Selected topics in chemistry

Submitted by: 14035

Submitted on: 15th April, 2020
Department: applied chemistry
Semester: 4th (morning)
Programme: Bs honors
GC UNIVERSITY FASILABAD
Question no. 1: [part -a]:

How molecular structure determines its reactivity patterns. Explain structure-reactivity relationship with
different suitable examples.

Answer: A change in structural corresponds to a chemical reaction. Reactivity is the term we use to
describe the potential of a structure to undergo chemical change. Some structures are more trending to
react with than others. Structures that are likely to undergo chemical change are said to be reactive.
Structures that are resistance to chemical change are said to be unreactive. We sometimes choose to speak
about the complementary property known as stability. Structures that are highly reactive are generally
unstable. Structures that are unreactive are generally stable. We want to view molecular structure from
the perspective of potential to undergo chemical change. A goal is to establish trends that will allow you to
examine a structure and make predictions about its chemical characteristics. Just like a physician diagnoses
patients, chemists learn to associate certain features of structure with the tendency to react. From these
trends emerge the structure-reactivity relationship.
Potential energy is the link between structure and reactivity. The greater a chemical potential of structure,
the greater its reactivity. Understanding the link between structure and reactivity will help us decide which,
among several possible changes, are most reasonable.
Structure reactivity

Chemical Potential

Following things contribute to chemical potential are:

 Bond energy changes

 Strength of electrophiles
 Strength of nucleophiles or bases.

Factors contributing to change stability:

Four factors listed below are some of the most important aspects of structure that contribute to charge
stability.

1. Atom type and periodic table trends: The electronegativity and size of charged atoms contribute to its
ability to stabilize charge.

2. Delocalization: All other things being equal, greater charge delocalization leads to greater stability.

3. Hybridization: All other things being equal, if negative charge is localized on an atom, the greater the
s-character of that atom’s hybrid orbitals, the greater the stability. Conversely, if positive charge is
localized on an atom, the lesser the s-character of the atom’s hybrid orbitals, the greater the stability.
Sp3 is more stable than sp2, which in turn is more stable than sp.

4. Columbic: Like charges repel; opposite charges attract.

Examples:

1. Reactivity of ammonia: in ammonia N is central atom. 4 pairs of electrons are present between 1N and
3H. N from a sigma bond between 3 hydrogen atoms.
Remaining electrons on N acts as a lone pair. These lone pair future react with other atoms.

2. Brontriflouride BF3+:

Hence, by sharing 1 electron with each fluorine atom, boron has 3 sigma bonds around it. In order to
have the stable octet configuration it is need of 2 more electrons. Since it can accept a pair of electrons it
is a Lewis acid.

3. Reactivity of alkene

A carbon-carbon double bond consists of a pi bond and sigma bond. It is easy to break the pi bond. Pi
bond in the alkene contain pi electrons that act as a source of electrons. That’s why alkene electrophilic
addition reaction.

4. Reactivity of alkynes:

A carbon-carbon molecule contain 3 bonds: 2 pi and 1 sigma bond. More number of electrons are
available. They give addition reaction. Alkynes are more reactive than alkenes.

5. Reactivity of benzene: benzene gives electrophilic substitution reaction. Addition reactions would
interrupt the p orbital ring and destroy the aromatic stability.
Question no. 1: [part-B]:

How the expected and actual reactivity of benzene differs. Explain different concepts describing the
reactivity of benzene ring?

Answer:

Expect: Benzene undergo addition reaction typical of other highly unsaturated compounds, including
conjugated dynes.

Actual: Benzene undergo electrophilic substitution reaction.

Just like an alkene, benzene has clouds of pi electrons above and below its sigma frame work.

Although the pi electrons are in a stable aromatic system, they are still available for the reaction with
strong electrophiles. This generate a complex unstable carbocation which is resonance stabilized but not
aromatic.
This cation is a sigma complex because the electrophile is joined to the benzene ring through a sigma
bond. This sigma complex is not aromatic since it contains a sp3 carbon which disrupt the required loop
of p orbitals.

This sigma complex wishes to regain its aromaticity, and it may do so by either a reversal of the first step
(regeneration of the starting material) or by loss of the proton on the sp2 carbon (leading to a
substitution product).

When a reaction proceed this way, it is electrophilic aromatic substitution. Benzene does not undergo
electrophilic addition reaction because:

 It has a cyclic structure.

 It has a 6 H-atoms.
 Double bonds in it are very strong.
 Resonance stabilized system is to be preserved.

Benzene show electrophilic substitution reactions.

Benzene does not react with Br2 to yield addition product. Instead, in the presence of a Lewis acid, bromine
substitutes for a hydrogen atom, yielding a product that retains the benzene ring. Bromination follows the
same general mechanism for the electrophilic aromatic substitution (EAS).Bromine itself is not electrophilic
enough to react with benzene. But the addition of a strong Lewis acid (electron pair acceptor), such as
FeBr3, catalysis the reaction, and leads to the substitution product. The bromine molecule reacts with
FeBr3 by donating a pair of its electrons to the Lewis acid, which creates a more polar Br-Br bond, and thus
a more reactive electrophile. Benzene will now attack this electrophile to generate the sigma complex.
Different concepts about the reactivity of benzene:

Concept number # 1:

Benzene undergo electrophilic aromatic substitution maintaining the aromatic core. Electrophilic aromatic
substitution replaces a proton on benzene with another electrophile.

Concept number # 2:

Benzene can behave as electron donating and electron withdrawing group. It is dependent upon the
substituents that are attached to the benzene ring.

Benzene is an electron withdrawing by inductive effect.

Benzene is an electron donating by resonance effect.

Concept number # 3:

Ortho-para and Meta directing substituents:

When substituted benzene undergo further substitution, the substituted group present on the benzene
derivative will influence electrophilic substitution on two ways:

1- Reactivity
2- Orientation

 Ortho-para directors: the group that tend to direct electrophilic substitution to the C2 and C4
position.
 Meta directors: the group that trends to direct electrophilic substitution to the C3 position.

Effect of substitution on the reactivity:

Electron donating group make the ring more reactive. Reaction becomes more faster. These are also called
activating groups.

Electron withdrawing group make the ring less reactive. Reaction becomes slow. These are called
deactivating group.

Effect on orientation:

General example:
Examples:

Some specific reactions of benzene:

Some example of side chain reaction:

1.

2. Reduction of aromatic ketones:

3. Reduction of nitro group:

Question no. 2 # [part-a]

How electrophiles are generated. Generate at least three electrophiles with mechanism.

Answer:

Electrophiles are electron-deficient species that are attracted to an electron-rich center. Electrophiles
react by accepting an electron pair in order to form a bond to a nucleophile including the interactions
of a proton and a base. Electrophiles are often positively charged as a result of possessing an atom
with a positive charge or an atom that does not have an octet of electrons.

 Examples: Positive charged ions are electrophiles; H+, NH4+.

 Neutral molecules in which central atom is electron deficient; BF3+, ZnCl2+.
 Lewis acids are used as electrophiles.
Generation of electrophile: Anhydrous aluminum chloride is a very useful Lewis acid in the
generation of electrophile from the chlorination, alkylation and acylation of an aromatic ring. The
resulting electrophiles are Cl+, R+ and RC+O respectively.

Cl-Cl + AlCl3 Cl+ + {AlCl4}-

CH3-Cl + AlCl3 CH3+ + {AlCl4}-

CH3-CO-Cl + AlCl3 CH3CO+ + {AlCl4}-

Cl, CH3+ and CH3CO are act as electrophiles.

Examples of electrophilic generation with mechanism:

All electrophilic aromatic substitution reactions share a common mechanism. This mechanism
consists of a series of steps.

1. An electrophile — an electron‐seeking reagent — is generated. For the Bromination of benzene

reaction, the electrophile is the Br+ ion generated by the reaction of the bromine molecule with
ferric bromide, a Lewis acid.

2. The electrophile attacks the π electron system of the benzene ring to form a nonaromatic
carbocation.

3. The positive charge on the carbocation that is formed is delocalized throughout the molecule.

4. The aromaticity is restored by the loss of a proton from the atom to which the bromine atom (the
electrophile) has bonded.
5. Finally, the proton reacts with the FeBr4− to regenerate the FeBr3 catalyst and form the product
HBr.

The nitration of benzene: In another example of an electrophilic aromatic substitution reaction,

benzene reacts with a mixture of concentrated nitric and sulfuric acids to create nitrobenzene.

The mechanism for the nitrobenzene reaction occurs in following steps.

1. Sulfuric acid ionizes to produce a proton.

2. Nitric acid accepts the proton in an acid‐base reaction.

3. The protonated nitric acid dissociates to form a nitronium ion ( +NO 2). 2. Nitric acid accepts the
proton in an acid‐base reaction.

4. The nitronium ion acts as an electrophile and is attracted to the π electron system of the benzene
ring.

5. The aromaticity of the ring is reestablished by the loss of a proton from the carbon to which the
nitro group is attached.
The sulfonation of benzene:

The reaction of benzene with concentrated sulfuric acid at room temperature produces
benzenesulfonic acid.

The mechanism for the reaction that produces benzenesulfonic acid occurs in the following steps:

1. The sulfuric acid reacts with itself to form sulfur trioxide, the electrophile.

This reaction takes place via a three‐step process:

2. The sulfur trioxide is attracted to the π electron system of the benzene molecule.

The charge around the ring is delocalized, and then the loss of a proton reestablishes the aromaticity
of the ring.

Question no. 2 [Part b]

Explain the reactivity of alkenes.

Answer:

Alkenes, also known as olefins, are organic compounds that consist of carbon and hydrogen atoms
with one or more carbon-carbon double bonds in their chemical structure. Alkenes are unsaturated
hydrocarbons. They are hydrocarbons because they are made of only carbon and hydrogen atoms,
and they are unsaturated because they have one or more double bonds in their chemical structure.

Reactions of alkene:

Because single bonds (sigma bonds) are more stable than pi bonds, the most common reactions of
double bonds transform the pi bond into a sigma bond.

Three major reaction types we have studied: addition, elimination, and substitution.
  In an addition, two molecules combine to form one product molecule. When an alkene
undergoes addition, two groups add to the carbon atoms of the double bond and the
carbons become saturated.
 In many ways, addition is the reverse of elimination, in which one molecule splits into two
fragment molecules.
 In a substitution, one fragment replaces another fragment in a molecule.

Examples:

MARKOVNIKOV’S RULE: The addition of a proton acid to the double bond of an alkene results in a
product with the acid proton bonded to the carbon atom that already holds the greater number of
hydrogen atoms
Questi0n no.3: [Part a]

Explain the reactivity of carbonyl compounds with at least three examples.

Answer:

Carbonyl compounds are molecules containing the carbonyl group, C=O.

These include: • Aldehydes • Ketones • Carboxylic acids

Carboxylic acid derivatives: • Esters • Anhydrides • Acid halides • Amides

Reaction of carbonyl compounds:

The reactions of aldehydes and ketones can be divided into two main categories:

– Reactions of the carbonyl group

– Reactions involving the carbon

Carbonyl group reactions fall into three main groups:

 Reactions with acids

 Addition reactions
 Oxidation

• Reactions with acids:

– The carbonyl oxygen is weakly basic

– Both Bronsted and Lewis acids can interact with a lone pair of electrons on the carbonyl oxygen.

For example, when the Bronsted acid H3O+ is used:

• Addition Reactions

– Carbonyl groups in aldehydes and ketones undergo addition reactions.

– This is one of the most important reactions of the carbonyl group.

Addition reactions occur by two different mechanisms:

– Base-catalyzed addition (under basic or neutral conditions)

– Acid-catalyzed addition (under acidic conditions)

• In some cases, we can carry out the same overall reaction using either set of conditions (acidic or
basic).

Addition of water to carbonyl compounds under acidic conditions is analogous to addition of water
to alkenes.

The reaction occurs in three steps:

– Protonation

– Addition

– Deprotonation
Addition of water to carbonyl compounds under basic conditions has no analogy in reactions of
alkenes

The reaction occurs in two steps:

– Addition of OH- to carbonyl carbon

– Protonation of carbonyl oxygen

Addition occurs directly because OH- is a more reactive nucleophile than H2O.

Formation of hemiketal and hemiacetal:

Reaction with girnard reagent:

Reaction with nucleophilic: A nucleophilic addition reaction is a chemical addition reaction in which
a nucleophile forms a sigma bond with an electron deficient species. These reactions are considered
very important in organic chemistry since they enable the conversion of carbonyl groups into a
variety of functional groups. Generally, nucleophilic addition reactions of carbonyl compounds can
be broken down into the following three steps.
  The electrophilic carbonyl carbon forms a sigma bond with the nucleophile.
 The carbon-oxygen pi bond is now broken, forming an alkoxide intermediate (the bond pair
of electrons are transferred to the oxygen atom).
 The subsequent protonation of the alkoxide yields the alcohol derivative.

The carbon-oxygen double bond is directly attacked by strong nucleophiles to give rise to the
alkoxide. However, when weak nucleophiles are used, the carbonyl group must be activated
with the help of an acid catalyst for the nucleophilic addition reaction to proceed.

Reaction with amines:

The reaction between primary amines and aldehydes/ketones yields imine derivatives along with
water. The reaction can be illustrated as follows.

Initially, the nucleophilic nitrogen belonging to the amine attacks the carbonyl carbon. The carbon-
oxygen double bond is broken and a new carbon-nitrogen sigma bond is formed. Now a proton is
transferred from the amine to the oxygen atom. In the next step of this nucleophilic addition
reaction, The OH group is further protonated and water is removed. The carbon atom now forms a
double bond with the nitrogen belonging to the amine. This nitrogen is now deprotonated to afford
the required imine product.

Question no. # 3 [part b]

Explain one method for the preparation of nucleophiles. Explain substitution reaction of nucleophile
with at least three suitable examples.

Answer: A nucleophile, a species with an unshared electron pair (lone-pair electrons), reacts with
an alkyl halide (substrate) by replacing the halogen substituent (leaving group).
In nucleophilic substitution reactions, the C–X bond of the substrate undergoes heterolysis, and the
lone-pair electrons of the nucleophile is used to form a new bond to the carbon atom.

Examples:

Some typical nucleophiles are the hydroxyl group (−OH), the alkoxide group (RO −), and the cyanide
ion (−CN).

Nucleophilic substitution reactions:

Reaction of these nucleophiles with an alkyl halide gives the following reactions and products:

The halogen ion that is displaced from the carbon atom is called the leaving group, and the overall
reaction is called a nucleophilic substitution reaction.

Question no. # 4 [Part a] What are Grignard’s reagent? How they are produced and explain their
reaction with at least three different types of molecule.

Answer: Reactions that form carbon-carbon bonds are among the most useful to the synthetic
organic chemist. In 1912, Victor Grignard received the Nobel Prize in chemistry for his discovery of a
new series of reactions that result in the formation of a carbon-carbon bond.

Grignard reagents are made through the addition of magnesium metal to alkyl or alkyl halides. The
halide can be Cl, Br, or I (not F). It’s slightly easier to make Grignard’s from the iodides and bromides,
however. Note what’s happening here – the magnesium is “inserting” itself between the carbon and
the halide. This halide the “X” referred to when we refer to Grignard reagents as “RMgX”.

Formation of Grignard reagent:

 Reaction of Grignard Reagents with Aldehydes to Give Secondary Alcohols:

One of the most common uses of Grignard reagents is in their reaction with aldehydes and ketones
to form alcohols. In the first step, the Grignard forms the carbon-carbon bond. This results in an
alkoxide (the conjugate base of an alcohol). To form the alcohol, it’s necessary to add acid at the end
of the reaction (in what’s called the “workup” step). This is shown here as “H3O+” (the “X” is just the
counter-ion, a spectator here).

Reaction with aldehyde to form secondary alcohols:

Reaction of Grignard Reagents with Ketones to Give Tertiary Alcohols:

The reaction behaves similarly with ketones. Again, there’s nothing special about the Cl here – it all
depends on how you made the Grignard in the first place.

Reaction with ketones to give tertiary alcohols:

Reaction of Grignard Reagents with Carbon Dioxide to Give Carboxylic Acids

Grignard reagents also add to carbon dioxide (CO2) to form carboxylates, in a reaction similar to
their reactions with ketones and aldehydes. The carboxylates are converted to carboxylic acids after
addition of acid (such as our trusty H3O (+)).

Reaction with carbon dioxide to form carboxylic acid

Question no # 3: [Part b]

How imines are produced. Write mechanism for the synthesis of imines from at least two different
starting materials.

Answer: Imines are the nitrogen analogues of aldehydes and ketones, containing a C=N bond
instead of a C=O bond. They are formed through the dehydration reaction of an aldehyde or ketone
with an amine. Imines derived from aldehydes are sometimes called aldimines, imines derived from
ketones are sometimes called ketamine. Enamines are the nitrogen analogues of enols.

Mechanism of imine formation:

The mechanistic sequence; protonation/1, 2-addition/proton transfer/1, 2-elimination /

Deprotonation.

The reaction starts by stirring an aldehyde or ketone in solution with a little bit of acid. You might
recall that acid makes carbonyl carbons more electrophilic – it binds to the carbonyl oxygen and
weakens the C=O bond. Now comes the exciting part.

Upon addition of an amine, the carbonyl carbon (an electrophile) is attacked by the amine nitrogen
(a nucleophile) and there is a 1, 2-addition. The next step is a proton transfer. This serves two
purposes. First of all, the OH is protonated to give OH2 (+), which is a tremendously better leaving
group.

Secondly, proton transfer frees up the lone pair on the amine nitrogen.
Finding itself free again, the amine lone pair now descends upon the neighboring carbon like a
horned owl swooping down on a moonlit field mouse, expelling the OH2 (+) as a neutral water
molecule.

The final step is a simple Deprotonation of the resulting positively charged imine (iminium, we call it
– most positively charged organic molecules end with -ium), resulting in our neutral product, the
imine.

In practice, this reaction is usually run with a dessicant like magnesium sulfate to soak up the water
that is formed along the way. That’s Le Chatelier’s principle at work again: you’ll notice that the
reaction is an equilibrium. If you take your imine and then dissolve it water, you can get back the
original aldehyde/ketone plus the amine.

Examples:

Question no, # 5; [Part a]

Explain conjugate nucleophilic additions with at least three examples.

Answer: (The carbon atom next to a carbonyl group is often called the carbon, the next carbon is the
β carbon, and so on. Thus, α, β-unsaturated aldehyde or ketone has a double bond conjugated with
the carbonyl group.) The initial product of conjugate addition is a resonance-stabilized enolate ion,
which typically undergoes protonation on α carbon to give a saturated aldehyde or ketone product.

The conjugate addition of a nucleophile to α, β-unsaturated aldehyde or ketone is caused by the

same electronic factors that are responsible for direct addition. The electronegative O atom of theα,
β-unsaturated carbonyl compound withdraw selections from the β C, thereby making it electron-
poor and more electrophilic than a typical alkene carbon.

Conjugate addition can be divided into four steps:

Examples:

Question no. #5[Part b]

Explain the synthesis of aromatic amines. How they are important for the synthesis of different
compounds in organic chemistry.
Answer: The alkylation of ammonia, Gabriel synthesis, reduction of nitriles, reduction of amides,
reduction of nitrocompounds, and reductive amination of aldehydes and ketones are methods
commonly used for preparing amines.

Aromatic amines:

1. These are the derivatives of aromatic hydrocarbon in which a hydrogen of benzene ring has been
replace by amino group.

2. All such compounds in which an amino group is bonded directly to an aromatic ring is termed as
aromatic amines.

Example of aromatic amines:

Reduction of nitrocompounds

Aromatic amines are normally prepared by reduction of the corresponding aromatic nitrocompound.

Another examples:
Importance of aromatic amines:

Aromatic amines, such as phenylamine, are important industrially for the production of dyes.
Modern dyes are formed in a two-stage synthesis:

 The aromatic amine is converted into a diazonium salt

 The diazonium salt is coupled with an aromatic compound such as phenol, forming an azo
dye.

Using benzene for the synthesis of dyes:

Benzene is used as the raw material for the synthesis of dyes.

A four-stage synthesis is shown below:

i. Benzene is nitrated to nitrobenzene

ii. Nitrobenzene is reduced to phenylamine (see above)
iii. Phenylamine is converted into a diazonium salt
iv. The diazonium salt is coupled with an aromatic compound such as phenol, forming an azo
dye.