CLASSIFICATION TEST FOR ORGANIC HALIDES

ABSTRACT
Organic compounds containing a halogen which is attached to a carbon atom are called organic halides. These
compounds often undergo reactions through SN1 or SN2, varying based on the strength of the nucleophile. In the
experiment, the organic halides were classified as primary, secondary, or tertiary and were differentiated in terms of
SN1 and SN2 mechanisms. Organic halides, n-butyl chloride, sec-butyl chloride, tert-butyl chloride, and chlorobenzene
were subjected to Beilstein test and were reacted with ethanolic AgNO3 and NaI in anhydrous acetone. All the sample
compounds gave a positive result with Beilstein test, which signified the presence of Chloride. In the reaction with 2%
ethanolic AgNO3, all compounds except chlorobenzene produced a white precipitate or became turbid, as the latter was
observed to be unreactive. In addition, tert-butyl chloride formed a precipitate first, followed by sec-butyl chloride, and
lastly, the n-butyl chloride. Moreover, the reaction with 15% NaI in anhydrous acetone was expected to give the fastest
reaction with n-butyl chloride, followed by sec-butyl chloride, then by tert-butyl chloride. Due to its stability,
chlorobenzene was also unreactive to this test.

INTRODUCTION In this experiment, it is expected to be able to

Organic halides are organic compounds that achieve the following objectives: (1) to
have a halogen atom attached to a carbon atom. differentiate primary, secondary, and tertiary
The reactivity of organic halides depends on the organic halides based on their SN reactivity. (2) It
halogen atom bonded to the carbon atom in the also aims to be able to identify SN1 and SN2
particular compound [8]. mechanisms, as well as being able to distinguish
In an sp3 hybridized atom, an alpha (α) carbon the differences between the two.
atom is a carbon attached to the organic halide. It
can further be classified depending on the position EXPERIMENTAL
of the halogen atom on the chain of carbon atoms. A. Samples used
It can be considered as primary when an alkyl n-butyl chloride (C4H9Cl)
group is attached to the α-carbon atom, secondary
when two groups are attached to the α-carbon
atom, and tertiary when three groups attached to
the α-carbon atom [8].
Nucleophilic substitution are reactions that
sec-butyl chloride (C4H9Cl)
involve a nucleophile attacking a substrate,
donating an electron pair to the new bond, and
replacing a leaving group. It is further subdivided
into SN1 and SN2 reactions. The former are
nucleophilic substitutions involving a nucleophile
replacing a leaving group, and are unimolecular. tert-butyl chloride (C4H9Cl)
This means that the rate of this reaction depends
only on the concentration of one reactant. This
particular type of reactions occurs in two steps:
the leaving group leaves forming a carbocation
intermediate, and the attack of nucleophile in the
carbocation, forming the product. S N1 reactions
only take place in a polar protic solvent, and if the
nucleophile is weak. On the other hand, the latter Chlorobenzene (C6H5Cl)
is considered to be a bimolecular reaction since it
depends on the concentration of two reactants.
SN2 reactions happen simultaneously — the
nucleophile attacks the substrate as the leaving
group leaves the substrate. This reaction occurs in
polar aprotic solvents and if the nucleophile is
strong as it is supplementary for the backside B. Procedure
attack [6]. 1. S 1 Reactivity: Reaction with Alcoholic
N

The sample compounds were subjected to AgNO 3

Beilstein test, a simple qualitative chemical test for Five drops of the sample was added to 20 drops
the presence of halides. It was developed by of 2% ethanolic AgNO3, and the mixture was
Friedrich Konrad Beilstein. In this method, a shaken. The time for a silver halide precipitate to
positive result acquires a greenish to blue flame form was recorded in seconds or minutes. The
[7]. color of the precipitate was described.
 detected by Beilstein test since copper fluoride is
not volatile [9]. A green colored flame indicates
the presence of chloride; a blue-green flame
indicates the presence of bromide while a blue
flame indicates the presence of iodide. In the
experiment, all samples would produce a green
flame since all of them contained chloride.

2. SN1 and SN2 Reactivity

Organic halides can be classified as primary,
secondary, or tertiary organic halides depending
on the number of R-groups or alkyl groups
attached to the α-carbon atom [8], and the type
of organic halide greatly affects its susceptibility to
Figure 1. SN1 Reactivity Test of n-butyl chloride, undergo unimolecular nucleophilic substitution
sec-butyl chloride, tert-butyl chloride, and (SN1) or bimolecular nucleophilic substitution
chlorobenzene (SN2). SN1 reaction involves two steps, forming
intermediate products in between these two steps
while SN2 mechanism only involves one step [2].
2. S 2 Reactivity: Reaction with NaI in
SN1 and SN2 reactions are given by the following
N

Acetone reaction mechanisms:

Five drops of the sample was added to two R-X ---> R+ + X- unimolecular (SN1)
drops of 15% NaI in anhydrous acetone. The
R+ + Nu- ---> R-Nu + X- two steps
contents were mixed and the time required for a
precipitate to form was recorded in seconds or
Nu- + R-X ---> Nu-R + X- bimolecular (SN2)
minutes. The color of the precipitate was
one step
described.
In SN1 reaction, the substrate is heterolytically
broken, thus forming a carbocation intermediate
in the rate determining step. The more stable the
carbocation is means that it would be more
reactive with SN1 reaction [2]. Therefore, an
organic halide, which produces a tertiary
carbocation, the most stable carbocation, would be
the most reactive under SN1 conditions [3].
On the other hand, SN2 reaction only involves
one step since the departure of the leaving group
and the attachment of the nucleophile to the
substrate happen simultaneously; one bond
breaks while another forms as the nucleophile
attacks the opposite side of the substrate, a
process called as backside attack [6]. Primary
Figure 2. SN2 Reactivity Test of n-butyl chloride, organic halides are more reactive with SN2
sec-butyl chloride, tert-butyl chloride, and reaction because these organic compounds are the
chlorobenzene least sterically crowded [2]. Steric effect refers to
the repulsive interaction between atoms that are
RESULTS AND DISCUSSION close to each other [3]. When there are many
1. Beilstein Test groups attached to the α-carbon atom, such as in
Beilstein test is a qualitative test for halides. It tertiary organic halides, the reaction occurs slowly
involves the ignition of a copper wire in a flame, [3]; thus, SN2 reaction is not favored.
thus oxidizing it and forming a coat of copper (II) In the experiment, the 2% ethanolic AgNO3 was
oxide on its surface [7]. The heated copper wire is used for the SN1 reaction since this mechanism is
then dipped into the sample and is heated in the favored by polar protic solvents such as ethanol
flame again. A positive test is indicated by a [3]. Polar protic solvents stabilize the carbocation
greenish to blue flame [7]. The reaction between intermediate, thus increasing the reaction rate.
copper (II) oxide and halogenated organic Moreover, polar protic solvents also reduce the
compounds would form copper halides [4], and reactivity of the nucleophile, making the reaction
copper halides produce a greenish to blue flame favor SN1 over SN2 [5]. On the other hand, the
when chloride, bromide, or iodide is present. 15% NaI in anhydrous acetone was used for the
However, the presence of fluoride cannot be SN2 reaction since this reaction is favored by polar
aprotic solvents such as acetone [3]. Polar aprotic is already stabilized by pi-electron delocalization
solvents do not contain positively polarized or resonance.
hydrogen atoms, and the reactivity of the To summarize, for SN1 reactions, carbocation
nucleophile is enhanced, making it immediately stability increases from primary to secondary then
attack the organic halide without the formation of to tertiary carbocations; therefore, tertiary organic
intermediate products [1]. halides are the most reactive and have the fastest
reaction rate during SN1 reactions, whereas
Table 1. Results of Reaction With a) 2% ethanolic primary organic halides are the least reactive, thus
AgNO3 and b) 15% NaI in anhydrous acetone having a slow reaction rate. On the other hand, for
SN2 reactions, steric repulsion increases from
For the SN1 reactions given by the reaction with primary to secondary then to tertiary organic
2% ethanolic AgNO3, tert-butyl chloride was first halides; therefore, primary organic halides are the
to form a precipitate; hence, it was the most most reactive and have the fastest reaction rate
reactive compound under SN1 conditions. This during SN2 reactions as compared to tertiary
result was in line with how tertiary organic halides organic halides which react slowly and is the least
should be the most reactive with SN1 reactions [3]. reactive. Moreover, aromatic halides are
The white precipitate that formed was silver unreactive with both SN1 and SN2 reactions since
they are already stabilized by pi-electron
Compounds Reaction with Reaction with 15% delocalization or resonance.
2% ethanolic NaI in anhydrous
AgNO3 acetone REFERENCES
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