Alkyl Halides

Chapter


Trihalogen Derivatives

The general formula of trihalogen derivative is CHX3
These are also called HALOFORMS.
Preparation
(i) Haloform test is given by compounds having COCH3 group.


CH3COOH cannot give haloform test due to resonance and does not contain pure COCH3 group.
C6H5COC6H5 Benzophenone does not give haloform test due to absence of COCH3 group.









2-alkanol but cannot give haloform test because it is inert towards first
step oxidation.










Acetoacetic ester even though contains COCH3 group but does not
give haloform test due to active methylene group in the molecule
where first halogenation occurs.


The reacting compounds for haloform test are halogen and alkali which are responsible for halogenation, oxidation and hydrolysis.
Reactions involved in haloform test are :
(a) Oxidation (b) Halogenation (3 equivalent) (c) Hydrolysis in presence of base


Halogen and alkali are used as they form OQ Cl or hypohalite ion which is a strong base to replace all 3-H


The haloform reaction
Halogenation of the - carbon atom takes place when an enolate ion is generated in the presence of chlorine, bromine, or iodine
(any halogen).


In the acid-catalyzed halogenation of aldehydes and ketones, rate is independant of the concentration of the halogen; chlorination,
bromination, and iodination all at the same rate. Formation of the enolate is rate-determining, and once formed the enolate ion
reacts rapidly with the halogen but remember three equivalents are required for haloforms.



Unlike its acid-catalyzed route, a-halogenation in base catalysed cannot normally be limited at monohalogenation. Methyl ketones,
for example, undergo polyhalogenation and cleavage on treatment with a halogen in aqueous base.



This is called the haloform reaction because the trihalomethane produced is chloroform, bromoform, or iodoform depending, of
course, on the halogen used. Remember this reaction is done by three equivalent of halogen but if there is only one equivalent of
halogen then mono halo product is formed.
Normally in seperation test of 2-alkanol or 2-alkanone with other alkanol or alkan one we prefer I2 and alkali for test because
formation of yellow ppt of CHI3 takes place.
The mechanism of first phase of the haloform reaction begin with a-halogenation through the enolate. The electron-attracting I
effect of an a-halogen increases the acidity of the protons on the carbon to which it is bonded, making each H active and undergo
halogenation at that carbon faster than the preceding one.











Alkyl Halides

The trihalomethyl ketone (RCOCX3) so formed when undergoes nucleophilic addition reaction of hydroxide ion to its carbonyl
group, and finally its dissociation by cleavage, of the bond to the CX3 group.



The three I effect halogen group stabilize the negative charge of the trihalomethide ion (CX3) converting it to weak conjugate
acid and permitting it to act as a good leaving group in the carbon bond-cleavage step or 2-alkanone.

This reaction is also used for the preparation of carboxylic acid from methyl ketones.



(ii) Haloform test from bleaching powder (CaOCl2)
It is also used as reagent for haloform test due to the presence of OQCl which is a strong base.


(iii) From chloral hydrate


It shows intramolecular H-bonding and is thus stable. This method is used to prepare fresh and pure chloroform.
(iv) Reduction of CCl4


Properties of chloroform
(i) Oxidation



Storage of CHl3
a. It is stored in amber coloured bottles up to the brim in dark.
b. Small amount of ethyl alcohol is added which converts poisonous phosgene into nontoxic compound, diethyl carbonate.



(ii) Testing of Chloroform
a. Pure chloroform does not react with AgNO3 due to absence of Cl ion
b. Impure chloroform or oxidised chloroform gives white ppt with AgNO3 due to presence of HCl which contains Cl
-
ion.

(iii) Reaction with HNO3



(iv) Reaction with acetone
















(v) Reaction with Benzene
Substitution of halogen by phenyl group occurs in the presence of Lewis acids




In case of CCl4 only 3Cl atoms are replaced by phenylgroup, while 4th Cl atom donot undergo replacement by phenyl group
due to high stable intermediate triphenyl methyl carbocation.



(vi) Reaction with aq. KOH
Nucleophilic substitution reaction occurs where Cl is substituted by OH group.




Hoffmann?s Carbylamine Reaction
(vii) Hoffmanns Carbylamine Reaction







When all primary amines reaction with chloroform and alc.
KOH theyform isocyanides with bad smell. It is the most
versatile test for all primary amines. In this a-elimination
occurs.






Mechanism



Separation Tests of some Pairs ?



(viii) Reimer Tiemanns Reaction
Process of formylation of phenols with chloroform in alkaline solution is known as ReimerTiemann reaction.
A mixture of ortho-and para-isomers is obtained in which the ortho isomer predominates due to more thermodynamical stability. If
one of the ortho positions is occupied the para-isomer is the major product.



The reaction is carried out by refluxing an alkaline solution of phenol and chloroform at 60C for sometime (1/2 h). Excess
chloroform is distilled off, the mixture acidified with sulphuric acid and steam distilled. Unreacted phenol and the ortho-isomer
distil over leaving behind the para isomer. The two isomers are further purified by sodium bisulphite.



Applications
The reaction mainly used for introducing aldehyde or carboxyl group in phenols.
(i) Preparation of vanillin



(ii) Preparation of piperonal



(iii) Formylation of heterocyclic compounds



















(v) Preparation of acid (salysylic acid)
When carbon tetrachloride in place of chloroform is used, a carboxyl group is introduced.



(vi) Abnormal ReimerTiemann reaction (where ring expansion takes place due to electrocyclic rearrangement)



1. Pyrrole undergoes normal and abnormal RTR
Normal reaction (pyrrole is ortho & para activating compound).



Abnormal reaction (ring expansion)






Pyrene CCl4

Pyrene CCl4


CCl4 does not react with H2O while SiCl4 reacts due to presence of vacant dorbital in Si atom used by water molecule as
nucleophile. CCl4 at high temperature reacts with H2O where vacant orbital of carbon at high temperature as used by water to form
phosgene.


Freons : Poly chloro fluoro alkanes are known as freons. They are colourless, odourless, non toxic, non inflammable liquids with
very less chemical reactivity & high stability. They are used in refrigerators and air conditioners for cooling purpose and as
propellents in rockets and jets.


Ozone hole
Chloroflorocarbons known as freons, commercially used for refrigeration purpose they are highly volatile and stable in nature (life
time is more than 100 years) due to this they easily move up into the higher zone of atmosphere (stratosphere), and reacts with
ozone causing hole resulting in to as ozone depletion.
Reaction follows free radical mechanism
(i) Chain initiation step


(ii) Chain propagation step



The damage of ozone layer in stratosphere clear the path for harmful ultraviolet radiation to come on earths surface.
Now a days hydroflorocarbons (HFCS) are used as substitutes for CFCS because CFCS are involved in depletion of ozone layer .
Ozone has a tendency to absorb uv rays and works as natural shield from harmful rays.
DIHALOGEN DERIVATIVES


Preparation


Properties
Ethyledene chloride and Ethylene chloride gives reactions with following reagents in almost same pattern by nucleophilic
substitution reaction, for example





Preparation of Mono halogen derivatives (RX)
(i) From alcohol


It is the (Darzons) best method for preparation of halide from alcohol because pyridine forms a complex with HCl. SO2 is
liberated, thus pure RX is obtained. Pyridine behaves as a weak base due to the presence of lone pair of electrons.



















alcohols do not react directly with HCl but react in presence of ZnCl2 because in its presence they form a complex which is
stronger acid than HCl itself.


Alkyl Halides
Order of reactivity of halogen acid HI > HBr > HCl, because acid which give quickly. Proton is maximum reactive while order of
reactivity of alcohol is 3o > 2o >1o > CH3OH due to intermediate carbocation formation where more the stability of intermediate
higher the reactivity.


(iv) From 1 amines with NOCl or Tildens reagent (nitrosyl chloride)


(v) From alkenes


(vi) Halogenation of alkanes


This reaction involves decarboxylation and Bromination both simultaneously. This reaction is used for bromides only. It is used to
prepare lower homologues (to step down) in alkyl halide series.


(viii) Substitution of one halogen by another (Halogen exchange)
In the reaction described in earlier part of this chapter, we have already taken examples of nucleophilic substitutions involving
halide leaving groups. Halide ions may also works as nucleophiles. In a reaction known as halogen exchange, one halogen
displaces another from an alkyl halide.


Since the halide which undergo displacement is also a nucleophile, an equilibrium is established. Synthetic chemistry application is
how to shift the position of equilibrium so as to make this reaction an effective and spontaneous one for the preparation of alkyl
fluorides and alkyl iodides.
In the preparation of alkyl fluorides, an alkyl chloride, bromide, or iodide is heated with potassium fluoride in a high boil ing
alcohol solvent such as propylene glycol.


Alkyl fluorides have the lowest boiling points (Lowest mass) of all the alkyl halides and are removed from the reaction mixture by
distillation as they are formed. According to Le Chateliers principle, the system responds by forming more alkyl fluoride at the
expense of the original alkyl halide. Even if the alkyl fluoride were not removed by distillation, it would predominate at
equilibrium because the reaction favours spontaneity of the stronger C F bond in place of weaker C I, C Br, or C Cl
bonds of low dissociation energy. Since synthetic method for these compounds, this reaction is known as Swarts reaction.

Alkyl iodides may be prepared from alkyl chlorides and bromides by treatment with sodium iodide in acetone as the solvent,
known as (Finkelstein) connent reaction.



Le Chateliers principle under go application in this reaction. Sodium iodide is soluble in acetone due to more covalent nature but
sodium bromide and sodium chloride are not. In these reactions, sodium chloride and sodium bromide precipitate from the react ion
mixture, causing the position of equilibrium to shift in forward direction (activemass is unity for solid) so as to favour formation of
the alkyl iodides.
Physical Properties
(a) Bond strength: In haloalkanes bond strength of carbonhalogen bond decrease with an increase in bond length, as one moves
from fluorine to iodine. This is attributed to the size of p orbital, which increases from fluorine to iodine and thus makes the sp3 -p
overlap less effective.



(b) Solubility and state of matter: Haloalkanes are insoluble in water but soluble in organic solvents. Lower molecular mass
haloalkanes are gases at room temperature while higher molecular mass haloalkanes are liquid at room temperature.



(c) Boiling point: Boiling point of haloalkanes is higher compared to corresponding alkanes due to dipoledipole interaction. With
an increase in molecular mass, there is an increase in boiling point. For the same alkyl group the boiling point increases from
fluoroalkane (RF) to iodoalkane (RI). Iodine has a larger surface area and outer electrons are loosely bound. This makes iodine a
highly polarizable atom. A polarizable atom has increased London forces of attraction (section 1.7), which causes an increase in
boiling point. The branched chain haloalkanes follow a similar increasing order of boiling points.
(d) Density: The densities of haloalkanes increase with atomic mass of the halogen and decrease with increasing size of the alkyl
group. In monohaloalkanes, iodomethane (CH3I) has the maximum density.














The general characteristics of monohaloalkanes can be enumerated as follows:

(a) Fluoro and chloroalkanes are less dense than water whereas bromo and iodoalkanes are denser than water.

(b) Monofluroalkanes are unstable and on heating, HF is eliminated to produce alkene.

(c) Bromo and iodoalkanes are generally photosensitive and are stored in brown opaque bottles. Otherwise, they liberate free
bromine and iodine respectively.

Properties of mono halogen derivatives
Mono halogen derivatives follows nucleophilic substitution reactions which are mainly of S
N
1, S
N
2 type. Reaction follows which type of mechanism is mainly decided by halide quality and medium (solvent). Detail study of
mechanism is given in the next chapter of the book.

















Synthesis of cyanide and Isocyanide
(i) Synthesis of cyanide and Isocyanide





With KCN, halides mainly form cyanides because in KCN molecule ionic bonding occurs which produces CN
-
with ambident
nature where two sites of attachment are there as negative charge and lone pair of electrons. Attachment prefers at carbon si te
because negative charge is more active than pure lone pair. Reaction with AgCN (covalent bonding) produces isoaganides as major
product.










NO2 also works as ambident nucleophile because it has two sites for attachment one is nitrogen lone pair while other is negative
charge on oxygen atom. There is ionic bonding in KNO2 molecule so it produces exclusively alkyl nitrite while with AgNO2
(covalent) attachment prefer from nitrogen site because lone pair of nitrogen is more reactive than lone pair of oxygen.











When primary halides reacts with ammonia to form primary amines as major product but when excess of alkyl halides are taken
than exhaustive alkylation occurs, where synthesis of quaterary ammonium salts takes place. By heating they undergo b-
elimination through Hoffmanns orientation forms less substituted alkenes as major product.





In above cases alkene formation takes place by ethyl group & not by propyl group because bcarbon of propyl is 2 in nature &
abstraction of proton order in case of Hoffmanns beliminations is 1>2>3 carbon atom otherwise CH2NO2 > CH2Cl > 1. If
any I effect group is present on b carbon it increases the reactivity for elimination from that site.





Other chemical reaction mainly follows E-1 or E-2 reaction for elimination (dehydration and dehydrohalogenation) where sytzeffs
rule for stabilization occurs for example.





(iv) Some other synthetic methods from alkyl halide