Prelab 6 Cyclohexyl Chloride

Carlos Emilio A.
Palencia 27C
6 Preparation of Cyclohexyl Chloride April 22, 2019
Objectives
The experiment aim to
● Synthesize Cyclohexyl Chloride from cyclohexanol through a Sn1 reaction
● Verify the product with qualitative tests and IR Spectroscopy
Introduction
In Sn1 reactions, the rate limiting step is the formation of the carbocation
intermediate through the spontaneous, unimolecular dissociation of the leaving group.
Therefore only factors that affect the stability of the carbocation intermediate will have an
overall effect on the rate of the reaction. The nature of the substrate, leaving group, and
solvent used are the primary factors which should be accounted for in analyzing the reaction
rate. As a result, the nature of the nucleophile, which attacks the carbocation intermediate,
will not have an bearing on the reaction rate (AtQ1)(1).
Due to the positive charge of the carbocation intermediate and the dipole moment
present in water molecules, the intermediate and solvent will have a certain orientation
during the reaction. The electron rich domains of the water molecules will be attracted to the
positive charge of the carbocation which will mean the oxygen atoms in water will face the
carbon with the positive charge. The orientation also stabilizes the carbocation which,
therefore, affects the reaction rate as mentioned before. The figure below illustrates the
orientation of the water molecules around the carbocation intermediate (AtQ2)(1).
Figure 1. Solvent Orientation around

Carbocation
In the process of synthesizing cyclohexyl chloride, it is necessary that actions must

be done in order to avoid the product from reverting back into its original form or from
participating in any unwanted reaction. During the reaction, traces of acid, unreacted alcohol,
and water may still be present alongside the product. The presence of water with the product
is problematic as it can react with it to revert back to cyclohexanol or cyclohexene. The
products is washed with sodium bisulfate in order to avoid this outcome. The step is able to
remove the unwanted side products without compromising the product of interest (AtQ3)(1).
However , sodium bisulfite can also react with the unreacted concentrated hydrochloric acid
which will evolve the very toxic gas sulfur dioxide. The reaction goes of the evolution of
sulfur dioxide from the interaction of hydrochloric acid and sodium bisulfite can be seen
below.
NaHSO3 + HCl → NaCl + H2O + SO2
To address the build-up of pressure in the separatory funnel, venting must be done
once in while after agitating the solution. The technique entails flipping the separatory 180
degrees so that the drain drip is pointing upward. Once inverted, the stop clock is opened in
order to release the gases creating the pressure build up (AtQ4)(2). In order to evolve the
least amount possible of the toxic gas, the acid layer is separated from the separatory funnel
before the addition of the sodium bisulfate. It is imperative that the washing is done inside
the fume hood to avoid the inhalation of any toxic gas by the students (AtQ 5).
After obtaining the product, it can be verified by carrying out qualitative tests. To test
for the presence of cyclohexyl chloride, the alcoholic silver nitrite test can be administered. It
tests positive for haloalkanes through the formation of a gray to white precipitate. Qualitative
tests can also be carried out for the presence of the cyclohexanol reactant. The lucas and
chromic acid tests can both indicate the presence of a secondary alcohol like cyclohexanol.
The formation of a second layer is the positive signal for the lucas test while the formation of
precipitate if the signal for the chromic acid test (AtQ 6)(1).
Reagents
Reagents Physical and Chemical Safety Precautions
Properties
Cyclohexanol Physical State: Liquid; Slightly hazardous in case of

C6H11OH MW: 100.16 g/mol ingestion or absorption
Density: 0.96 𝑔/𝑐𝑚3 through skin, as well as,
Odor: Camphor/menthol inhalation and contact with
BP: 161 deg C the eyes.
MP: 23 deg C
Solubility: soluble in water
Concentrated. HCl Physical State: Liquid; Corrosive through all entries.

MW: 34.46 g/mol Toxic by
Density: 1.18 𝑔/𝑐𝑚3 inhalation/ingestion.
Odor: Pungent
BP: 85 deg C
MP: -114 deg C
Zinc Chloride Physical State: Solid; Causes burns through all

ZnCl2 MW: 136.29 g/mol routes. Harmful if swallowed.
Density: 2.91 𝑔/𝑐𝑚3 Toxic to aquatic organisms.
Odor: odorless Corrosive to metal.
BP: 732 deg C
MP: 293 deg C
Sodium bisulfite Physical State: Solid; Hazardous to eyes and skin.

NaHSO3 MW: 104 g/mol Slightly hazardous in case of
Density: 1.48 𝑔/𝑐𝑚3 inhalation.
Odor: sulfur like
BP: 150 deg C
MP: 58.5 deg C
Magnesium sulfate Physical State: Solid May be hazardous in case of
MgSO4 MW: 120.361 g/mol ingestion. Avoid inhalation
Density: 2.66 𝑔/𝑐𝑚3 and contact with eyes.
Odor: odorless
BP: N/A
MP: 1124 deg C
Cyclohexyl chloride Physical State: liquid Flammable liquid. Toxic in

Chlorocyclohexane MW: 118.61 g/mol case of inhalation. Irritant to
C6H11Cl Density: 1.0 𝑔/𝑐𝑚3 eyes. Slightly hazardous in
Odor: strong case of skin contact.
BP: 142 deg C
MP: -44 deg C
Solubility: low
Equipment
● Boiling Chips
● Sample Vials
● Recovery Container
● Waste Container (washes)
● Waste Container (HCl)
Reaction
Procedure
Synthesis of Cyclohexyl Chloride
*Perform in fume hood*
5.0 ml cyclohexanol + 1.0g → Swirl until yellow. Vertically → Heat for 30 min after the
ZnCl2 + 15 ml con. HCl + attach water condenser to formation of a second layer.
boiling chips into rb flask. flask. Check for leaks.
Workup
*Perform in fume hood*
Cool mixture. Decant into → Rinse rb flask w 8 ml water. → Wash remaining mix w 8 ml
separatory funnel. Shake Use to wash separatory NaHSO3. Shake. Wash w 5 ml
vigorously until room funnel. Drain aqueous layer water. Decant organic layer into
temp.Drain lower layer (HCl + into separate waste erlenmeyer flask.
ZnCl2) into “Waste HCl”. container.
Obtain IR spectroscopy. Do ← Record Volume. Calculate ← Decant organic layer into

quali test. Store in vial percent yield. erlenmeyer flask. Dry over
MgSO4. Distill to purify.
Set-Up
Data and Observations

Data Values
Cyclohexanol used (ml)
ZnCl 2 used (g)
Con. HCl used (ml)
Cyclohexyl Chloride obtained(ml)
Qualitative Test Result (+/-) Implication
Alcoholic Silver Nitrate
Chromic Acid
Lucas
References
(1) Guidote, A., del Rosario, D., Abuzo, A. (2005). Experiencing Organic Chemistry.
Office of Research and Publication, Ateneo de Manila University, QC.
(Comprehensive).
(2) Gable, K. USA: Oregon State University;[date unknown] [updated 2014 December
23; cited 2019 April 14]. Available from:
http://chemistry.oregonstate.edu/courses/ch361-464/ch362/sepfunnel.htm
(3) Pubchem [Internet]. USA: National Center for Biotechnology Information; [date
unknown] [updated date unknown; cited 2019 March 21]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/cyclohexanol. (Cyclohexanol)
(4) Fisher Scientific [Internet]. Pittsburgh: Thermo Fisher Scientific; 1998 [cited 2019
2019 April 14]. Available from: https://fscimage.fishersci.com/msds/25350.htm (Zinc
chloride)
2019 April 14]. Available from:
https://www.fishersci.com/shop/msdsproxy?storeId=10652&productName=S6543
(Sodium bisulfite)
2019 April 14]. Available from:
https://www.fishersci.com/store/msds?partNumber=AAL043490B&productDescriptio
n=CHLOROCYCLOHEXANE+98%25+1KG&vendorId=VN00024248&countryCode=
US&language=en (Cyclohexyl chloride)
(7) Pubchem [Internet]. USA: National Center for Biotechnology Information; [date
unknown] [cited 2019 April 14]. Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/magnesium_sulfate#section=Density
(Magnesium sulfate)
(8) ScholAR chemistry. NY: [Publisher Unknown}; 2009 [cited 2019 April 14]. Available
from:https://www.mccsd.net/cms/lib/NY02208580/Centricity/Shared/Material%20Safe
ty%20Data%20Sheets%20_MSDS_/MSDS%20Sheets_Hydrochloric_Acid_329_00.p
df (conc. HCl)

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Carlos Emilio A.

Figure 1. Solvent Orientation around

In the process of synthesizing cyclohexyl chloride, it is necessary that actions must

Cyclohexanol Physical State: Liquid; Slightly hazardous in case of

Concentrated. HCl Physical State: Liquid; Corrosive through all entries.

Zinc Chloride Physical State: Solid; Causes burns through all

Sodium bisulfite Physical State: Solid; Hazardous to eyes and skin.

Cyclohexyl chloride Physical State: liquid Flammable liquid. Toxic in

Obtain IR spectroscopy. Do ← Record Volume. Calculate ← Decant organic layer into

Data and Observations

Cyclohexanol used (ml)

ZnCl 2 used (g)

Con. HCl used (ml)

Cyclohexyl Chloride obtained(ml)

Qualitative Test Result (+/-) Implication

Alcoholic Silver Nitrate

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