(To Study hydro halogenation reaction with different mechanism

involved in it )

A PROJECT WORK SUBMITTED FOR THE PARTIAL

FULFILMENT OF THE REQUIREMENT IN CHEMISTRY OF
GRADE 11.

Submitted By:
Bickey Ray kurnmi
Class:11 "B2”
Roll No.:13

Submitted To: .Tirtha Binadi

DEPARTMENT OF CHEMISTRY
NOBEL ACADEMY
NEWBANESHOWR, KATHMANDU, Nepal
April, 2024

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 RECOMMENDATION LETTER

This is to certify that the project work entitled “To study hydro halogenation reaction
with different mechanism involved in it” submitted by Mrs Dipika Chaudhary of
Nobel Academy, New Baneshwor has been prepared under my supervision as a
partial fulfillment for the class 11 of Chemistry course. I, therefore, recommend the
project work report for evaluation.

Tirtha Binadi
………………………..
Name of Supervisor
Department of Chemistry
Nobel Academy, Kathmandu, Nepal.

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 CERTIFICATE OF APPROVAL

This project work entitled “To study hudro halogeation reaction with different
mechanism involved in it.” by Mr. Bickey Ray Kurmi ,Roll no:13 of Nobel Academy,
New Baneshwor Kathmandu prepared under the supervision of Mr …Tirtha
Binadi….. submitted for the partial fulfillment of prerequisite of chemistry of class
11 has been accepted.

Paramatma Mishra. Tirtha Binadi……………….

Head of Department Supervisor
Department of Chemistry Department of chemistry
Nobel Academy, New Baneshwor Nobel Academy, New Baneshwor
Kathmandu,Nepal Kathmandu,Nepal

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 DECLARATION

I hereby declare that the project work entitled “To study hydro halogenation reaction
with different mechanism involved in it.” Submitted to the Department of Chemistry
Nobel Academy, New Baneshwor, Kathmandu is an original piece of work carried out
under the supervision and guidance of Mr .Tirtha Binadi… Department of Chemistry,
New Baneshwor Kathmandu, Nepal and is submitted for the partial fulfillmett of the
requirement for chemistry of grade 11.

Name of student: Bickey ray kurmi

Email: ……………………………..
Grade: 11
Date:2081-02-23

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 ACKNOWLEDGEMENT
I would like to thank Mr .Tirtha Binadi.., my supervisor, for giving me the chance to
develop a project. He/ she gave me a chance to conduct study on the subject, which
will help me learn new information. Along with the principal Mr. Rabin Dahal, the
administration’s top official Mr. Raj Kumar Acharya and especially to our
coordinator, Mr Ravi Kumar Sharma, I want to express my gratitude.

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 Content
Introduction ................................................................................................................... 7
Alkenes:Hydrohalogenation .......................................................................................... 8
Hydrohalogenation—Electrophilic Addition of HX .................................................... 11
Reaction Overview....................................................................................................... 15
Source of information .................................................................................................. 18

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Introduction
Halogenation and hydrohalogenation of unsaturated polymers are of interest because
it can improve heat and chemical resistance and yield precursors for further chemical
transformations. Many halogenation and hydrohalogenation techniques have been
discussed in previous reviews and have focused on noncatalytic methods.2,5,8 The
noncatalytic halogenation of polymers is difficult and complicated owing to the
complex nature of the halogenation mechanism. For example, halogenation of
unsaturated polymers may result in cyclization, cross-linking, and elimination,
substitution, and addition reactions.2,5 Furthermore, control of the regioselectivity of
the electrophilic addition reaction in classical hydrohalogenation is typically limited,
and the reaction yields mostly Markovnikov addition products.
In 2012, Zheng and coworkers demonstrated selective anti-Markovnikov halogenation
of PBD via hydrozirconation followed by halogenation (Fig. 21).60 In this case,
hydrozirconation was conducted using Schwartz's reagent (Cp2ZrHCl) and resulted in
quantitative conversion of PBD terminal alkenes. Halogenation was then carried out
with various sources of cationic halogen, such as N-chloro-, N-bromo-, and N-
iodosuccinimide (NCS, NBS, and NIS, respectively), or molecular iodine. The
halogens (Cl, Br, or I) are incorporated into the pendant groups of PBD in anti-
Markovnikov addition form. It was noted that some unreacted zirconium moieties
remained on the polymer chains after halogenation; however, these zirconiums could
easily be converted to methyl groups by quenching the polymer with deoxygenated
methanol. Unfortunately, some chain scission occurred during the hydrozirconation
process of PBD with 88% vinyl group concentration and was ascribed to β-alkyl
elimination of the hydrozirconated internal C C bond of the backbone. This side
reaction was greatly reduced by using PBD with a higher vinyl group concentration
(98%). The halogenated side chain of PBD was subsequently converted to various
functional groups via reaction with nucleophiles such as amines, imides,
phenols, carbanions, alcohols, carboxylates, azide, and macromolecular nucleophiles,
thereby affording a diverse range of functionalized polymers with controlled
structures.

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Alkenes: Hydrohalogenation

Unlike halogens, hydrogen halides are polarized molecules, which easily form ions.
Hydrogen halides also add to alkenes by electrophilic addition.

The addition of hydrogen halides to asymmetrically substituted alkenes leads to two

products.

The major product is predicted by the Markovnikov rule, which states that when a
hydrogen halide is added to an asymmetrically substituted alkene, the major product
results from the addition of the hydrogen atom to the double‐bonded carbon that is
attached to more hydrogen atoms, while the halide ion adds to the other double‐
bonded carbon. This arrangement creates a more stable carbocation intermediate.

Hydrohalogenation mechanisms. The first step in the addition of a hydrogen halide

to an alkene is the dissociation of the hydrogen halide.

The H + ion is attracted to the π‐bond electrons of the alkene, which forms a π
complex.

The π complex then breaks, creating a σ single bond between one carbon of the
double‐bonded pair and the hydrogen. The carbon atom that loses a share of the π
bond then becomes a carbocation. In asymmetrically substituted alkenes, two different
carbocations are possible. The major product is generated from the more stable
carbocation, while the minor product forms from the less stable one.

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Thus, the major product is 2‐bromopropane.

Hydrogen bromide can also be added to an alkene in an anti‐Markovnikov fashion.

In anti‐Markovnikov additions, the hydrogen atom of the hydrogen halide adds to
the carbon of the double bond that is bonded to fewer hydrogen atoms. For this to
result, the reaction must proceed by a noncarbocation intermediate; thus in the
presence of peroxide, the reaction proceeds via a free‐radical mechanism, with the
major product being generated from the more stable free radical.

The mechanism for this reaction starts with the generation of a bromine free radical
by the reaction of hydrogen bromide with peroxide.

The bromine free radical adds to the alkene, forming a more stable carbon free
radical.

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The secondary free radical is more stable than the primary free radical because the
secondary molecule is better able to delocalize the stress placed on the carbon atom
by the free‐radical electron. The major product then forms from the intermediates by
reacting with hydrogen bromide.

In all additions of hydrogen halides across carbon‐carbon double bonds, the major
product always comes from the more stable intermediate. In Markovnikov additions,
the major product results from the more stable carbocation, while in anti‐
Markovnikov additions, such as the hydrogen bromide addition in the presence of
peroxide, the major product results from the more stable free radical.

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Hydrohalogenation—Electrophilic Addition of HX

This page looks at the reaction of the carbon-carbon double bond in alkenes such as
ethene with hydrogen halides such as hydrogen chloride and hydrogen bromide.

Symmetrical alkenes (like ethene or but-2-ene) are dealt with first. These are alkenes
where identical groups are attached to each end of the carbon-carbon double bond.

Addition to symmetrical alkenes

What happens?

All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom
joins to one of the carbon atoms originally in the double bond, and a halogen atom to
the other.

For example, with ethene and hydrogen chloride, you get chloroethane:

With but-2-ene you get 2-chlorobutane:

What happens if you add the hydrogen to the carbon atom at the right-hand end of the
double bond, and the chlorine to the left-hand end? You would still have the same
product.

The chlorine would be on a carbon atom next to the end of the chain - you would
simply have drawn the molecule flipped over in space.

That would be different of the alkene was unsymmetrical - that's why we have to look
at them separately.

Mechanism

The addition of hydrogen halides is one of the easiest electrophilic addition reactions
because it uses the simplest electrophile: the proton. Hydrogen halides provide both a
electrophile (proton) and a nucleophile (halide). First, the electrophile will attack the
double bond and take up a set of π electrons, attaching it to the molecule (1). This is
basically the reverse of the last step in the E1 reaction (deprotonation step). The
resulting molecule will have a single carbon- carbon bond with a positive charge on
one of them (carbocation). The next step is when the nucleophile (halide) bonds to the
carbocation, producing a new molecule with both the original hydrogen and halide
attached to the organic reactant (2). The second step will only occur if a
good nucleophile is used.
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Mechanism of Electrophilic Addition of Hydrogen Halide to Ethene

Mechanism of Electrophilic Addition of Hydrogen Halide to Propene

All of the halides (HBr, HCl, HI, HF) can participate in this reaction and add on in the
same manner. Although different halides do have different rates of reaction, due to the
H-X bond getting weaker as X gets larger (poor overlap of orbitals)s.

Reaction rates

Variation of rates when you change the halogen

Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen fluoride reacts
much more slowly than the other three, and is normally ignored in talking about these
reactions.

When the hydrogen halides react with alkenes, the hydrogen-halogen bond has to be
broken. The bond strength falls as you go from HF to HI, and the hydrogen-fluorine
bond is particularly strong. Because it is difficult to break the bond between the
hydrogen and the fluorine, the addition of HF is bound to be slow.

Variation of rates when you change the alkene

This applies to unsymmetrical alkenes as well as to symmetrical ones. For simplicity

the examples given below are all symmetrical ones- but they don't have to be.

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Reaction rates increase as the alkene gets more complicated - in the sense of the
number of alkyl groups (such as methyl groups) attached to the carbon atoms at either
end of the double bond.

For example:

There are two ways of looking at the reasons for this - both of which need you to
know about the mechanism for the reactions.

Alkenes react because the electrons in the pi bond attract things with any degree of
positive charge. Anything which increases the electron density around the double
bond will help this.

Alkyl groups have a tendency to "push" electrons away from themselves towards the
double bond. The more alkyl groups you have, the more negative the area around the
double bonds becomes.

The more negatively charged that region becomes, the more it will attract molecules
like hydrogen chloride.

The more important reason, though, lies in the stability of the intermediate ion formed
during the reaction. The three examples given above produce these carbocations
(carbonium ions) at the half-way stage of the reaction:

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The stability of the intermediate ions governs the activation energy for the reaction.
As you go towards the more complicated alkenes, the activation energy for the
reaction falls. That means that the reactions become faster.

Addition to unsymmetrical alkenes

What happens?

In terms of reaction conditions and the factors affecting the rates of the reaction, there
is no difference whatsoever between these alkenes and the symmetrical ones
described above. The problem comes with the orientation of the addition - in other
words, which way around the hydrogen and the halogen add across the double bond.

Orientation of addition

If HCl adds to an unsymmetrical alkene like propene, there are two possible ways it
could add. However, in practice, there is only one major product.

This is in line with Markovnikov's Rule which says:

In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group
has more hydrogens than the CH group.

Notice that only the hydrogens directly attached to the carbon atoms at either end of
the double bond count. The ones in the CH3 group are totally irrelevant

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 Reaction Overview
The hydrohalogenation of alkenes involves breaking a carbon to carbon double bond,
followed by the electrophilic addition of a hydrogen atom and halogen. The halide
will add to the more substituted carbon following Markovnikov's rule. The product is
a haloalkane also called an alkyl halide.

Summary of Hydrohalogenation Mechanism

▪ Nucleophilic pi bond reaches for electrophilic H in H-X, pi bond breaks in the

process
▪ H adds to the less substituted carbon atom following Markovnikov's rule
▪ More substituted carbon is now deficient getting a formal charge of +1
▪ Negative halide in solution attacks the carbocation forming a bond
▪ Product is a haloalkane – also known as alkyl halide

Mechanism Overview and Explanation

(watch my Hydrohalogenation video to see the detailed step-by-step mechanism in

action)

Key Reaction Notes:

▪ This reaction has a carbocation intermediate and therefore follows Markovnikov's

rule
▪ Look out for carbocation rearrangements
▪ This reaction must be carried out in an ‘inert' solvent
▪ This reaction is regioselective – halide adds to more substituted carbon
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Mechanism for hydrohalogenation with a hydride-shift (carbocation
rearrangement)

What's Really Going On In This Reaction?

Hydrohalogenation, an electrophilic alkene addition reaction, is highly useful as a
precursor reaction in multi-step organic chemistry synthesis.

Understanding the Molecules:

H-X molecules such as H-I, H-Br and H-Cl are highly polar molecules. The halogen
is highly electronegative and will ‘hog' the electrons between itself and hydrogen.
This concentration of electrons on the halogen makes it partially negative, while
pulling the electrons away from hydrogen makes H partially positive.

(You will seldom see this reaction for H-F due to fluorine's high electronegativity and
poor reactivity)

Unlike sigma (single) bonding electrons, the pi bond sits very high and very low on
the carbon skeleton. This allows it to be easily ‘distracted' by other nearby molecules.
These electrons are highly nucleophilic (attracted to positive) and will reach out for a
passing electrophile (positive or partially positive).

Breaking The Pi Bond:

When an H-X bond such as H-Cl or H-

Br gets close to the alkene, the pi bonds will reach out to grab the partially positive

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hydrogen atom. In order to form this bond, one of the pi electrons must let go of the
carbon atom that it's bound to.

In deciding which carbon atom we must follow Markovnikov's rule and ask ourselves
which pi bond is more capable of holding a positive charge. The more substituted the
carbon atom, the more stable the resulting carbocation.

The other carbon atom hasn't let go of its pi electrons and is now singly bound to the
hydrogen atom. This is how the less substituted carbon atom winds up bound to
hydrogen.

The hydrogen atom is capable of forming just a single bond. As it forms a bond with
carbon it must let go of the halogen. This allows the halogen to grab the electrons that
used to bind it to hydrogen, and float away in solution with a complete octet and
negative charge.

Attack of the Halide:

Negative halogens are nucleophiles. Nucleophiles are attracted to electrophiles

(positive charges).

The lone halogen will use one of it's lone electron pairs to attack the carbocation
forming a sigma bond. Since the carbocation was on the more substituted carbon, the
halogen winds up attached at the more substituted carbon as well.

Purpose Of Inert Solvent:

The choice of solvent will make a big difference in the overall reaction. Think of your
inert solvents as ‘I don't care' solvents. They serve the single purpose of dissolving the
reactants and reagents, but they don't interfere in the actual process. Inert solvents for
this reaction include CH2Cl2, CCl4 and more. Notice that they are NOT polar protic.

The use of a non-inert solvent or polar protic solvent like water will result in a very
different reaction. At the point where the halide breaks away from hydrogen, the
solvent ‘butts in'. The polar protic solvent will use its partially positive hydrogen
atoms to surround or ‘cage' the negative halogen. This prevents the halogen from
attacking the carbocation. Instead, one of the polar protic solvent molecules will use a
lone pair of electrons to attack the carbocation.

For example, if carried out in water, the final product will be an alcohol. If carried out
in alcohol the product will be an ether.

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 Source of information
⚫ Google

⚫ Chemistry book

⚫ Sj sir note

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