Preparation of Alkyl Halides Lab

DEPARTMENT OF PURE &
APPLIED CHEMISTRY
Visca, Baybay City, Leyte, PHILIPPINES
Telefax: + 63 563-7747
Email: dpoac@ vsu.edu.ph
Website: www.vsu.edu.ph
DEPARTMENT OF PURE AND APPLIED CHEMISTRY

VSU, Visca, Baybay City, Leyte
Name: Lab Schedule: MW, 10:00 AM – 1:00 PM

Instructor: Rating: ________________
Preparation of Alkyl Halides

Experiment No. 1
ABSTRACT:
This experiment aimed to accomplish successful preparation of alkyl halides from an alcohol and a
hydrogen halide via substitution reaction which was also the most common of the variety of methods
available. An in-depth understanding of the concept of the nucleophilic aliphatic substitution reactions were
also discussed as significant reaction mechanism were illustrated and presented correspondingly. The
identification of the functional factors affecting the mechanism including substrate, nucleophile, leaving
group, and reaction conditions characteristics were recognized which gave some elaborative insights into
the more structurally complex reactions and how these possibly occurred. Distinct proper procedures of the
synthesis of the alkyl halides includes some techniques of successive washing and purification such as
distillation and extractions for obtaining a maximum amount of yield as possible for the final products. At the
end of this experiment, a characteristic of an SN2 mechanism was observed in the primary alkyl halide n-
Butyl Bromide, while characteristic of an SN1 reaction mechanism was observed in the synthesis of tert-
Butyl Chloride, a tertiary alkyl halide. The alkyl halides of end products were also classified using a
qualitative test of selected solvents, with protic and aprotic in nature. Different colors of precipitates as to
the resulting metal halide being insoluble in of the chosen solvents among reactions were observed for the
determination of mechanism reactions.
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INTRODUCTION:
Alkyl halides are alkanes in which one or more hydrogen atoms have been replaced by a halogen
atom (general formula R-X). There were quite a number of methods presented in the synthesis of alkyl
halides, however one which was the most generally useful method used was to take an alcohol and add
excess H+ ions to protonate the hydroxyl group. Dehydrogenation will occur and the organic substance
becomes a carbocation which it accepts the halide group to form the alkyl halide.
This experimental procedure had the main objective of observing the process of the held synthesis
reactions of n-Butyl Bromide and tert-Butyl Chloride from n-Butanol and tert-Butanol, respectively.
Providing corresponding reaction mechanisms in regards with the reactions made possible as it was
included in the essential points in this laboratory exercise. The purposes of this experiment were primarily
centered on nucleophilic aliphatic substitution reactions also referred simply to as “substitution” reactions,
one of the most common and versatile reaction types in organic chemistry. Several distinct mechanisms
are possible for aliphatic nucleophilic substitution reactions, depending on the substrate, nucleophile,
leaving group, and reaction conditions (March, 2007). By far the most common are the S N1 and SN2
mechanisms, one was a one-step mechanism in which bond breaking and bond making are simultaneous,
and the other was the two-step mechanism in which bond breaking comes before bond making. In depth
discussion concerning the discernible definitions and underlying concepts was given in the preceding parts
of the report.
As to classify the alkyl halides, qualitative test in solvents were also provided. Usually, the primary
function of a solvent is to provide a medium in which reactants and products can come into contact with
one another and interact. Accordingly, solubility dictates the choice of solvent for many organic reactions.
However, the nature of the solvent can influence the mechanism of a reaction, and sometimes the choice of
solvent dictates the pathway by which a reaction proceeds. In terms of effect on the mechanism,
interactions of polar solvents with polar reagents are the most important (Solomon, 1999).
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SCHEMATIC DIAGRAM:
A. PREPARATION OF n-BUTYL BROMIDE
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B. PREPARATION OF tert-BUTYL CHLORIDE
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C. CLASSIFICATION TESTS FOR ALKYL HALIDES
RESULTS AND OBSERVATIONS:

A. Preparation of n-butyl bromide (CH3CH2CH2CH2Br)
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Preparation of n-butyl bromide

Reaction Equation CH3(CH2)3OH + HBr → CH3(CH2)3Br + H2O The
Actual Yield (Distillate Collected) 10.3 mL (13.14g)
Temperature Range During Collection 101.5 oC
Theoretical Yield 21.92 g
Percent Yield 59.8%
table below were the experimental results obtained from the experiment procedure followed by calculations
involved in obtaining the theoretical yield and the percentage yield from the amount of purified n-Butyl
Bromide product obtained after the final distillation.
Given: Density of CH3(CH2)3OH = 0.806g/mL Density of CH3(CH2)3Br = 1.276g/mL

MM of CH3(CH2)3OH = 74.121 g/mol MM of CH3(CH2)3Br = 137.02g/mol
Theoretical Yield:
mol of CH 3 ( CH 2 ) 3 OH =15 ml CH 3 ( CH 2 ) 3 OH ( 0.8060 g CH1mL3 ( CH 2) 3 OH )( 74.121

1 mol CH 3 ( CH 2 ) 3 OH
g CH 3 (CH 2 ) 3 OH )
=0.16 mo
1 mol CH 3 ( CH 2 ) 3 Br 137.02 g CH 3 ( CH 2 ) 3 Br
g of CH 3 ( CH 2 ) 3 Br=0.16 mol CH 3 ( CH 2 ) 3OH
( 1 mol CH 3 ( CH 2 ) 3OH )( 1 mol CH 3 ( CH 2 ) 3 Br )
=21.9 g
Actual Yield:
g of CH 3 ( CH 2 ) 3 Br=10.3 mL of CH 3 (CH 2 ) 3 Br ( 1.276 g

1 mL )
=13.1 g
Percent Yield:
Actual Yield
% yield= x 100 %
Theoretical Yield
13.1 g
% yield= x 100 %=59.8 %
21.9 g
B. PREPARATION OF tert-BUTYL CHLORIDE ((CH3)3C-Cl)
The table below displayed the results from the laboratory procedure for the synthesis of tert-Butyl
Chloride followed by the sample calculations
Preparation of n-butyl bromide

Reaction Equation
Actual Yield (Distillate Collected) 15.1 mL (12.9g)
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Temperature Range During Collection 52.7 oC

Percent Yield 65.5%
Given: Density of (CH3)3COH= 0.775 g/mL Density of (CH3)3CCl = 0.851g/mL

MM of (CH3)3COH = 74.12 g/mol MM of (CH3)3CCl= 92.57g/mol
Theoretical Yield:
0.775 g ( CH 3 ) 3 COH 1mol (CH 3 ) 3 COH

mol of ( CH 3 ) 3 COH =20 ml ( CH 3 ) 3 COH ( 1 mL )( 74.12 g ( CH 3 ) 3COH )
=0.21 mol (CH 3)3 COH
1 mol ( CH 3 ) 3 CCl 92.57 g ( CH 3 ) 3 CCl

g of ( CH 3 ) 3 CCl=0.21 mol ( CH 3 ) 3 COH ( 1 mol ( CH 3 ) 3 COH )( 1 mol ( CH 3 ) 3 CCl )
=19.4 g ( CH 3 ) 3 CCl
Actual Yield:
g of ( CH 3 ) 3 CCl=15.1 mL of CH 3 ( CH 2 ) 3 Br ( 0.851 g
1 mL )
=12.9 g(CH 3) 3 CCl
Percent Yield:
Actual Yield 12.9 g
% yield= x 100 %= x 100 %=66.5 %

The table below shows the results obtained from qualitative test of the final alkyl halides products with
selected solvents.
Compoun Ethanolic Silver Silver Iodide in

d Nitrate Acetone
n-Butyl pale cream yellow precipitate

Bromide precipitate
t-butyl white precipitate no precipitate forms
chloride
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DISCUSSION:
A. PREPARATION OF n-BUTYL BROMIDE (CH3CH2CH2CH2Br)
The synthesis of n-Butyl Bromide from n-butyl alcohol with Hydrobromic acid was characterized by a
nucleophilic substitution of SN2 mechanism. This particular synthesis followed the SN2 pathway due to
primary nature of the substrate (1o) which was sterically unhindered and the relatively good nucleophile
present (Br-) by virtue of its basicity. The reaction between the starting materials Sodium Bromide and
Sulfuric acid at the beginning of the experiment produced the Hydrobromic acid that was used in the later
proceeding step of the reaction. The reaction presented below showed that the H 2SO4 shifts the equilibrium
more or less towards the production of more HBr.
The oxygen from the n-butyl alcohol added was protonated before substitution takes place. The
hydrogen from the hydrobromic acid converted its weakly basic hydroxyl group which was a poor leaving
group into protonated alcohol and later formed the good leaving group which was the H 2O. According to
Smith (2011), the more stable the leaving group, the better able it is to accept an electron pair, H 2O is a
better leaving group than –OH because H2O is a weaker base.
Then comes the dissociated strong Br- ion from the hydrobromic acid acted as a nucleophile
attacked the alkyl halide carbon 180° away from the departing water that leads to a transition state with a
partially formed C–Br bond and a partially broken C–OH 2 bond. Also, the structure of the substrate being
sterically unhindered made the approach of the nucleophile and bond formation easy and faster. This one
step mechanism occurred simultaneously forming the major end product n-Butyl Bromide, and minor
products of sodium bisulfate and water. This was achieved during the reflux portion of the experiment.
↓Transition state
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As for the successive washing, the water removed the inorganic impurities, traces of n-butanol as
well as for dissolution and migration of the inorganic compounds (NaBr, NaHSO4) to the aqueous layer. The
addition of cold concentrated sulfuric acid removed any unreacted alcohol that may still be present as it
would have protonated the n-butanol and made it soluble in the aqueous sulfuric acid. The treatment with
the 10% sodium carbonate solution would then essentially removed any of the leftover sulfuric acid in an
acid-base neutralization reaction: Na2CO3 + H2SO4 → Na2SO4 + H2O + CO2. After separation, few
anhydrous calcium chloride, a good drying agent being added to the crude n-butyl bromide sample
removed the possible excess water in the solution. CaCl(s) + H2O(l) → CaCl.nH2O(s)
B. PREPARATION OF tert-BUTYL CHLORIDE ((CH3)3C-Cl)
The synthesis of tert-Butyl Chloride was characterized by a nucleophilic substitution of SN1
mechanism, opposite to the mechanism involved with the synthesis of n-Butyl Bromide. This particular
pathway on the other hand, is a two-step mechanism. The first step involves the slow ionization to form a
carbocation, where in this process involves the breaking away of the leaving group from the substrate. The
highly substituted carbocation like the tertiary alcohols (3 O) are more preferred as it formed a more stable
carbocation. The second step is a fast attack on the carbocation center by a nucleophile. The carbocation
is a strong electrophile; it reacts very fast with nucleophiles, including weak nucleophiles (Wade, 2013).
The reaction of a tert-butyl alcohol with HCl take placed by an S N1 mechanism when the acid
protonates the hydroxyl oxygen atom of the alcohol to generate a better leaving group (McMurry, 2017).
The t-Butyl Alcohol by definition also acted as a Bronsted-Lowry base because it accepted a proton from
the hydrogen from hydrochloric acid. At the first step, the water which made into a better leaving group was
expelled to generate heterolysis of the C–O bond and that formed the stable tertiary intermediate
carbocation. This step was rate-determining as it involves only bond cleavage (Smith, 2011).
Spontaneous dissociation of the protonated alcohol occurs in a slow, rate limiting step to yield a
carbocation intermediate plus water. The next step was the nucleophilic attack of nucleophilic chloride ion
Cl- on the stable carbocation intermediate and formed the new C–Cl bond in the alkyl product. Step two
was faster than step one because no bonds were broken and one bond was formed. The carbocation acts
as a Lewis acid in this step since it accepted an electron pair from the chloride ion that also acts as a Lewis
base to form the tert-Butyl Chloride.

Test with Alcoholic Silver Nitrate
Functional classification tests among the end product alkyl halides (tert-Butyl Chloride and n-Butyl
Bromide) were done in with two different solvent-nucleophile systems. The test with alcoholic silver nitrate
in SN1 mechanism was more favorable for tertiary alkyl halides rather than primary since it can have formed
stable carbocation. The SN1 reaction goes much more readily in polar solvents like ethanol that stabilize
ions. The rate limiting step forms two ions, and ionization was taking place in the transition state. This was
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also where the initial loss of the leaving group by the substrate happened. Polar solvents solvate these ions
by an interaction of the solvent’s dipole moment with the charge of the ion. Wade (2013) stated that protic
solvents such as alcohols and water were more effective solvents because anions form hydrogen bonds
with the –OH hydrogen atom, and cations complex with the nonbonding electrons of the –OH oxygen atom.
Two reactions were made in this test; one was for the classification test for the haloalkanes. Below
was the example mechanism of tert-Butyl Chloride as its negatively charged chloride ions in solution paired
up with the positively charged free floating silver ions and thus formed the Silver Chloride which precipitates
out as white solids in the result observation since it was insoluble in ethanol. The second reaction was the
second step of the SN1 reaction where the ethanol acts as a weak nucleophile and attacks the electrophilic
carbocation that formed the tert-butyl ethyl ether. These steps were illustrated below:
As for
the n-butyl bromide, the positive reaction should not have happened supposedly due to the nature of the
substrate which was a primary alkyl halide, meaning, it would preferably undergo the S N2 mechanism.
Furthermore, the polar protic nature of the alcohol discourages the its bulky sizes and the relative
weakness as a nucleophile. The positive results observed in the reaction with silver nitrate might due to the
impurities of the n-butyl sample.
Test with Sodium Iodide in Acetone
The less common sodium iodide in acetone test gives a partial differentiation of primary, secondary,
and tertiary alkyl bromides and chlorides. The only difference it has with the alcoholic AgNO 3 test was that
the reaction involves the one-step, concerted, SN2 mechanism. The reaction occurred most quickly when
the attack at the carbon that bears the halogen and is at least hindered sterically. Hence, primary alkyl
halides were much favored than the secondary and tertiary. This reaction was also called the Finkelstein
reaction since in the SN2 reaction involves the exchange of one halogen atom for another. This SN2
reactions work best in polar aprotic solvents, solvents that can’t hydrogen bond such as acetone,
(CH3)2C=O. As a result, the electrons of the anion were more available for reaction. The anion is at a higher
energy level because of the small stabilization by the solvent (Carey & Sundberg, 2007).
The illustrated mechanism below showed the n-Butyl Bromide being much more suitable for the said
reaction. When the salt NaI was dissolved in acetone, the Na+ cations were solvated by ion-dipole
interactions with the acetone molecules, but, with no possibility for hydrogen bonding, the I- anions were not
well solvated. The Br- ions after leaving from the n-Butyl Bromide would then approach the Na+ ions to form
↓
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the NaBr which precipitates out of solution, since it was insoluble in acetone, driving the reaction to the
right.
CONCLUSION:
Therefore, based on the experiment done, the conversion of an alcohol into an alkyl halides
governed two characteristics of substitution reaction mechanism namely the S N1 and SN2. The SN2
mechanism exhibited in the nucleophilic attack of Bromide ions on n-Butanol to form n-Butyl Bromide while
the SN1 mechanism on the other hand was observed with the formation of tert-Butyl Chloride from tert-
Butanol. The relative percent yields results obtained from the experiment were quite favorable as for aiming
greater production of alkyl halides samples that can be used for future laboratory experiments. Though
there were quite few sources for error that impacted the final percentage yield of the products, improvement
on good laboratory practice in accords with carefulness should be sort in by the experimenters for better
production in future experiments. The much deeper comprehension of the substitution reaction
mechanisms that is significant in organic chemistry had also been obtained from this activity along with the
worthy proper laboratory procedures involved in the synthesis of the haloalkanes. To put it briefly, the study
of the substitution reaction mechanisms through these alkyl halides had provided an insight into the more
structurally complex reactions and how they might possibly occur.
REFERENCES:
 Carey, F., Sundberg, R. (2007). Advanced Organic Chemistry. Part A: Structure and Mechanisms.
Fifth Edition. Springer Science+Business Media, LLC, 233 Spring Street, New York, NY 10013,
USA. p.363
 March, J., Smith, M. (2007) March’s Advanced Organic Chemistry. Reactions, Mechanisms, And
Structure. Sixth Edition. John Wiley & Sons, Inc., Hoboken, New Jersey & Canada. p.246
 McMurry, J. (2017). Organic Chemistry, Ninth Edition. Cengage Learning. 20 Channel Center
Street. Boston, MA 02210, USA. p.544
 Miller, A., Solomon, P. (1999) Writing Reaction Mechanisms in Organic Chemistry. Second Edition.
Elsevier Science & Technology Books. p.86-87
 Smith, J.G. (2011) Organic Chemistry, Third Edition. The McGraw-Hill Companies, Inc., 1221
Avenue of the Americas, New York, NY 10020. p.236
 Wade L. G. (2013) Organic Chemistry. Eight Edition. GEX Publishing Services. Pearson Education,
Inc., Permissions Department, 1900 E. Lake Ave., Glenview, IL 60025. p.247 & p.250

Preparation of Alkyl Halides Lab

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DEPARTMENT OF PURE &

DEPARTMENT OF PURE AND APPLIED CHEMISTRY

Name: Lab Schedule: MW, 10:00 AM – 1:00 PM

Preparation of Alkyl Halides

B. PREPARATION OF tert-BUTYL CHLORIDE

C. CLASSIFICATION TESTS FOR ALKYL HALIDES

RESULTS AND OBSERVATIONS:

Preparation of n-butyl bromide

Given: Density of CH3(CH2)3OH = 0.806g/mL Density of CH3(CH2)3Br = 1.276g/mL

mol of CH 3 ( CH 2 ) 3 OH =15 ml CH 3 ( CH 2 ) 3 OH ( 0.8060 g CH1mL3 ( CH 2) 3 OH )( 74.121

g of CH 3 ( CH 2 ) 3 Br=10.3 mL of CH 3 (CH 2 ) 3 Br ( 1.276 g

Preparation of n-butyl bromide

Actual Yield (Distillate Collected) 15.1 mL (12.9g)

Temperature Range During Collection 52.7 oC

Given: Density of (CH3)3COH= 0.775 g/mL Density of (CH3)3CCl = 0.851g/mL

0.775 g ( CH 3 ) 3 COH 1mol (CH 3 ) 3 COH

1 mol ( CH 3 ) 3 CCl 92.57 g ( CH 3 ) 3 CCl

C. CLASSIFICATION TESTS FOR ALKYL HALIDES

Compoun Ethanolic Silver Silver Iodide in

n-Butyl pale cream yellow precipitate

C. CLASSIFICATION TESTS FOR ALKYL HALIDES

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