Classification Tests for Organic Halides Based on S

N
Reactivity and
Identification of Organic Halides Using Beilstein Test
Authors: *Corpuz, Khrisna Dasha S.; Chua, Holiday O.; Coning, Jumel D.;
Elmubarak, Fatima S.; Encabo, Jana Q.; Flores, Lyka J.
Group No. 3
Abstract:
Organic halides are organic compounds containing a halogen atom bonded to a
carbon atom. Most organic halides are synthetic and not flammable. This experiment
was conducted to differentiate primary, secondary, and tertiary organic halides based
on their S
N
reactivity and to differentiate S
N
1 and S
N
2 mechanisms with organic halides.
The samples used were n-butyl chloride, sec-butyl chloride, tert-butyl chloride, and
chlorobenzene. For detecting the presence of halides in the sample, the Beilstein test,
also known as the Copper halide test, was conducted. This test resulted to all the
samples producing a blue-green flame upon heating the copper wire containing the
samples. In determining the S
N
1 reactivity of the samples, the samples were made to
react with 2% ethanolic silver nitrate. As observed, all the samples produced a white
precipitate except for chlorobenzene. This was because chlorobenzene is already
stabilized by resonance. Among all the samples that produced a precipitate with the
addition of the 2% ethanolic silver nitrate, tert-butyl chloride was the fastest while n-
butyl chloride was the slowest, showing that during S
N
1 reactions, tertiary halides are
most favored. In determining the S
N
2 reactivity of the samples, the samples were made
to react with 15% sodium iodide in anhydrous acetone. As a result, all the samples
produced a white precipitate except for chlorobenzene due to the strong resonance
within its structure. Among all the samples that produced a precipitate, n-butyl chloride
was the fastest while tert-butyl chloride was the slowest, showing that in S
N
2 reactions,
primary substrates are most favored.
Introduction:
Organic halides are organic
compounds containing a halogen atom
bonded to a carbon atom, known as the
alpha carbon. The alpha carbon can be
classified as primary, secondary, or
tertiary depending on the number of
alkyl group attached to it. The organic
halide is primary if an alkyl group is
attached to the alpha carbon. The
compound is secondary if two alkyl
groups are attached to the alpha
carbon, and tertiary if three groups are
attached to the alpha carbon
[1]
.
Organic halides can easily be
prepared from other compounds, such
as alcohols and alkenes. In turn, they
are the starting materials for the
synthesis of a large number of new
functional groups
[1]
. The syntheses are
often carried out by nucleophilic
substitution reactions in which the
halide is replaced by another group
[1]
.
Nucleophilic substitution is any reaction
in which one nucleophile is substituted
for another
[2]
. A carbocation is often
formed as a reactive intermediate in
these reactions. The structure of a
carbocation is trigonal-planar with a
vacant p-orbital and is sp
2
hybridized
[1]
.
The alkyl groups stabilize the positive
charge of the carbocation by displacing
or releasing electrons toward the
positive charge. The stabilization
increases as the number of alkyl groups
attached to the carbocation increases
[1]
.
Substitution reactions can occur
in one smooth step or it can occur in
two discrete steps, depending primarily
on the structure of the R group
[1]
. In a
smooth one-step reaction, the
nucleophile must collide with the alkyl
halide. This reaction is dependent on
the concentration of both the
nucleophile and the halide. Such
reaction is said to be a bimolecular
nucleophilic substitution reaction, S
N
2
[1]
. This type of substitution reaction is
classified as bimolecular because both
the haloalkane and the nucleophile are
involved in the rate-determining step
[2]
.
S
N
2 reaction occurs with Walden
inversion of configuration to give a
product of the opposite chirality from
the starting material
[1]
.

Figure 1: This figure shows inversion of
a compound in an S
N
2 reaction, which
inverts the R-S configuration of the
compound.
In a two-step process, the rate of
the slow step depends only on the
concentration of the halide and is said
to be unimolecular nucleophilic
substitution reaction, S
N
1
[1]
. In this
reaction bond breaking between carbon
and the leaving group is completed
before bond forming with the
nucleophile begins
[2]
. S
N
1 reactions
proceed through a planar carbocation
and occurs with racemization of
configuration. Racemization is the
process by which the product is a 50:50
mixture of enantiomers because the
planar intermediate can form a bond
with the nucleophile on either face
[1]
.

Figure 2: The figure shows the
formation of two enantiomers from the
chiral alkyl halide, known as
racemization.
There are different factors
concerning S
N
reactivity. S
N
1 reactions
are governed mainly by electronic
factors
[2]
. This means that the primary
factor in the order of reactivity in S
N
1
reactions is the relative stability of the
carbocation that is formed
[1]
. Tertiary
halides are most favored by this reaction
due to the stability of their carbocation.
S
N
2 reactions, by contrast, are governed
mainly by steric factors
[2]
. This means
that primary and secondary halides are
most favored in this reaction because of
the ease by which the nucleophile can
come within bonding distance of the
alkyl halide; tertiary halides are usually
not reactive due to the steric hindrance
[1]
.
Relative nucleophilicity also plays
an important role in S
N
reactions. It is
defined as the relative rates at which a
nucleophile reacts in a reference
nucleophilic substitution reaction
[2]
. The
strength of a nucleophile, an atom that
donates a pair of electrons, can easily
differentiate between S
N
1 and S
N
2
reactions. S
N
2 reactions occur in smooth
one-step reactions, therefore, a strong
nucleophile is needed to attack the
halogen. The better or stronger the
nucleophile, the more likely it is that the
reaction will occur by an S
N
2 reaction
[2]
.
Thus, an S
N
1 reaction can, in principle,
occur at approximately the same rate
with any of the common nucleophiles,
regardless of their relative
nucleophilicities
[2]
.
Solvents provide the medium in
which reactants are dissolved and in
which nucleophilic substitution reactions
take place
[2]
. The solvents for these
reactions are divided into protic and
aprotic. If the solvent is polar and protic
(a hydrogen bond donor solvent), S
N
1
reaction will react much faster because
the solvent stabilizes the carbocation
intermediate by solvation thereby
increasing the reaction rate
[2]
. Since the
hydrogen atom in a polar protic solvent
is highly positively charged, it can
interact with the anionic nucleophile
which would negatively affect an S
N
2
reaction, so a solvent that is polar and
aprotic (solvent that cannot serve as a
hydrogen bond donor) is needed for S
N
2
reactions to occur much faster
[3]
.
The rate of S
N
1 and S
N
2 reactions
also depend on the leaving group. The
ability of a group to function as a
leaving group is related to how stable it
is as an anion
[2]
. Weak bases are
usually the most stable anions and the
best leaving groups because they can
hold the charge
[3]
. Among the
halogens, the iodide ion is the best
leaving group, followed by bromide and
lastly chloride; fluorines
electronegativity affects its ability of
becoming a good leaving group. The
hydroxide ion, methoxide ion, and
amide ion are such poor leaving groups
that they are rarely displace in
nucleophilic aliphatic substitution
reactions
[2]
. S
N
2 reactions are usually
associated with the best leaving groups
since they occur in one step reactions.
In contrast, S
N
1 reactions are more
associated with the weaker leaving
groups since they occur in a slower two-
step reaction.
Included in the experiment is a
qualitative test called the Beilstein
Test. It tests organic compounds that
contain halogens namely chlorine,
bromine or iodine
[4]
. Hydrogen
decomposes on ignition in the presence
of copper oxide to yield the
corresponding hydrogen halides. These
hydrogen halides react to form the
voltaic cupric halides that impart a
green or blue-green color to a
nonluminous flame.

Figure 3: The figure above shows the
general reactions involved in the
Beilstein Test in which CuX
2
reacts with
the flame to produce a green or blue-
green color.
Objectives:
The objectives of this experiment
includes differentiating between
primary, secondary, and tertiary organic
halides based on their S
N
reactivity, and
also to differentiate between S
N
1 and
S
N
2 as reactive mechanisms with
organic halides.
Materials and Methodology
The materials that were needed
in this experiment were test tubes,
matches, copper wire, burner, calibrated
droppers and test tube holder and rack.
Copper oxide was also used in the
Beilstein test. The reagents that were
used were 2% ethanolic AgNO3 and
15% NaI in anhydrous acetone while
the sample compounds used were n-
butyl chloride, sec-butyl chloride, tert-
butyl chloride, and chlorobenzene.
In the Beilstein test, copper wires
with a small loop with one end were
needed. The loop of each copper wire
was heated directly in the oxidizing zone
of a non-luminous flame until the green
color imparted to the flame disappears.
While the loop was still hot it was
dipped in some copper oxide powder
and was reheated until the oxide
adhered to the loop (this step is
optional). Then the loop of the copper
wire was cooled slightly and was dipped
into the solid or liquid sample. The loop
with the sample was heated in a non-
luminous flame: first in the inner zone,
then in the outer zone near the edge of
the flame. If the flame was blue to
green in color, it indicated the presence
of a halide.
In the S
N
1 reactivity, 20 drops of
2% ethanolic AgNO3 was placed in a
test tube. Then 5 drops of the sample
was added. The test tube was shaken
and the time (in seconds or minutes) for
a silver halide precipitate to form was
recorded. This process was repeated
using the remaining sample compounds.
In S
N
2 reactivity, 2 drops of 15%
NaI in anhydrous acetone was placed in
a dry test tube. Then 5 drops of the
sample was added. The contents of the
test tube were mixed and the time (in
seconds or in minutes) required for a
precipitate to form and also the color of
the precipitate was noted. This process
was repeated using the remaining
sample compounds.
Results:
Table 1. This table presents the
condensed structural formula of the
given sample compounds.
Compounds Studied: Condensed
Structural
Formula:
n-butyl chloride CH
3
CH
2
CH
2
CH
2
Cl
sec-butyl chloride

tert-butyl chloride

Chlorobenzene

Table 2. This table represents the
results of the Beilstein Test.
Compounds Studied: Beilstein Test:
n-butyl chloride
Blue-Green
Flame
sec-butyl chloride
Blue-Green
Flame
tert-butyl chloride
Blue-Green
Flame
Chlorobenzene
Blue-Green
Flame

Table 3. This table presents the results
of the S
N
1 and S
N
2 reactivity Tests.
Compounds
Studied:
Rxn w/
2%
Ethanolic
AgNO
3
:
Rxn w/
15% NaI
in
Anhydrous
Acetone:
n-butyl chloride
3
rd
: 50
secs
Cloudy
1
st
: 1 sec
White ppt.
Soln
sec-butyl
chloride
2
nd
: 20
secs
Cloudy
Soln
2
nd
: 2 secs
White ppt.
tert-butyl
chloride
1
st
: 2 secs
Cloudy
Susp.
3
rd
: 2.5
secs
White ppt.
Chlorobenzene
2.63 secs
White ppt.
2.25 secs
White ppt.

Figure 4: The picture shows a blue-
green flame, a positive result of the
Beilstein Test.
Discussion:
The Beilstein test, reaction with
ethanolic silver nitrate and reaction with
sodium iodide in anhydrous acetone
were performed for the organic
compounds to be classified accordingly.
In the Beilstein test, all of the
samples, namely n-butyl chloride, sec-
butyl chloride, tert-butyl chloride and
chlorobenzene produced a blue-green
flame. The Beilstein test checks for the
presence of a halogen and all of the
compounds contain a chloride ion,
resulting in a positive result
[4]
.
Organic halides that undergo S
N
1
substitution reaction react with alcoholic
silver nitrate to form a white precipitate
of the corresponding silver halide
[3]
.
The solvent used is polar and protic,
which stabilizes the transition state
more than it does the reactants,
lowering the energy of activation for the
reaction and thus, increasing the
reaction rate
[1]
. All the sample reacted
with the alcoholic silver nitrate except
chlorobenzene. The formation of a white
precipitate was not due to nucleophilic
substitution reaction but it is because
chlorobenzene is insoluble in the given
solvent
[4]
. Chlorobenzene is not reactive
towards nucleophilic substitution
reaction because of its aromacity; its
resonance gives stability to the
compound, which would not react
unless used with a catalyst. Tertiary
chloride reacted with the reagent
immediately. The primary factor in the
order of reactivity in S
N
1 reaction is the
relative stability of the carbocation that
is formed. The carbocation formed by
tertiary chloride is the most stable out of
all of the compounds, therefore it
reacted the fastest. Sec-butyl chloride
and n-butyl chloride reacted very slowly,
only proving further that the more
stable the carbocation intermediate, the
faster the rate of S
N
1 reaction.
Primary alkyl halides can be
distinguished from aryl and alkenyl
halides by reaction with sodium iodide in
acetone
[3]
. S
N
2 substitution reaction
reacts with solvents that are polar and
aprotic such as acetone used in the
sodium iodide anhydrous acetone
reaction, increasing the reaction rate.
Amongst the four compounds, n-butyl
chloride reacted the fastest. The
structure of primary halides like n-butyl
chloride allows for an easy attack of the
nucleophile. In S
N
2 reactivity, the
primary factor in the order of reactivity
is steric hindrance, therefore tert-butyl
chloride resulted with the least reactivity
with sodium iodide in acetone due to its
structure, which hinders the nucleophilic
attack of the alpha carbon from the
backside. Chlorobenzene showed a false
positive result due to its insolubility in
the given solvent. Chlorobenzene does
not react in S
N
2 reactions due to its
bulky ring, which hinders the attack of
the nucleophile.
In conducting the experiment,
there were a few sources of error. First,
the glassware that were used during the
experiment could have contained other
substances like contaminants,
contributing to wrong results. Also, the
reagents that were used needed to be
completely clear liquids, otherwise,
turbidity of the solution could have
given false positive results in testing S
N
1
and S
N
2 reactions. Lastly, the droppers
could have contained water, a polar and
protic solvent, which could have
intervened in the conduction of S
N
2
reactions, a reaction favoring polar and
aprotic solvents.
References: