Pre-Lab: #5

Heading: Alkenes: Preparation, Reactions and Properties

Name: Susan W. Mburu

Experiment: # 5
Instructor: Dr E. Thornton

Date: 8/04/2005 TA: Tom Loschiavo

Title: Dehydration of 2-methylcyclohexanol.

Reference: Experimental Organic Chemistry: A Miniscale and Microscale Approach,
By Gilbert and Martin, section 10 pages 286-289.

Introduction:
The purpose of this lab is to demonstrate the acid-catalyzed dehydration of cis-and trans-
2-methylcyclohexanol to form a mixture of 1-metyl and 3-methylcyclohexene. Samples
of the products will be tested for unsaturation and another sample will be analyzed by
Gas chromatography to determine the percentage composition of each product. The major
product will indicate the more stable carbocation formed during the intermediate step.

Overall Reaction:
2-methylcyclohexanol undergoes a dehydration reaction when reacted with conc. Sulfuric
acid to give the two main products shown in the overall reaction below.

H2SO4
OH + + H2O
Heat

CH3 CH3 CH3

cis-and trans- 2-methylcyclohexanol 1-methylcyclohexene 3-methylcyclohexene water

1
Mechanism:

There are two mechanisms. The E1 reaction mechanism will be described for the
formation of the two main products.

(1) E1 reaction mechanism for the formation of 1-methlcyclohexene.

H H

OH O O H + H2O
H
H

CH3 water
H CH3 acid H

(cis /ns) 2-methylcyclohexanol

H3O
+

CH3

1-methylcyclohexene acid

2
(2) E1 reaction mechanism for the formation of 3-methylcycolhexene.

H H H H
H
H

OH O H + H2O
O
H
H

CH3
CH3

(cis / trans) 2-methylcyclohexanol acid water

+ H3 O+

CH3

3-methylcyclohexene acid

Table of reagents:

name of structure mol.wt. Vol. density mass moles phy.

compo- used (g) used prop.
und (ml) (g/ml) (theo.)
Cis-and 114.18 5 0.93 4.65 0.0407 163-
trans-2- 166 oC
OH
methyl-
Cyclo-
hexanol
CH3

Reference: http://Chemfinder.cambridgesoft.com
Limiting Reagent: Cis-and trans-2-methylcyclohexanol.

3
Table of Products:

Name Structure Mol.wt Theoretical Actual Density Boiling color

of yeild moles g/ml Point
Comp- obtained obtained (oC)
ound (g)

2- 114.18 0.93 163- Color-

methy- OH 166 less
Cyclo-
hexanol

CH3

1- 96.17 110 Color-

methyl- 0.811 less
Cyclo- 3.914
hexene

CH3

3- 96.17 0.801 104 Color-

methyl- less
Cyclo-
hexene

CH3
Color-
water O 18 0.732 1.00 ~96 less
H H
Reference: http://Chemfinder.cambridgesoft.com

Procedure:
1. Place a small magnetic stirbar and 5ml of the mixture of cis-and trans- 2-
methylcyclohexanol in a 25ml round bottomed flask, and add 3ml of 9M sulfuric
acid. Gently swirl the flask to thoroughly mix the liquids.
2. Set up apparatus for fractional distillation as shown in the diagram on the next
page. And attach the flask prepared in procedure (1). Use a 10ml graduated
cylinder, cooled in an ice-water bath as the receiver.
3. Heat and stir the reaction mixture using a Thermowell heater and a magnetic
stirrer. Adjust the voltage, to get a steady distillation rate.
4. Maintain the distillation temperature between 95-100oC, collect the distillate at a
rate of about one drop, every one or two seconds, until 3-4ml of the organic olefin

4
 mixture is collected. If the distillation rate becomes very slow, add 3ml of water
to the reaction flask and resume the distillation.
5. Transfer the distillate to a small separatory funnel and wash the organic product
successively with 10ml of water,10ml of 3N aqueous sodium hydroxide solution,
and 10ml of saturated sodium chloride solution.
6. Drain the organic layer into a 25ml Erlenmeyer flask and add a small amount of
anhydrous calcium chloride. After swirling for a few minutes, if the solution is
not clear, add more of the drying agent swirl and wait until it clears. Decant the
organic solution away from the CaCl2 using a Pasteur pipet, and transfer the solution
to a tared vial.
7. Weigh the products and calculate the percentage yield.
8. Test the product mixture for unsaturation: Work at a hood.
(A) The Bromine test:
• Put 1-2ml of 0.1M bromine in dichloromethane in a test tube.
• Add 1-2drops of the product under test to the test tube.
• The rapid disappearance of the orange bromine color to give a colorless solution,
is a positive test for unsaturation.
• Repeat the above experiment to carry out two control test one cyclohexane, and
another on cyclohexene.
(B)The Baeyer Test with potassium permanganate.
• Put 0.5ml of the product under test into a test tube.
• Add 2-3 drops of potassium permanganate solution.
• The formation of a heavy brown precipitate (MnO2) is a positive test for
unsaturation.
• Repeat the Baeyer test for control tests with cyclohexane and cyclohexene.

9. Analyze the products by gas chromatography to determine the percentage composition of each
product in the mixture.

Yield Data:

Theoretical yield of the two organic products = moles of limiting reagent (cis-and trans-
2-methylcyclohexanol) * Mol.W of 1-methlcyclohexene or(3-methylcycolhexene)
= 0.0407*96.17
= 3.914g
Theoretical yield of water = 0.0407*18
= 0.733g

5
 Flow chart of the distillate work-up

OH

CH3 CH3 CH3

2 3
1
cis-and trans- 2-methylcyclohexanol 1-methylcyclohexene 3-methylcyclohexene
(unreacted reagent)
O

HO S OH O
H H
O
4 5

sulfuric acid water

wash with 10ml,water

Aqueous layer Organic layer

and 2, 3 and some 1
4 5
Also traces of 4 and 5

wash with 10ml, 3N aqueous

sodium hydroxide

Aqueous layer Organic layer

4 and 5 2, 3 some 1 Traces of 5,
4 , OH-, and Na+
wash with 10ml, saturated
sodium chloride

Aqueous layer Organic layer

1, 2, 3, and traces of 5
4, 5, Na+ and OH-

Dry organic products add some anhydrous

2, 3, and some of the calcium chloride to remove 5
unreacted 1