You are on page 1of 14

International Journal of Chemical

& Petrochemical Technology (IJCPT)
ISSN(P): 2277-4807; ISSN(E): 2319-4464
Vol. 5, Issue 3, Oct 2015, 9-22
© TJPRC Pvt. Ltd.

SURVEY ON ALKYL HALIDE COMPOUNDS
NAGHAM MAHMOOD ALJAMALI
Organic Chemistry,
Chemistry Chemistry Department, College of Education,, Iraq

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".

KEYWORDS: Reaction, Synthesis, Bromide,
Bromide Iodide, Alkyl Halide, E1, E2, SN1, SN2
INTRODUCTION
Synthetic organic halogen compounds are readily available by direct halogenation of hydrocarbons and by
addition reactions to alkenes and alkynes. Many of these have proven useful as intermediates in traditional synthetic
processes.
Nomenclature of Alkyl Halide
It should follow IUPAC nomenclature,
nomenclature which put the halogen as a prefix to the alkane. For example, ethane with
bromine becomes bromo ethane, methane with four chlorine groups becomes tetrachloromethane.
tetrachloromethane However, many of these
compounds have already an established trivial name, which is endorsed by the IUPAC nomenclature, for
example chloroform (trichloromethane) and methylene chloride (dichloromethane).
(
Examples

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.

www.tjprc.org

editor@tjprc.org

10

Nagham Mahmood Aljamali

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.

Impact Factor (JCC): 3.5367

Index Copernicus
Cope
Value (ICV): 3.0

11

Survey on Alkyl Halide Compounds

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

By Reaction of Alcohols: with thionyl chloride or with phosphoryl chloride

www.tjprc.org

editor@tjprc.org

12

Nagham Mahmood Aljamali

Figure 9

By Addition HX: to double or trible bond :

Figure 10

By Reaction of HX with N- Bromo Succinamide

Figure 11
Alkyl Halide Reaction

Figure 12

Figure 13
Impact Factor (JCC): 3.5367

Index Copernicus
Cope
Value (ICV): 3.0

13

Survey on Alkyl Halide Compounds

Figure 14

Figure 15

Figure 16

Figure 17

www.tjprc.org

editor@tjprc.org

14

Nagham Mahmood Aljamali

Figure 18

Figure 19

Figure 20

Impact Factor (JCC): 3.5367

Index Copernicus
Cope
Value (ICV): 3.0

15

Survey on Alkyl Halide Compounds

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:(–
)

reactants vary as shown in the following

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

www.tjprc.org

editor@tjprc.org

16

Nagham Mahmood Aljamali

The E2 Reaction
We have not yet considered the factors that influence elimination reactions, such as example 3 in the group

presented at the beginning of this section.
(CH3)3C-Br + CN(–) ——> (CH3)2C=CH2 + Br(–) + HCN
We know that t-butyl
butyl bromide is not expected to react by an SN2 mechanism. Furthermore, the ethanol solvent is
not sufficiently polar to facilitate an SN1 reaction. The other reactant, cyanide anion, is a good nucleophile; and it is also a
decent base, being about ten times weaker than bicarbonate. Consequently, a base-induced
base induced elimination seems to be the only
plausible reaction remaining for this combination
combination of reactants. To get a clearer picture of the interplay of these factors
consider the reaction of a 2º-alkyl
alkyl halide, isopropyl bromide, with
with two different nucleophiles.
SN1 and SN2 Mechanism
Where the rate-determining
determining step of a nucleophilic substitution reaction is unimolecular, it is known as an SN1
reaction.. In this case, the slowest (thus rate-determining
rate determining step) is the heterolysis of a carbon-halogen
carbon
bond to give a
carbocation and the halide anion. The nucleophile (electron donor) attacks the carbocation to give the product.
SN1 reactions are associated with the racemization of the compound, as the trigonal planar carbocation may be
attacked from either face. They are favored mechanism for tertiary haloalkanes, due to the stabilization of the positive
charge on the carbocation by three electron-donating
electron
alkyl groups. They are also preferred where the substituents are
sterically bulky, hindering the SN2 mechanism

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

Survey on Alkyl Halide Compounds

Examples

Figure 25

Figure 26

Table 1
Nucleophile

Alkyl Group

Primary
RCH2–

Secondary
R2CH–

Tertiary
R3C–

www.tjprc.org

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 β-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
β-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

Rapid SN2 substitution. E2
elimination may also occur.
e.g. ClCH2CH2Cl + KOH
——> CH2=CHCl

SN2 substitution. (N ≈ S >>O)

E2 elimination will
dominate.

SN2 substitution. (N ≈ S >>O)
In high dielectric ionizing
solvents, such as water,
dimethyl sulfoxide &
acetonitrile, SN1 and E1
products may be formed
slowly.

E2 elimination will
dominate. No SN2
substitution will occur. In
high dielectric ionizing
solvents SN1 and E1
products may be formed.

E2 elimination with nitrogen
nucleophiles (they are bases).
No SN2 substitution. In high
dielectric ionizing solvents
SN1 and E1 products may be
formed.

editor@tjprc.org

18

Nagham Mahmood Aljamali

Table 1: Contd.,

Allyl
H2C=CHCH2–

Rapid SN2 substitution for
1º and 2º-halides. For 3ºhalides a very slow SN2
substitution or, if the
nucleophile is moderately
basic, E2 elimination. In
high dielectric ionizing
solvents, such as water,
dimethyl sulfoxide &
acetonitrile, SN1 and E1
products may be observed.

Rapid SN2 substitution for
1º halides. E2 elimination
will compete with
substitution in 2º-halides,
and dominate in the case of
3º-halides. In high
dielectric ionizing solvents
SN1 and E1 products may
be formed.

Benzyl
C6H5CH2–

Rapid SN2 substitution for
1º and 2º-halides. For 3ºhalides a very slow SN2
substitution or, if the
nucleophile is moderately
basic, E2 elimination. In
high dielectric ionizing
solvents, such as water,
dimethyl sulfoxide &
acetonitrile, SN1 and E1
products may be observed.

Rapid SN2 substitution for
1º halides (note there are no
β hydrogens). E2
elimination will compete
with substitution in 2ºhalides, and dominate in
the case of 3º-halides. In
high dielectric ionizing
solvents SN1 and E1
products may be formed.

Nitrogen and sulfur
nucleophiles will give SN2
substitution in the case of 1º
and 2º-halides. 3º-halides will
probably give E2 elimination
with nitrogen nucleophiles
(they are bases). In high
dielectric ionizing solvents
SN1 and E1 products may be
formed. Water hydrolysis will
be favorable for 2º & 3ºhalides.
Nitrogen and sulfur
nucleophiles will give SN2
substitution in the case of 1º
and 2º-halides. 3º-halides will
probably give E2 elimination
with nitrogen nucleophiles
(they are bases). In high
dielectric ionizing solvents
SN1 and E1 products may be
formed. Water hydrolysis will
be favorable for 2º & 3ºhalides.

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).

Impact Factor (JCC): 3.5367

Index Copernicus Value (ICV): 3.0

19

Survey on Alkyl Halide Compounds

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.

Secondary halides can react in all ways (hard to predict).

High temperatures favor elimination.

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:
R−X + OH−→R−OH + 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
-

I

-

Observation
white precipitate
very pale cream precipitate
very pale yellow precipitate

Comparing the Reaction Rates (Type of Halogen)
You would have to keep the type of halogenoalkane (primary, secondary or tertiary) constant, but vary the
halogen. You might, for example, compare the times taken to produce a precipitate from this series of primary
halogenoalkanes:

www.tjprc.org

editor@tjprc.org

20

Nagham Mahmood Aljamali

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 iodo compound produces a precipitate quite quickly.

A primary bromo compound takes longer to give a precipitate.

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:

Impact Factor (JCC): 3.5367

Index Copernicus Value (ICV): 3.0

21

Survey on Alkyl Halide Compounds

The tertiary halide produces a precipitate almost instantly.

The secondary halide gives a slight precipitate after a few seconds. The precipitate thickens up with time.

The primary halide may take considerably longer to produce a precipitate.
It is more difficult to explain the reason for this, because it needs a fairly intimate knowledge of the mechanisms

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.

S . George ., ''Organic Chemistry" Mosby-Year Book . 1995, Chp.14, p. 589-649 (1995).

2.

P. Sykes ; "Agide Book to Mechanism in Oaganic Chemistry'', 5th Ed ., Longman, (1974) .

3.

R . E . Brewster, W. E. McEwen ; ''Organic Chemistry", Ch . 30ed Ed ., p.638, (1971) .

4.

B.A. Marry ; "Organic Reaction Mechanism", Ch . 1, Jon Willey sons,(2005)

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.

Nagham M Aljamali ., As. J. Rech., 2014, 7,9, 810-838.

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.

Nagham M Aljamali ., As. J. Rech., 2014, 7,11.

10. Nagham M Aljamali., Int. J. Curr.Res.Chem.Pharma.Sci. 1(9): (2014):121–151.
11. Nagham M Aljamali., Int. J. Curr.Res.Chem.Pharma.Sci. 1(9): (2014):88- 120.
12. Y. Ju, D. Kumar, R. S. Varma, J. Org. Chem., 2006, 71, 6697-6700.
13. N. Iranpoor, H. Firouzabadi, B. Akhlaghinia, R. Azadi, Synthesis, 2004, 92-96.
14. Y. Liu, Y. Xu, S. H. Jung, J. Chae, Synlett, 2012, 2663-2666.
15. D. S. Bhalerao, K. G. Agamanchi, Synlett, 2007, 2952-2956.
16. Louis D. Quin and Tohn A. Tyrell, ''Fundamentals of Heterocyclic Chemistry'' 9th Ed.,Wiley, New York, (2010)
17. Paula YurkanisBruice, ''Organic Chemistry '', 6th Ed., publishing as prentice hall, (2011) .
18. TheophilEicher and Siegfried Hauptmann, ''The Chemistry Of Heterocycles'' 2nd Ed., Wiley, (2003) .
19. Julio AlVarez–Builla, Juan Jose Vaquero and Jose Barluenga, "Moderen Heterocyclic Chemistry", Wiley, (2011)
.

www.tjprc.org

editor@tjprc.org