Course: Organic Chemistry I Laboratory

Laboratory report №7
Synthesis of 2‐chloro‐2‐methylbutane
Student: Adelina Zeinolla
Section: Section-2
Date performed: 31.10.2021
Course Instructor: Aisulu Zhanbossinova

Fall 2021

I. INTRODUCTION
Title of Experiment: Synthesis of 2‐chloro‐2‐methylbutane
Purpose: to perform synthesis of 2‐chloro‐2‐methylbutane from 2-methyl-2-butanol and to
analyze the obtained product to assess the success of synthesis using GC analysis, IR
spectroscopy and characterization tests.
Theory:
Alkyl halides are a group of chemical compounds, in which one or more hydrogen atoms
in an alkane have been replaced by halogens. Their general formula is R-X, where R is an alkyl
group and X is a halogen. Preparation of alkyl halides include direct ha;ogenation of alkanes by
radical chain reaction, by treatment of alcohols with hydrogen halides (HX), phosphorus halides
(PX3), thionyl chloride (SOCl2). Alternatively, alkyl chlorides can be prepared by the addition of
HX to alkenes. Alkyl halides are used in the production of polymers, pharmaceuticals and
pesticides. They were also extensively used as fire retardants, aerosol propellants, anesthetics,
refrigerants. In organic synthesis they also act as a precursor of synthesis of various compounds
and take part in an elimination, substitution, and reactions with metals.
Alkyl halides can be obtained by reacting alcohols with hydrogen halides. In this
substitution reaction, carbocation acts as an electrophile, electron-deficient center that is attracted
to an electron-rich nucleophile. Such nucleophilic substitution reactions with hydrogen halides
occur via different mechanisms: primary and secondary alcohols undergo SN2 mechanism, while
tertiary alcohols undergo SN1 mechanism. In bimolecular substitution, or SN2 mechanism, the
first step includes protonation of alcohols. Since alcohols are weak Lewis bases, they get
protonated, which is a fast step of a mechanism. The next step includes the attack of nucleophile
from the backside of the carbon atom, thus one molecule of water is lost, which is a leaving
group. This step is a rate-limiting step, and since the transition state results from the collision of
two molecules, it is called bimolecular substitution. In unimolecular nucleophilic substitution,
the transition state involves only one molecule. Since protonated tertiary alcohols due to steric
hindrance cannot be attacked by a nucleophile from the backside, they decompose to give a
carbocation and water molecule in its rate-limiting step. Since primary alcohols are less reactive,
their substitution is a slow process and should be carried out at high temperatures. Tertiary
alcohols are more reactive, thus they undergo substitution with halides more quickly.
Characterization tests can be performed to identify the presence of an alkyl halide group.
The easiest and more sensitive method for identifying the presence of chlorine, bromine and
iodine in an organic compound is a Beilstein test. It includes burning of the alkyl and aryl halides
on the surface of the copper, which should give a characteristic green color to the flame. Green
color results from the reacting organic halides with a Copper (I) oxide to give volatile cuprous
halides. Alkyl halides also react with silver nitrate to give in ethanol to give silver halide
precipitate. This reaction undergoes by an SN1 mechanism and can be represented as follows:
R−X + AgN O3 → R−ON O2 + AgX ↓
Formation of an AgX precipitate gives a positive result for the presence of alkyl halides.
Generally, alkyl iodides react faster than alkyl bromides or chlorides and tertiary alkyl halides
react faster. Alkyl chlorides and bromides react with sodium iodide in acetone via S N2
mechanism. As a result, alkyl iodide and corresponding sodium halide are formed. Since sodium
chloride and sodium bromide are insoluble in acetone, it forms precipitate, giving a positive test
for identification. This reaction for alkyl chloride can be represented as follows (alkyl bromide
undergoes the same reaction):
R−Cl+ NaI → R−I + NaCl↓
In this experiment, synthesis of 2-chloro-2-methylbutane will be performed by mixing
corresponding 2-methyl-2-butanol tertiary alcohol with a concentrated solution of HCl at room

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temperature. Since reaction takes place by a SN1 mechanism, a catalyst is not required. The
overall reaction for this process is represented by the following equation:

In this reaction, side products such as alkenes are not formed because reagents react under room
temperature. Therefore, purification of 2-chloro-2-methylbutane is not complicated, products can
be washed with sodium bicarbonate and water.
II. MATERIALS
The following glassware and chemical equipment was used:
● Micropipettes with tips ● Thermometers
● 5-ml conical vial ● Hot plate
● 3-ml conical vial ● Balance
● Beaker ● IR spectroscopy
● Evaporating dish ● Gas chromatography
● Spatulas ● Test tubes
● Pasteur pipettes ● Test tube rack
● Cotton ● Tongs
● Hickman still ● Copper wire
● Air condenser ● Alcohol burner
III. CHEMICALS
Table 1. Used chemicals and their physical properties.
Compound MM Mp Bp Densit Solubility Flammabilit Toxicity/Hazard
(gm (℃ ) (℃ ) y y
ol-1) (g/cm 3

2-methyl-2- 88.1 -9.1 102.4 0.8096 120 Highly LD50 1.0-2.0 g/kg
butanol 50 at 20 mg/L at Flammable (oral, rat)
°C 25 °C liquid and Causes skin
vapor (3rd irritation, harmful if
degree) inhaled, may cause
respiratory irritation

Hydrochlor 36.4 - -85.1 1.639 67.3 Not LD50 1449 mg/kg

ic acid 6 114.2 at 20 g/100 g flammable (oral, mouse)
(conc.) 2 °C water at Corrosive, causes
30 °C severe skin burns
and eye damage,
toxic if inhaled,

5% sodium 84.0 Deco Deco 2.20 7.8 Not LD50 4220 mg/kg
bicarbonate 07 mpose mpos g/100g at flammable (oral, rat)
s es 18 °C May cause eye

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 aroun irritation
d 50
°C

Magnesium 120. 1124 - 2.66 35.1 Not LD50 1200 mg/kg

sulfate 366 g/100 mL combustible (oral, rat)
(20 °C) May be harmful if
swallowed or in
contact with skin

DI water 18.0 0 100 1.00 - - -

1

Boiling Boili - 800 - - Insoluble -

chips ng
chips

Sand 60.0 1710 2230 2.2- Insoluble Noncombust Not expected to be

(Silicon 84 2.6 ible solid acutely toxic
dioxide) (one
mole
cule)

1-butanol 74.1 -89.8 117.8 0.8098 73 g/L at Flammable LD50 0.79 to 4.36
2 5 at 20 25 °C liquid and g/kg (oral, rat)
°C vapor (3rd Harmful if
degree) swallowed, causes
skin irritation,
serious eye damage,
May cause
respiratory irritation
and drowsiness or
dizziness

n-butyl 137. -112.4 101.3 1.276 8.69 Highly LD50 2761 mg/kg
bromide 02 mg/L at Flammable (oral, rat)
25 °C liquid and Causes skin, eye
vapor (3rd irritation, may cause
degree) respiratory irritation,
toxic to aquatic life

2-chloro-2- 106. -73.5 85.5 0.866 Insoluble Highly May cause skin, eye
methylbuta 59 in water Flammable irritation;
ne liquid and may cause
vapor respiratory irritation

t-butyl 137. -16.2 73.3 1.2125 600 mg/L Highly LD50 1250 mg/kg

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 bromide 02 at 25 at 25 °C Flammable (oral, rat)
°C liquid and May cause toxic
vapor (3rd effects if inhaled or
degree) absorbed through
skin

bromobenz 157. -30.6 156.0 1.49 0.041 Flammable LD50 3300 mg/kg
ene 01 g/100 mL liquid and (oral, rat)
vapor (2nd Causes skin
degree) irritation, toxic to
aquatic life

15% 149. 651 1304 3.67 1.84 Not LD50 4340 mg/kg
sodium 8942 g/ml at 25 flammable (oral, rat)
iodide in °C Causes skin
acetone irritation, serious eye
irritation, may cause
respiratory irritation,
very toxic to aquatic
life

0.1M silver 169. 212 440 5.35 245 g/100 Not LD50 (oral, rat)
nitrate in 873 (deco g of flammable, Oxidizer (may
ethanol mpos water increases intensify fire),
es) flammability corrosive, causes
of severe skin burns
combustibles and eye damage,
very toxic to aquatic
life
IV. PROCEDURE
Part I. Synthesis of 2-chloro-2-methylbutane
1. 1 ml of 2-methyl-2-butanol and 2.5 ml of hydrochloric acid were transferred into a 5 ml
conical vial. The vial was capped and let to stand for a minute. Mixture was carefully
shaken with occasional venting.
2. Two phases were allowed to completely separate. Using a pasteur pipet, the upper layer
was transferred into a separate vial and an organic layer containing alkyl halide was kept.
3. Organic layer was washed using 1 mL of DI water. Phases were separated again and the
organic layer was saved. Organic layer was washed again, using 1 ml of 5% aqueous
sodium bicarbonate. Vial was shaken again and vented carefully, since CO 2 is produced
in this step. Phases were allowed to separate and the organic layer was separated again.
Organic layer was washed again, using 1 mL of DI water.
4. Small amount of magnesium sulfate, a drying agent, was added to the organic layer and
allowed to stand for 5 minutes.
5. Crude alkyl halide was filtered using a filter-Pasteur pipet into a clean 3 ml conical vial.
Boiling chip was added and a microscale distillation apparatus was assembled, as

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 depicted in figure 1. In order to prevent the loss of product, an air condenser was placed
on top of the Hickmann still.

Figure 1. Schematic representation of a microscale distillation apparatus.

6. Apparatus was placed in the sand bath, which is heated and kept at 130-140℃.
Thermometer was placed in the apparatus and ice was transferred to the upper part of a
Hickmann still. The fraction that boils between 80-86℃ was collected into a pre-tared
vial.
Part II. Analysis of 2-chloro-2-methylbutane
7. Crystal and pressure tower of the IR spectrometer were cleaned with acetone and tissue
paper. “OMNIC” software was used for data collection and representation. Firstly, the
starting material, 2-methyl-2-butanol, was placed on the crystal and IR spectrum was
obtained. Spectrum of the product was also generated in the same way.
8. Starting material and obtained product were also analyzed using a gas chromatograph.
“Xcalibur” software was used to create a method for autosampler and gas chromatograph.
Samples were analyzed at 50℃ for 5 minutes.
9. Characterization tests were also performed and the Beilstein test was done first. Copper
wire was dipped into the 2-methyl-2-butanol and heated in the flame of an alcohol
burner. The same procedure was repeated with the obtained product and the color of the
flame for two cases was recorded.
10. The next test was performed with a silver nitrate in ethanol. To seven clean labeled test
tubes 0.5 ml of 0.1M solution of silver nitrate in ethanol was added. 1 drop of n-butanol
was added into the first tube. The same procedure was repeated with the rest compounds:
2-methyl-2-butanol, 1-bromobutane, 2-chloro-2-methylbutane, t-butyl bromide,
bromobenzene, reaction product. Absence or presence of a precipitate was recorded for

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 each tube. Tubes, where no precipitate was formed within 5 minutes, were heated and
boiled in a water bath at 80℃.
11. To perform a sodium iodide in acetone test, 0.5 ml of 15% solution of sodium iodide in
acetone was added to seven labeled test tubes. One drop of each compound studied in the
previous step was added into the corresponding test tubes. Formation of the precipitate
was checked and recorded for each compound. Tubes, where no precipitate was formed
within 3 minutes, were heated and boiled in a water bath at 50℃ for five minutes.
V. RESULTS AND DISCUSSION
Results
Since 1 ml of 2-methyl-2-butanol was used in this experiment, its mass can be calculated
by multiplying volume to the density of the 2-methyl-2-butanol:
m2−methyl−2−butanol =1ml × 0.8096 g/ml=0.8096 g
To find the number of moles of 2-methyl-2-butanol, its mass was divided by its molar mass:
−3
n=0.8096 g/88.15 g /mol=9.18 ×1 0 moles
Since reactant 2‐chloro‐2‐methylbutane and a product 2-chloro-2-methylbutane are present in a
1:1 ratio, their number of moles are equal. Therefore, theoretical mass for the product can be
calculated by multiplying its number of moles to molecular weight:
mtheoretical =9.18 ×1 0−3 mol ×106.59 g/mol=0.979 g
Since 0.69 grams of product was formed in this experiment, % yield of the synthesis can be
calculated using the following approach:
actual yield 0.69 g
%yield =¿ ×100 %=¿ ×100 %=70.48 %
theoretical yield 0.979 g

Figure 2. IR spectrum of 2-methyl-2-butanol.

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 Figure 3. IR spectrum of the product.
Table 3. Result of GC analysis of 2-methyl-2-butanol, 2-chloro-2-methylbutane and product.
Compound Retention time, min

2-methyl-2-butanol in Acetone 2.75

acetone
2-methyl-2-butanol 3.53

2-chloro-2-methylbutane in Acetone 2.73

acetone
2-chloro-2-methylbutane 3.62

Products of synthesis Acetone 2.73

reaction in acetone
2-chloro-2-methylbutane 3.62
Table 4. Results of Beilstein, silver nitrate in ethanol, sodium iodide in acetone tests.
Characterization test Compound Observation

Beilstein test 2-methyl-2-butanol No change in flame color

product of synthesis Green colored flame

n-butanol No precipitate

2-methyl-2-butanol No precipitate

1-bromobutane Precipitate formation

Silver nitrate in 2-chloro-2-methylbutane Precipitate formation
ethanol test
t-butyl bromide Precipitate formation

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 bromobenzene No precipitate

product of synthesis Precipitate formation

n-butanol No precipitate

2-methyl-2-butanol No precipitate

1-bromobutane Precipitate formation

Sodium iodide in 2-chloro-2-methylbutane Precipitate formation
acetone
t-butyl bromide Precipitate formation

bromobenzene Precipitate formation

product of synthesis Precipitate formation

Discussion
In this experiment, 2-methyl-2-butanol was reacted with concentrated hydrochloric acid
to produce the 2-chloro-2-methylbutane. Product of the reaction was further analyzed by GC, IR
spectroscopy, characterization tests to assess the success of the performed synthesis reaction. As
a result of the experiment, 0.69 grams of product of 2-chloro-2-methylbutane was produced, a
percentage yield of which is 70.48%. There is a possibility of product loss during the separation
of aqueous and organic layers, where an organic layer containing crude alkyl halide may have
been pipetted out within the aqueous layer. There is a possibility of a product loss during
transfers or product and distillation.
When products were analyzed using GC, retention times of 2-methyl-2-butanol, 2-chloro-
2-methylbutane and product of synthesis were 3.53 min, 3.62 min, and 3.62 min, respectively.
Since the retention time of the product is exactly equal to the retention time of the 2-chloro-2-
methylbutane, it can be concluded that the synthesized product was 2-chloro-2-methylbutane and
its synthesis was performed successfully. Since the molecular mass of the 2-chloro-2-
methylbutane is larger than that of the starting compound, its retention time was slightly longer.
IR spectroscopy analysis was also performed for 2-methyl-2-butanol and the product of
the synthesis. As it can be seen from the IR spectrum of 2-methyl-2-butanol, strong broad
stretching at 3368.37 cm-1 indicates presence of the O-H group of alcohol. IR spectrum of the
synthesized product and IR spectrum of the 2-chloro-2-methylbutane were compared.
Characteristic bands of -CH stretching of alkyl halides at 1150-1350 cm -1 was observed in both
IR spectrums. Moreover, stretching at 550-800 cm-1 was also observed in both spectrums,
indicating the presence of the C-Cl bonds. Both spectrums had peaks at 2974 cm -1, indicating the
presence of C-H bonds of alkanes. Generally, both spectrums were very similar, which indicated
that the product obtained is a 2-chloro-2-methylbutane.
Characterization tests were also performed to indicate the presence of alkyl halides. Other
compounds were also used in these tests as positive and negative controls. Beilstein test gave a
positive result with the product of the synthesis, giving the characteristic green colored flame,
which indicated the presence of alkyl halide group. 2-methyl-2-butanol gave a negative result for
this test. Silver nitrate in ethanol test gave a positive result for the product of the synthesis and

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the formation of white precipitate was observed. Since 2-chloro-2-methylbutane also gave a
positive result with white precipitate of AgCl, it can be concluded that our product of synthesis
also contains Cl. 1-bromobutane and t-butyl bromide also have a positive result for this test and
characteristic yellow precipitate of AgBr was observed. Remaining n-butanol and 2-methyl-2-
butanol result in no precipitate formation, because they do not contain the alkyl halide group.
The last test with the sodium iodide in acetone was performed and n-butyl bromide, 2-chloro-2-
methylbutane, t-butyl bromide, bromobenzene and the reaction product gave a positive result for
this test. However, since it is an SN2 mechanism, tertiary alkyl chlorides, aryl and vinyl halides
should not react even upon heating. Such false-positive results may have resulted from the
impurities within the sodium iodide solution or cross contamination may have been introduced
during the samples transfer .

VI. CONCLUSION
The main objective of this experiment was achieved, since the synthesis of 2‐chloro‐2‐
methylbutane from 2-methyl-2-butanol was performed and the success of the synthesis was
assessed using GC analysis, IR spectroscopy and characterization tests. Percentage yield of the
synthesis was calculated to be 70.48%, which may have resulted from product loss during layers
separation. Results obtained from the GC and IR spectroscopy analysis indicated that the product
being analyzed is 2‐chloro‐2‐methylbutane. Characterization tests also gave a positive result for
the presence of alkyl halides. Beilstein test and silver nitrate in ethanol test gave positive results
for the presence of alkyl halide in the product. However, the last test with sodium iodide in
acetone gave false-positive results, it was assumed that the sodium iodide solution may have had
impurities within it or cross contamination may have affected the results.

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 References
1. Palleros, D. R. (2000). Experimental organic chemistry. New York: Wiley.
2. PubChem. (n.d.). https://pubchem.ncbi.nlm.nih.gov/

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