OBJECTIVES:

This experiment aims to:

- Produce chlorocyclohexane from cyclohexanol using the SN1 mechanism
- Successfully use the reflux setup for the substitution of cyclohexanol
- Understand mechanism involved in the reaction
- Successfully dry the chlorocyclohexane to prevent the reverting back to cyclohexanol

INTRODUCTION:

Alkyl halides are important reagents in many organic reactions and are generally prepared from
alcohols. Using zinc chloride as a catalyst, the SN1 mechanism is used to substitute the secondary alcohols from
cyclohexanol to form chlorocyclohexane. The oxygen atom from the alcohol group of cyclohexanol bonds with
zinc chloride to donate protons to the hydrogen atom of hydrochloric acid thus leaving a negatively charged
chloride ion. The use of zinc chloride as a catalyst for the reaction helps make the oxygen atom a better leaving
group. A carbocation is then formed from the removal of water and zinc chloride from the cyclohexane. This
carbocation is then attacked by chloride ions to form chlorocyclohexane. The SN1 mechanism is used because
the nucleophile, a chloride ion, is a weak base thus it is too weak to remove the proton from the adjacent carbon
of the carbocation.

PRELAB QUESTIONS:
1. How is the yield of the reaction maximized? Explain.
 The heating through reflux helps maximize the yield of the reaction because the reaction is
carried out at high temperatures without losing its reactants through evaporation. Since the
reaction is done in a closed isolated environment, the reactants collide more often with
greater force thus the yield of reaction heightens.
2. What is the use of the sodium bisulfite wash?
 The sodium bisulfite is used to dry the product to remove traces of acid, unreacted
cyclohexanol, and water. The drying of the product is also meant to prevent the reverting
back of chlorocyclohexane to cyclohexanol or to cyclohexene. The drying process is meant to
remove water to prevent the formation of a nucleophile so that it doesn’t attack the
carbocation or the proton of the adjacent carbon.
3. Why do you have to drain the aqueous layer before adding sodium bisulfite on the organic layer?
What gas is formed upon the addition of sodium bisulfite?
 The aqueous layer must be drained before adding sodium bisulfite on the organic layer to
separate the hydrochloric acid and zinc chloride from the organic layer. This is a more
efficient process than drying out the entire volume of the aqueous layer using sodium
bisulfite. The addition of sodium bisulfite forms the gas sulfur dioxide.
4. What step is undertaken to prevent chlorocyclohexane from reverting back to cyclohexanol or
forming cyclohexene? How does this prevent the reversal from taking place?
 To prevent chlorocyclohexane from reverting back to cyclohexanol or from forming
cyclohexene, the product must be dried to remove any presence of water. This process
prevents the reversal from taking place because the oxygen atom of water won’t be present
to attack the carbocation created from the chlorine atom becoming a leaving group. The
drying process also prevents the formation of cyclohexene because the oxygen atom of
water won’t be able to attack the proton on the adjacent carbon to the carbocation. It
prevents the formation of a nucleophile that attacks the carbocation or proton of the
adjacent carbon.
5. What are the qualitative tests to verify the presence of chlorocyclohexane and cyclohexanol? What
constitutes a positive test result?
 The qualitative test used to verify the presence of chlorocyclohexane is the alcoholic silver
nitrate test because it detects the presence of alkyl halides and acyl halides. The presence of
gray to white precipitate constitutes a positive result. The qualitative tests used to verify the
presence of cyclohexanol are the chromic acid test and the Lucas test which determine the
presence of alcohols. A positive result is seen in the formation of a blue-green precipitate for
the chromic acid test and the formation of a secondary phase for the Lucas test.
REAGENTS:
PHYSICAL AND CHEMICAL
REAGENTS
PROPERTIES
Cyclohexanol (IUPAC) [C6H12O] Molecular Weight: 100.161 g/mol
Boiling Point: 161.84oC
Melting Point: 25.93oC
Density: 0.96 g/cm3
Solubility: 42,000 mg/L (10oC) in
water
Appearance: Colorless needles or
viscous liquid with a camphor-
like odor
Hydrochloric Acid / Chlorane Molecular Weight: 36.458 g/mol
(IUPAC) [HCl] Boiling Point: -85.05oC
Melting Point: -114.22oC
Density: 1.639 g/L
Solubility: 67g/100mL in water
(30oC)
Appearance: colorless to slightly
yellow gas with pungent, irritating
odor
Zinc Chloride / Dichlorozinc Molecular Weight: 58.44 g/mol
(IUPAC) [ZnCl2] Boiling Point: 732oC
Melting Point: 290oC
Density: 2.9 g/cm3
Solubility: 432 g/100g (25oC) of
water
Appearance: white hygroscopic
solid in various forms; odorless
Sodium Bisulfite / Molecular Weight: 104.055 g/mol
Sodium;hydrogen sulfite (IUPAC) Boiling Point: 104oC –
[HNaO3S] decomposes
Melting Point: decomposes
Density: 1.48 g/cm3
Appearance: White crystals or
powder with a slight odor of
sulfur dioxide, disagreeable taste
SAFETY PRECAUTIONS
Has caused adverse reproductive
and fetal effects in animals
Potential cancer hazard
Skin and eye irritant: flush with
water for at least 15 mins. then get
medical assistance
Ingestion (hazardous): do not
induce vomiting unless instructed
by medical personnel
Inhalation (hazardous): to fresh
air, give oxygen, seek medical
assistance
Combustible
Skin and eye irritant (very
hazardous): flush with water if
contact
Serious skin contact: Wash with
disinfectant soap and cover
contaminated skin with anti-
bacterial cream. Seek medical aid
Ingestion (hazardous): do not
induce vomiting unless instructed
by medical personnel
Inhalation: remove to fresh air,
give oxygen, seek medical
assistance
Corrosive, irritant, permeator for
skin
Skin and eye irritant (hazardous):
flush with water if contact
Serious skin contact: Wash with
disinfectant soap and cover
contaminated skin with anti-
bacterial cream. Seek medical aid
Ingestion: do not induce vomiting
unless instructed by medical
personnel
Inhalation: remove to fresh air,
give oxygen, seek medical
assistance
Skin and eye irritant (hazardous):
flush with water if contact
Serious skin contact: Wash with
disinfectant soap and cover
contaminated skin with anti-
bacterial cream. Seek medical aid
Ingestion: do not induce vomiting
unless instructed by medical
personnel
 Inhalation: remove to fresh air,
give oxygen, seek medical
assistance

REFERENCES:
- Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City: Office of Research and
Publications, Ateneo de Manila University; 2005.
- [Author Unknown]. Pubchem compound database [Internet]. USA: National Centre for Biotechnology Information;
2004 September 16 [updated 2017 March 18; cited 2017 March 19]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/cyclohexanol
- [Author Unknown]. Sciencelab.com [Internet]. USA: Sciencelab.com, Inc.; unknown first publication [cited 2017
March 19]. Available from: http://www.sciencelab.com/msds.php?msdsId=9923625
- [Author Unknown]. Pubchem compound database [Internet]. USA: National Centre for Biotechnology Information;
2004 September 16 [updated 2017 March 18; cited 2017 March 19]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/hydrochloric_acid
- [Author Unknown]. Sciencelab.com [Internet]. USA: Sciencelab.com, Inc.; unknown first publication [cited 2017
March 19]. Available from: http://www.sciencelab.com/msds.php?msdsId=9924285
- [Author Unknown]. Pubchem compound database [Internet]. USA: National Centre for Biotechnology Information;
2005 March 25 [updated 2017 March 18; cited 2017 March 19]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/zinc_chloride
- [Author Unknown]. Sciencelab.com [Internet]. USA: Sciencelab.com, Inc.; unknown first publication [cited 2017
March 19]. Available from: http://www.sciencelab.com/msds.php?msdsId=9927328
- [Author Unknown]. Pubchem compound database [Internet]. USA: National Centre for Biotechnology Information;
2008 February 5 [updated 2017 March 18; cited 2017 March 19]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/sodium_bisulfite
- [Author Unknown]. Sciencelab.com [Internet]. USA: Sciencelab.com, Inc.; unknown first publication [cited 2017
March 19]. Available from: https://www.sciencelab.com/msds.php?msdsId=9927590
PROCEDURES:

Place 5mL cyclohexanol, 1.0g zinc chloride,
and 15mL concentrated hydrochloric acid into a
round bottom flask. Swirl flask to mix contents
until yellow color appears.

Attach water condenser vertically over mouth of
round bottom flask. Check setup for leaks and
heat RBF. A second layer will form after 10
mins. Continue heating RBF for ~30 mins.
 HCl gas will evolve from setup.
Perform experiment under hood.
 Condensation during reflux should
appear around halfway in water
condenser. Adjust flame accordingly

Let mixture in RBF cool down until cool enough

to be handled. Decant mixture into separatory  Don’t forget to vent gas out of
funnel and shake funnel vigorously to mix layers funnel

Continue shaking until mixture inside funnel

cools down to room temp. Allow mixture to
stand and let 2 layers separate.

Drain aqueous layer containing concentrated

hydrochloric acid and zinc chloride into flask  Discard into Waste Acid container
and discard.

Rinse RBF used for reflux with 8mL distilled

water and use to wash the organic layer in
separatory funnel. Drain aqueous layer.

Wash organic layer with 8mL 20% sodium

bisulfite and then with 5mL water. Discard
washings into sink.

Decant organic layer into Erlenmeyer flask and

dry over sodium sulfate. Distill if necessary and
store in scintillating vial. Perform qualitative
tests