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ABSTRACT
In this survey study, explanation about halide alkyl compounds, reactions, preparations, nomenclature, examples
has been done. Examining all the reagents that could affect the rate gives us the composition of the reacting "activated
complex" at the transition state. Then we explained the transformation of starting material into products as a series of
discrete steps, each of whichh produces a distinct intermediate compound or ion, called an "intermediate".
Figure 1
Alkyl halides are formally derived from alkanes by exchanging hydrogen for halogen (fluorine, chlorine, bromine,
and iodine). Depending on the degree of substitution at the carbon atom carrying the halogen, alkyl halides are classified
into primary, secondary
ary and tertiary alkyl halides.
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Figure 2
Primary, secondary and tertiary
tiary alkyl halides (X = F, Cl, Br, or I)
Figure 3
Different Representations of Vinyl Iodide
Io
Figure 4
Figure 5
Properties of Alkyl Halide
The alkyl halides are at best only slightly soluble in water. For a halogenoalkane to dissolve in water you have to
break attractions between the halogenoalkane molecules (van der Waals dispersion and dipole-dipole
dipole
interactions) and
break the hydrogen bonds between water molecules. Both of these cost energy.
Index Copernicus
Cope
Value (ICV): 3.0
11
Energy is released when new attractions are set up between the halogenoalkane and the water molecules. These
will only be dispersion forces and dipole-dipole
dipole
interactions. These aren't as strong as the original hydrogen bonds in the
water, and so not as much energy is released as was used to separate the water molecules. The energetics of the change are
sufficiently "unprofitable" that very little dissolves.
Primary Alkyl Halides
In a primary (1) halogenoalkane, the carbon which carries the halogen atom is only attached to one other alkyl
group.Some examples of primary alkyl halides include:
Figure 6
Notice that it doesn't matter how complicated the attached alkyl group is. In each case there is only one linkage to
an alkyl group from the CH2 group holding the halogen. There is an exception to this: CH3Br and the other methyl halides
are often counted as primary alkyl halides even though there are no alkyl groups attached to the carbon with the halogen on
it.
Secondary Alkyl Halides
In a secondary (2) halogenoalkane, the carbon with the halogen attached is joined directly to two other alkyl
groups, which may be the same or different. Examples:
Figure 7
Tertiary Alkyl Halides
In a tertiary (3) halogenoalkane, the carbon atom holding the halogen is attached directly to three alkyl groups,
which may be any combination of same or different. Examples:
Figure 8
Preparation of Alkyl Halide
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Figure 9
Figure 10
Figure 11
Alkyl Halide Reaction
Figure 12
Figure 13
Impact Factor (JCC): 3.5367
Index Copernicus
Cope
Value (ICV): 3.0
13
Figure 14
Figure 15
Figure 16
Figure 17
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Figure 18
Figure 19
Figure 20
Index Copernicus
Cope
Value (ICV): 3.0
15
Examples
Figure 21
Figure 22
Electrophile: An electron deficient atom, ion or molecule that has an affinity for an electron pair, and will bond to
a base or nucleophile.
Nucleophile: An atom, ion or molecule that has an electron pair that may be donated in forming a covalent bond
to an electrophile (or Lewis acid).
If we use a common alkyl halide, such as methyl bromide, and a common solvent, ethanol, we can examine the
rate at which various nucleophiles substitute the methyl carbon. Nucleophilicity is thereby related to the relative rate of
substitution reactions at the halogen-bearing carbon atom of the reference alkyl halide. The most reactive nucleophiles are
said to be more nucleophilic than less reactive members of the group. The nucleophilicities of some common Nu:(
)
Nucleophilicity
CH3CO2() < Cl() < Br() < N3() < CH3O() < CN() SCN() < I() < CH3S()
E1 and E2 Mechanism
A molecule with the halogen substituted with something else, one can completely eliminate both the halogen and
a nearby hydrogen, thus forming an alkene by dehydrohalogenation. For example, with bromoethane and sodium
hydroxide (NaOH) in ethanol, the hydroxide ion HO abstracts a hydrogen atom. Bromide ion is then lost, resulting
in ethylene, H2O and NaBr. Thus, haloalkanes can be converted to alkenes
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The E2 Reaction
We have not yet considered the factors that influence elimination reactions, such as example 3 in the group
As the number of substituents around the carbon centre undergoing reaction increases, the substituents block the
approach of the incoming nucleophile and consequently an SN2 mechanism becomes less favourable.
Figure 23
In the case of a tertiary alkyl halide, loss of the halide occurs first to give a carbocation which then reacts with the
nucleophile. This is called a SN1 reaction (Substitution,
(
Nucleophilic, first order).
Figure 24
Impact Factor (JCC): 3.5367
Index Copernicus
Cope
Value (ICV): 3.0
17
Examples
Figure 25
Figure 26
Table 1
Nucleophile
Alkyl Group
Primary
RCH2
Secondary
R2CH
Tertiary
R3C
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Anionic Nucleophiles
(Weak Bases: I, Br,
SCN, N3,
CH3CO2, RS, CN etc. )
pKa's from -9 to 10 (left to
right)
Rapid SN2 substitution. The
rate may be reduced by
substitution of -carbons,
as in the case of neopentyl.
SN2 substitution and / or E2
elimination (depending on
the basicity of the
nucleophile). Bases weaker
than acetate (pKa = 4.8)
give less elimination. The
rate of substitution may be
reduced by branching at the
-carbons, and this will
increase elimination.
E2 elimination will
dominate with most
nucleophiles (even if they
are weak bases). No SN2
substitution due to steric
hindrance. In high
dielectric ionizing solvents,
such as water, dimethyl
sulfoxide & acetonitrile,
SN1 and E1 products may
be expected.
Anionic Nucleophiles (
Strong Bases: HO, RO)
pKa's > 15
Neutral Nucleophiles
( H2O, ROH, RSH, R3N )
pKa's ranging from -2 to 11
E2 elimination will
dominate.
E2 elimination will
dominate. No SN2
substitution will occur. In
high dielectric ionizing
solvents SN1 and E1
products may be formed.
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Table 1: Contd.,
Allyl
H2C=CHCH2
Benzyl
C6H5CH2
In General
Figure 27
Figure 28
Substitution versus Elimination Guidelines
The strength of a base or nucleophile will dictate the order of a reaction. (Strong bases/nucleophiles will react
more quickly and create 2nd order kinetics).
19
Primary halides usually undergo SN2 with good nucleophiles. Also watch for rearrangements to more stable
cations if ionization is possible.
Tertiary halides usually do not undergo SN2 reactions. More likely to undergo E2 with a good base, or E1 and
SN1 otherwise.
The nucleophile/base will usually favor one or the other type of reaction. (t-butoxide favors elimination, bromide
and iodide favor substitution).
Figure 29
Identification Test of Halides
The halogenoalkane is warmed with some sodium hydroxide solution in a mixture of ethanol and water.
Everything will dissolve in this mixture and so you can get a good reaction. The halogen atom is displaced as a halide ion:
RX + OHROH + X
With X is any haligen atom.
There is no need to make this reaction go to completion. The silver nitrate test is sensitive enough to detect fairly
small concentrations of halide ions. The mixture is acidified by adding dilute nitric acid. This prevents unreacted hydroxide
ions reacting with the silver ions. Then silver nitrate solution is added. Various precipitates may be formed from the
reaction between the silver and halide ions:
Table 2
Ion
Present
ClBr
-
Observation
white precipitate
very pale cream precipitate
very pale yellow precipitate
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Figure 30
Obviously, the time taken for a precipitate of silver halide to appear will depend on how much of everything you
use and the temperature at which the reaction is carried out. But the pattern of results is always the same. For example:
A primary chloro compound probably won't give any precipitate until well after you have lost interest in the
whole thing!
The order of reactivity reflects the strengths of the carbon-halogen bonds. The carbon-iodine bond is the weakest
and the carbon-chlorine the strongest of the three bonds. In order for a halide ion to be produced, the carbon-halogen bond
has to be broken. The weaker the bond, the easier that is.
If you have looked at the mechanisms for these reactions, you will know that a lone pair on a water molecule
attacks the slightly positive carbon atom attached to the halogen. It is slightly positive because most of the halogens are
more electronegative than carbon, and so pull electrons away from the carbon.
It is tempting to think that the reaction will be faster if the electronegativity difference is greater. The slight
positive charge on the carbon will be larger if it is attached to a chlorine atom than to an iodine atom.
That means that there will be more attraction between a lone pair on the water and a carbon atom attached to a
chlorine atom than if it was attached to an iodine atom. The electro negativity difference between carbon and iodine is
negligible.
However, the fastest reaction is with an iodoalkane. In these reactions, bond strength is the main factor deciding
the relative rates of reaction.
Comparing the Reaction Rates of( Primary, Secondary and Tertiary Alkyl Halide)
You would need to keep the halogen atom constant. It is common to use bromides because they have moderate
reaction rates. You could, for example, compare the reactivity of these compounds:
Figure 31
Again, the actual times taken will vary with reaction conditions, but the pattern will always be the same. For
example:
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The secondary halide gives a slight precipitate after a few seconds. The precipitate thickens up with time.
involved in the reactions. It reflects the change in the way that the halide ion is produced as you go from primary to
secondary to tertiary halogenoalkanes.
REFERENCES
1.
2.
3.
4.
5.
L.F. Fieser and K.L. Eilliamson, ''Organic Experiment" 5th Ed ., DC . Heath and company Toronto, Canada, p.
270 . (1983) .
6.
F. A.Carey and R. J. Sundberg "Advanced Organic Chemistry" part A:strures and Mechanisms, 2nded ., Plenum
Press. New York, p. 243, (1983).
7.
8.
C.O.Wilson and O. Givold, "Text book of Organic Medicinal and pharmaceutical Chemistry", 5th Ed ., Pitman
Medical Publishing Co. LTD, London coppy right. Cby. J. B. LippinCott Company (1966) .
9.
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