CLASSIFICATION TESTS FOR ORGANIC HALIDES

Venus Tibalao, Cheene Meryll Urmatam, Abby Valdesancho,

Gian Paula Villamayor, Ramon Villanueva III and Thea Ferina Vital
Group 9 2C Pharmacy Organic Chemistry Laboratory

ABSTRACT

Alkyl halides or commonly known as haloalkanes are organic compounds that involves the replacement of a halogen
atom to an alkane. This study aimed to identify the rate of reaction of a haloalkene, chiefly n-butyl chloride, sec-butyl
chloride, tert-butyl chloride and chlorobenzene in an S
N
1 and S
N
2 mechanisms. Initially, the presence of a halogen in
an alkane was indicated by Beilstein Test. It was found out that the presence of a halogen gives of a green-flame to
the test. Thenceforth, reactivity of the said compounds in an S
N
1 reaction was tested by reacting them with Alcoholic
AgNO
3
. Only the secondary and tertiary butyl chloride produced a reaction (in the form of a white precipitate) in this
mechanism, but the former haloalkane acquired a faster reaction time because it produces the most stable
carbocation which is a prerequisite for a certain haloalkane to react in an S
N
1 reaction. Normal butyl chloride did not
react because of its high instability when it becomes a carbocation. Lastly in S
N
2 mechanism, the haloalkanes were
made to react with NaI in Acetone. All haloalkanes, except for chlorobenzene, produced a white precipitate
in the reaction mechanism. However, n-butyl chloride had the fastest response time because of its low steric
hindrance. The said property of normal butyl chloride explains its susceptibility to S
N
2 reaction. The unresponsiveness
of chlorobenzene is due to its high stability acted upon by the resonating effect of its conjugated double bonds.

INTRODUCTION
Haloalkanes are organic compounds having a
halogen atom covalently bonded to an sp
3
hybridized carbon. Since halogens are more
electronegative than carbons, the carbon-halogen
bond in a haloalkane is polarized.
Chlorofluorocarbon is a well-known example of a
haloalkane. They are used as refrigerants,
propellants for aerosols, for generating foamed
plastics and solvents for dry cleaning. However,
CFCs are responsible for the destruction of ozone
layer that is why the use of these compounds is
now in limitation.

The objective of this experiment is to identify the
different properties and reaction rate of
haloalkanes through the use of Beilstein Test,
Reaction with Alcoholic AgNO
3
and Reaction with
NaI in Acetone.

EXPERIMENTAL
A. Compounds tested (or Samples used)
The compounds tested were n-butyl chloride,
sec-butyl chloride, tert-butyl chloride and
chlorobenzene. The information of the said
compounds is stated below:

n-butyl chloride

The figure below is the structural formula of a
normal butyl chloride (n-butyl chloride). It is a
clear, colorless liquid. It is used as a solvent, as a
medicine to control worms, and to make other
chemicals. Exposure to the said substance can
infuriate the eyes, nose, throat and skin.
Highlevels of Butyl Chloride causes dizziness and
syncope. It is a flammable liquid and a fire
hazard.

Figure 1: Chemical Structure of n-butyl
chloride

sec-butyl chloride

Figure 2 presents a secondary butyl chloride or
2-Chlorobutane. It is a clear, colorless liquid with
a sharp odor. Its vapors may form explosive
mixtures with air.



Figure 2: Chemical Structure of sec-butyl
chloride

tert-butyl chloride

Figure 3 shows a tertiary butyl chloride. It is a
clear, colorless liquid which is slightly soluble in
water. Inhalation of high concentrations may
cause central nervous system effects
characterized by headache, dizziness,
unconsciousness and coma.



Figure 3: Chemical Structure of tert-butyl
chloride


Chlorobenzene

The figure beneath is a chlorobenzene. uses of
chlorobenzene are as a solvent for pesticide
formulations, diisocyanate manufacture, and
degreasing automobile parts and for the
production of nitrochlorobenzene.In the past,
chlorobenzene was used as an intermediate in
phenol and DDT production.


Figure 4: Chemical Structure of
chlorobenzene

B. Procedure
The following tests used in this study are
indicated as follows:
1. Beilstein Test: Copper Halide Test
a. A small loop was made with one end of
the copper wire. The loop was directly
heated in the oxidizing zone of a non-
luminous flame. The heating was
continued until the green color
imparted to the flame disappeared.
b. The loop was cooled slightly and dip it
into the solid or liquid sample. The loop
was heated with the sample in a non-
luminous flame: first in the inner zone,
then in the outer zone near the edge of
the flame.
2. S
N
1 Reactivity: Reaction with Alcoholic
AgNO
3

a. 5 drops of the sample was added to 20
drops of 2% ethanolic AgNO
3
. The
sample was shaked and the time for a
silver halide precipitate to form was
recorded in seconds or minutes.
3. S
N
2 Reactivity: Reaction with NaI in
Acetone
a. Dry test tubes was used for this
experiment. 5 drops of the sample was
added to 2 drops of 15% NaI in
anhydrous acetone. The contents were
mixed the time was noted (in seconds
or minutes) required precipitate to
form. The color of the precipitate was
described

RESULTS AND DISCUSSION
The sample of haloalkanes were subjected in the
following reactions, namely, Beilstein test, S
N
1
Reactivity (Reaction with Alcoholic AgNO
3
), and
S
N
2 Reactivity (Reaction with NaI in Acetone).
Primarily, the data acquired from Beilstein Test
was the haloalkanes color when exposed to
flame.

Table 1. Data obtained from Beilstein Test

Compound used Color of the flame
n-butyl chloride Green
sec-butyl chloride Green
tert-butyl chloride Green
chlorobenzene Green

Green flame, shown by Table 1, indicated the
presence of a haloalkane, particularly Chloride.
The equation for this test is presented below.

When you heat the copper wire in a flame, it is
oxidized on the surface to copper (II) oxide.

2Cu(s)+O
2
(g)2CuO(s)

A positive Beilstein test is based upon the
reaction of the Organic halide with the Copper
oxide:

CuO + RX --> CuX
2
+ CO
2
+ H
2
O

The volatile copper halide (CuX
2
) compound gives
the flame test a blue-green colered flame.
Table 2. Data obtained from S
N
1 Reactivity

Compound used Reaction and time
achieved from reaction
n-butyl chloride No precipitate
sec-butyl chloride White precipitate
(3 min and 10 sec)
tert-butyl chloride White precipitate
(1 sec)
chlorobenzene No precipitate

Secondly, S
N
1 Reactivity was acquired from
reacting 2% ethanolic AgNO
3
with the given
haloalkanes. This reaction will identify if the
samples given produced a precipitate. The time
of response or rate of reaction to generate a
precipitate indicates the nature of haloalkanes
toward S
N
1 reaction. It appears that n-butyl
chloride and chlorobenzene did not react with the
said reaction. A primary haloalkane does not
have an inherent effect in S
N
1 reaction because it
does not provide a stable carbocation. S
N
1
Reactivity depends on the stability of the
carbocation. The more stable a carbocation, the
more susceptible a haloalkane to react in an S
N
1
reaction. Chlorobenzene did not react in the
because of the stabilizing or resonating effect of
conjugated double bonds in benzene.


Figure 4: Reaction mechanism of S
N
1
Reaction
The figure above shows the reaction mechanism
of S
N
1 Reaction. This shows a two-step reaction
of the said mechanism. S
N
1 Reactions greatly
depend on the nature of the leaving group,
particularly the halogens. Reactivity depends on
the stability of the carbocation. The more stable a
carbocation, the more susceptible a haloalkane to
react in an S
N
1 reaction.

Table 3. Data obtained from S
N
2 Reactivity

Compound used Reaction and time
achieved from reaction
n-butyl chloride White precipitate
(1 sec)
sec-butyl chloride White precipitate
(2 sec)
tert-butyl chloride White precipitate
(3 sec)
chlorobenzene No precipitate

In this reaction, only chlorobenzene failed to
react in S
N
2 mechanism because of its high
stability due to Benzenes resonating effect. S
N
2
reaction prefers a primary haloalkane because
nucleophilic attack occurs simultaneously with
the leaving group. The more substituents
attached to the alpha carbon, the less tendency
for a nucleophile to attack the said carbon. This
accounts for the reason why a tert-butyl chloride
reacts slowly in an S
N
2 reaction. The figure below
explains the 1-step mechanism of S
N
2 reaction.
The said reaction depends on the nucleophile and
the leaving group.

Figure 5: Reaction mechanism of S
N
2
Reaction
The figure above explains the 1-step mechanism
of S
N
2 reaction. The said reaction depends on the
nucleophile and the leaving group.

REFERENCES

[1] Bayquen,A.,Cruz,C., De Guia,R. Lampa, F.,
Pena, G., Sarile, A., Torres,P. Laboratory Manual
in Organic Chemistry, pp.27-28
[2] Brown, H., and Poon, T. P. Introduction to
Organic Chemistry, pp. 250
[3] www.drugfuture.com/chemdata/sec-butyl-
chloride.html
[4]www.chemicalbook.com/ProductMSDSDetailCB
3372184_EN.htm
[5]chemwiki.ucdavis.edu/Organic_Chemistry/Alk
yl_Halides/Properties_of_Alkyl_Halides/Haloalkan
es