational state of a C=O bond.
If we add IR light energy at the correct
wavelength, we get excitation to the next
vibronic energy level.

Infrared Spectroscopy
(IR)

Q: What is an IR spectrum?

% transmittance
of IR radiation

Frequency of
vibration
(in wavenumbers)

EXPERIMENTAL
PROCEDURE:
IR Analysis
THINGS TO
CONSIDER
OH
CH3

What

kinds of bonds do
I have?
Ex. C-O, C=C,
CH3, etc.
If they appeared in the
IR spectrum, where
would they be?
Use a correlation
table to determine
the approximate
frequency for that
type of bond.

CH3

Now, look at the

spectrum. Are they

EXPERIMENTAL
PROCEDURE:
IR Analysis
Full IR Absorption Correlation Table in Appendix J

Base values for Absorptions of Bonds (cm-1)

OH

~3400

C-O

~1100

C-H (sp2)

~3100-3000

C-H (sp3)

~3000-2850

C=C

~1630

Table 10.3:
IR Spectral Analysis
Results
IR spectra are on page 87 in lab manual!
Functional
Group

2-methylcyclohexano
l

1-methyl-1cyclohexene

3-methyl-1cyclohexene

Methylenecyclohexane

Frequency
(cm-1)

Frequency
(cm-1)

Frequency
(cm-1)

Frequency
(cm-1)

3200-3500

N/A

N/A

N/A

1000-1200

N/A

N/A

N/A

Base
Values
(cm-1)

OH stretch
C-O stretch
2850-3000

sp3 CH
stretch
3000-3100

N/A

1600-1680

N/A

sp CH
stretch
2

C=C
stretch

Infrared Spectroscopy
(IR)
(How to answer the questions)

Your goal is to explain clearly how you were able to

use IR spectroscopy to DIFFERENTIATE between
reactant and product.
Always discuss the appearance of certain types of
absorptions, or the disappearance of others, which
indicate that functional groups have changed.
Always answer like this: (fill in the blanks)

In the IR spectrum of the product, the appearance of

the _____ (type of bond) absorption at _____ (actual
frequency) indicates the conversion of the reactant
to the product. The typical frequency for this type of
absorption is _____ (base value frequency).

SAFETY CONCERNS
The alcohol and resulting alkenes are
extremely flammable. Be very cautious
when applying heat.

Concentrated sulfuric acid is VERY

CORROSIVE and will burn skin on
contact. Please use gloves and goggles
at all times when in laboratory.

WASTE MANAGEMENT

Place all liquid waste in the container labeled

LIQUID WASTE.

Be careful when disposing of acidic waste

remaining in 50 mL round bottom flask! It is
extremely corrosive. Use a small amount of
water to rinse it into the waste container
before cleaning it thoroughly using directions
on next slide

CLEANING

After disposing of the liquid waste, clean the 50 mL

round bottom flask with soap, water, brush, and a final
rinse with wash acetone.

All other ground glass joint ware can simply be rinsed

with wash acetone into a waste container.

Be sure all ground glass joint ware is completely dry

before returning to plastic container in fume hood.

Be sure all other glassware used is completely dry

before returning to lab drawer.

IN LAB QUESTIONS

(The following questions should be answered in laboratory notebook.)

HO

Predict the products and draw a complete

mechanism for their formation from acidcatalyzed dehydration of 2-methyl-2pentanol. Be sure to show all steps and
intermediates. Circle the major product.
+

MW: 102.18 g/mol

SO3H

IN LAB QUESTIONS

(The following questions should be answered in laboratory notebook.)

Calculate the theoretical yield for the

reaction above based on 4.0 g of the
starting alcohol and a catalytic
amount
of sulfuric acid. The molecular weight of the
alcohol is given, but the molecular weight
of the product must be determined based
on the structure. Be sure to include units.