TERM PAPER CHEMISTRY (CHE 101)

Topic:

SUBSTITUTION REACTIONS

DOA: SEPT 2, 2010 DOR: SEPT30, 2010 DOS: NOV10, 2010

Submitted to: Ms. Vibhuti Walia Deptt. Of Chemistry

Submitted by: Mr. Amandeep Singh Khera Roll. No. RK6005A19 Reg.No. 11000597 Class K6005

ACKNOWLEDGEMENT

It acknowledges all the contributors involved in the preparation of this project. Including me, there is a hand of my teachers, some books and internet. I express most gratitude to my subject teacher, who guided me in the right direction. The guidelines provided by her helped me a lot in completing the assignment.

The books and websites I consulted helped me to describe each and every point mentioned in this project. Help of original creativity and illustration had taken and I have explained each and every aspect of the project precisely.

At last it acknowledges all the members who are involved in the preparation of this project.

Thanks AMANDEEP SINGH

ABSTRACT

In a substitution reaction, a functional group in a particular chemical compound is replaced by another group. In organic chemistry, the electrophilic and nucleophilic substitution reactions are of prime importance. After going through this one can easily understand what is substitution reaction. One can account for various types of substitution reaction n there mechanism i.e. SN1 and SN2. Here we will take account of substitution reactions like nucleophilic substitution and electrophillic substitution reactions. We will talk about substituted compounds, controlling ligand substitution reactions. We will talk about use of substitution reactions in day to day life and its importance. We will account for applications an d future prospective of substitutions reaction and its day to day need. We will come across how radical substitution reaction occurs n their importance. We will come across various steps required for radical substitution.

TABLE OF CONTENT

1. INTRODUCTION 2. NUCLEOPHILIC SUBSTITUTION 3. ELECTROPHILIC SUBSTITUTION

3.1 ELECTROPHILIC AROMATIC SUBSTITUTION 3.2 ELECTROPHILIC ALIPHATIC SUBSTITUTION

4. RADICAL SUBSTITUTION 5. SUBSTITUTED COMPOUNDS 6. MECHANISM OF REACTION

6.1 SN1 MECHANISM 6.2 SN2 MECHANISM

7. APPLICATIONS 8. FUTURE PROSPECTIVE 9. BIBLOGRAPHY

INTRODUCTION

In a substitution reaction, a functional group in a particular chemical compound is replaced by another group. The term substitution is derived from the word substitute which means putting one thing in place of other. In organic chemistry, the electrophilic and nucleophilic substitution reactions are of prime importance. Organic substitution reactions are classified in several main organic reaction types depending on whether the reagent that brings about the substitution is considered an electrophile or a nucleophile, whether a reactive intermediate involved in the reaction is a carbocation, a carbanion or a free radical or whether the substrate is aliphatic or aromatic. Detailed understanding of a reaction type helps to predict the product outcome in a reaction. It also is helpful for optimizing a reaction with regard to variables such as temperature and choice of solvent. A good example of a substitution reaction is the photochemical chlorination of methane forming methyl chloride.

In the above reaction Cl2 and CH4 are reactants and take part in a substitution reaction. In this reaction Cl replaces H from CH 4 in the presence of sunlight to form CH3Cl. There are various substitution reactions include Nucleophilic substitution

Electrophilic substitution Radical substitution Substituted compound

NUCLEOPHILIC SUBSTITUTION
In organic and inorganic chemistry, nucleophilic substitution is a fundamental class of substitution reaction in which an "electron rich" nucleophile selectively bonds with or attacks the positive or partially positive charge of an atom attached to a group or atom called the group. The positive or partially positive atom is referred to as an electrophile.Nucleophilic substitution happens when the reagent is a nucleophile, which means, an atom or molecule with free electrons. A nucleophile reacts with an aliphatic substrate in a nucleophilic aliphatic substitution reaction. These substitutions can be produced by two different mechanisms: unimolecular nucleophilic substitution (SN1) and bimolecular nucleophilic substitution (SN2). The SN1 mechanism has two steps. In the first step, the leaving group departs, forming a carbocation. In the second step, the nucleophilic reagent attacks the carbocation and forms a sigma bond. This mechanism can result in either inversion or retention of configuration. An SN2 reaction has just one step. The attack of the reagent and the expulsion of the leaving group happen simultaneously. This mechanism always results in inversion of configuration. When the substrate is an aromatic compound the reaction type is nucleophilic aromatic substitution. Carboxylic acid derivatives react with nucleophiles in nucleophilic acyl substitution. This kind of reaction can be useful in preparing compounds. The most general form for the reaction may be given as Nuc: + R-LG R-Nuc + LG:

The electron pair (:) from the nucleophile (Nuc) attacks the substrate (R-LG) forming a new bond, while the leaving group (LG) departs with an electron pair. The principal product in this case is R-Nuc. The nucleophile may be electrically neutral or negatively charged, whereas the substrate is typically neutral or positively charged. An example of nucleophilic substitution is the hydrolysis of an alkyl bromide, R-Br, under alkaline conditions, where the attacking nucleophile is the OH and the leaving group is Br-. R-Br + OH R-OH + Br

ELECTROPHILIC SUBSTITUTION

Electrophilic

substitution reactions a group

are in a aromatic

chemical

reactions typically

in but

which not

an electrophile displaces

compound,

always hydrogen. Electrophilic

substitution is

characteristic

of aromatic compounds and is an important way of introducing functional groups onto benzene rings. The other main reaction type is electrophilic aliphatic substitution.

ELECTROPHILIC AROMATIC SUBSTITUTION In electrophilic substitution in aromatic compounds, an atom appended to the aromatic ring, usually hydrogen is replaced by an electrophile. The most important reactions of this type that take place are aromatic nitration, aromatic halogenation, aromatic sulfonation and acylation and alkylating Friedel-Crafts reactions.

ELECTROPHILIC ALIPHATIC SUBSTITUTION In electrophilic substitution in aliphatic compounds, an electrophile displaces a functional group. This reaction is similar to nucleophilic aliphatic substitution where the reactant is a nucleophile rather than an electrophile. Mechanism is same that of nucleophillic substitution reaction.

RADICAL SUBSTITUTION
In free radical halogenation reactions radical substitution takes place with halogen reagents and alkane substrates. Another important class of radical substitutions involves aryl radicals. One example is the hydroxylation of benzene by Fenton's reagent. Many oxidation and reduction reactions in organic chemistry have free radical intermediates, for example the oxidation of aldehydes to carboxylic with chromic acid. Coupling reactions can also be considered radical substitutions. Certain aromatic substitution takes place by radical-nucleophilic aromatic substitution. Auto-oxidation is a process responsible for deterioration of paints and food and lab hazards such as diethyl ether peroxide. The reaction always involves at least two steps, and possibly a third. In the first step called initiation a free radical is created by homolysis. Homolysis can be brought about by heat or light but also by radical initiators such as organic peroxides or azo compounds. Light is used to create two free radicals from one diatomic species. The final step is called termination in which the radical recombines with another radical species. If the reaction is not terminated, but instead the radical group(s) go on to react further, the steps where new radicals are formed and then react is collectively known as propagation because a new radical is created available for secondary reactions.

Examples

SUBSTITUTED COMPOUNDS

Substituted compounds are chemical compounds where one or more hydrogen atoms of a core structure have been replaced with a functional group like alkyl, hydroxy, or halogen.

For example benzene is a simple aromatic ring and substituted benzenes are a heterogeneous group of chemicals with a wide spectrum of uses and properties: Compou general nd formula Benzene C6H6 Toluene C6H5-CH3 general structure

o-Xylene C6H4(-CH3)2

Mesityle C6H3(-CH3)3 ne Phenol C6H5-OH

Just a few substituted benzene compounds

MECHANISM OF REACTIONS

SN1 MECHANISM

The SN1 reaction is a substitution reaction in organic chemistry. "SN" stands for nucleophilic substitution and the "1" represents the fact that the rate-determining step is unimolecular. The reaction involves a carbocation intermediate and is commonly seen in reactions of secondary or tertiary alkyl halides under strongly basic conditions or, under strongly acidic conditions, with secondary or tertiary alcohols. An example of a reaction taking place with an SN1 reaction mechanism is the hydrolysis of tert-butyl bromide with water forming tert-butyl alcohol:

This SN1 reaction takes place in three steps:

Formation of a tert-butyl carbocation by separation of a leaving group (a bromide anion) from the carbon atom: this step is slow and reversible.
[4]

Nucleophilic attack: the carbocation reacts with the nucleophile. If the nucleophile is a neutral molecule (i.e. a solvent) a third step is required to complete the reaction. When the solvent is water, the intermediate is an oxonium ion. This reaction step is fast.

Deprotonation: Removal of a proton on the protonated nucleophile by water acting as a base forming the alcohol and a hydronium ion. This reaction step is fast.

SN2 MECHANISM

The SN2 reaction (also known as bimolecular nucleophilic substitution or as backside attack) is a type of nucleophilic substitution, where a lone pair from a nucleophile attacks an electron deficient electrophilic center and bonds to it, expelling another group called a leaving group. Thus the incoming group replaces the leaving group in one step. Since two reacting species are involved in the slow, rate-determining step of the reaction, this leads to the

namebimolecular nucleophilic substitution, or SN2. Among inorganic chemists, the SN2 reaction is often known as the interchange mechanism. The reaction most often occurs at an aliphatic sp3 carbon center with an

electronegative, stable leaving group attached to it - 'X' - frequently a halide atom. The breaking of the C-X bond and the formation of the new C-Nu bond occur simultaneously to form a transition state in which the carbon under nucleophilic attack is pentacoordinate, and approximately sp2 hybridised. The nucleophile attacks the carbon at 180 to the leaving group, since this provides the best overlap between the nucleophile's lone pair and the C-X * antibonding orbital. The leaving group is then pushed off the opposite side and the product is formed. If the substrate under nucleophilic attack is chiral, this can lead, although not necessarily, to an inversion of stereochemistry, called the Walden inversion.

SN2 reaction of bromoethane with hydroxide ion. The products are ethanol and a bromide ion. In an example of the SN2 reaction, the attack of OH (the nucleophile) on a bromoethane (the electrophile) results in ethanol, with bromide ejected as the leaving group. SN2 attack occurs if the backside route of attack is not sterically

hindered by substituents on the substrate. Therefore this mechanism usually occurs at an unhinderedprimary carbon centre.

APPLICATIONS

1. Total Synthesis of dl-Physostigmine

A concise, highly efficient formal total synthesis of dl-physostigmine is described, using a relatively simple method that should be adaptable to the synthesis of homologous members of this type of alkaloid. The key step in the synthesis is a new vicarious nucleophilic substitution reaction between p-nitroanisole and a C-silylated derivative ofN-methylpyrrolidinone. Subsequent conversion of the initial adduct to the tricyclic framework of physostigmine follows a well-established protocol and provides the key intermediate 8 in high yield. The vicarious nucleophilic substitution reaction has also been extended to six-membered lactams,

with

encouraging

result.

2. Nucleophilic Substitution Reactions In Ionic Liquids

This paper presents a quantitative comparison of the rates of nucleophilic reactions in ionic liquids and molecular solvents. Both neutral and ionic nucleophiles and electrophiles were used and the solvent effects on these various systems were determined using a Linear Solvation Energy Relationship based on the Kamlet-Taft solvent scales. These correlations reveal that different hydrogen bonding and dipolar interactions provide the dominant effects in determining the rate of reaction, depending upon the specific system under study. The results of this system are useful for predicting nucleophilic interactions at metal centres involved in catalytic processes.

FUTURE PROSPECTIVE

MICROWAVE ASSISTED SYNTHESIS OF AZIDES,THIOCYANATES AND SULFONES IN AN AQUEOUS MEDIUM

A practical, rapid, and efficient microwave (MW) promoted synthesis of various azides, thiocyanates, and sulfones is described in an aqueous medium. This general and expeditious MW-enhanced nucleophilic substitution approach uses easily accessible starting materials such as halides or tosylates in reaction with alkali azides, thiocyanates, or sulfinates in the absence of any phase-transfer catalyst, and a variety of reactive functional groups are tolerated.

BIBLOGRAPHY

1.

http://en.wikipedia.org/wiki/SN1_reaction

2. http://en.wikipedia.org/wiki/Substitution_reaction 3. http://en.wikipedia.org/wiki/Substitution_reaction#Electrophilic_substit
utions

4. http://en.wikipedia.org/wiki/Substitution_reaction#Radical_substitution
s

5. http://pubs.acs.org/doi/abs/10.1021/jo061114h 6. dinkneshethiopiatour.com/0s178w3Dr/ 7. R CHANG CHEMISTRY 8. PRADEEP CHEMISTRY 9. DINESH CHEMISTRY