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Mechanism of Organic Reactions How the reactions occurs in organic compounds? Breaking of bonds in organic reactions(cleavage): Heterolytic cleavage, Homolytic.

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Presentation on theme: "Mechanism of Organic Reactions How the reactions occurs in organic compounds? Breaking of bonds in organic reactions(cleavage): Heterolytic cleavage, Homolytic."— Presentation transcript:

1 Mechanism of Organic Reactions How the reactions occurs in organic compounds? Breaking of bonds in organic reactions(cleavage): Heterolytic cleavage, Homolytic cleavage Types of organic reactions Terms in reaction: substrate, attacking reagent, Leaving group & product Attacking reagents- Electrophile, Nucleophile & Free radicals Addition reaction Substitution reaction- S N 1 & S N 2 Elimination reaction- E1 & E2 Rearrangement reaction- Hoffman rearrangement reaction

2 Fundamentals of Organic reactions: How the reaction occurs in organic compounds? In an organic reaction some covalent bonds are broken and to form a new compound some covalent bonds are formed. Difference of energy for bond breaking and new bond formation defines the type or possibility of reactions. The chemical properties of attacking reagent and medium also plays a key role in a organic reaction. The different type of reaction medium or polarity differences determines the reaction type between substitution or elimination. We will see it in the later topics. Organic reactions and its products or reaction mechanism is determined by the functional groups present in the reactants. The reaction can be defined as a characteristic reaction in organic chemistry. As example, alcohols produce ester reacting with organic acid or organic acid derivatives. CH 3 –CO- Z + C 2 H5-O-H CH 3 -CO-O-C 2 H 5 + HZ *Z=Cl/OH/-O-CO-R

3 Transition state: In the transition state theory, the mechanism of interaction of reactants is not considered; the important criterion is that colliding molecules must have sufficient energy to overcome a potential energy barrier (the activation energy) to react. For a bimolecular reaction, a transition state is formed when the two molecules’ old bonds are weakened and new bonds begin to form or the old bonds break first to form the transition state and then the new bonds form afterward. The theory suggests that as reactant molecules approach each other closely they are momentarily in a less stable state than either the reactants or the products. In the example below, the first scenario occurs to form the transition state:

4 It takes a lot of energy to achieve the transition state, so the state is a high- energy substance. The potential energy of the system increases at this point because: The approaching reactant molecules must overcome the mutual repulsive forces between the outer shell electrons of their constituent atoms Atoms must be separated from each other as bonds are broken This increase in potential energy corresponds to an energy barrier over which the reactant molecules must pass if the reaction is to proceed. The transition state occurs at the maximum of this energy barrier. The transition state is an unstable transitory combination of reactant molecules that occurs at a potential energy maximum

5 Breaking bonds in organic reactions Homolysis: When a bond breaks and of the two electrons making up the covalent bond, one goes to each fragment; such bond-breaking is called homolysis. Heterolysis: In heterolysis both bonding electrons go to the same fragment. A:B A + B Homolysis A:B A + B Heterolysis

6 Terms in reaction Substrate: a substrate is a molecule upon which an attacking reagent acts. Attacking reagent: a molecule or groups of molecules or atom which acts on the substrate and sometime initiate a reaction is called attacking reagent. Leaving groups: In a type of reaction the group which readily leaves from the reaction state and facilitate the specific type of reaction is said the leaving group. Nu: - + R-L R-Nu + :L - Leaving group Substrate Attacking reagent

7 Attacking reagents Nucleophile: Nucleophile is a species with an unshared electron pair. Its nucleus attracting group and able to donate electron in a reaction. Expressed as Nu: - or Nu: 2 types of nucleophiles : Negatively charged: :CH 3 -, :Cl -, :Br -, :CN -, :OH -, :OR - Neutral nuclephiles: NH 3, H 2 O, R-OH Reaction: 1. With (-)ve nucleophiles: 2. With neutral Nu:

8 Attacking reagents Electrophile: Electrophiles are electron attracting group. They are deficient of a pair of electron at the outermost orbital or outermost bonding orbital and can accept a pair of electron at the deficient orbital. Expressed as E or E + Electrophiles are of 2 types: 1. (+)vely charged: + CH 3, Br +, H +, H 3 O +, NO 2 +, + NO 2. Neutral Electrophile: AlCl 3, BF 3, FeCl 3, SO 3 Reaction: 1. With (-)ve electrophiles: 2. With neutral lectrophiles:

9 Free radicals: Free radicals are the molecules which are produced by homolysis of a sigma bond and contains an unpair electron. They are highly reactive and chargeless as the unpair electron is their own electron. Being highly reactive these free radicals exist a while and creates a stable compound by reacting instantly with another molecule or another free radical. Free radical reaction or chain reaction: The halogenation reactions of alkanes take place by the free radical chain reaction mechanism. The homolysis of Cl 2 is necessary to produce the initiator free radical Cl. This light promoted reaction is highly efficient.

10 Step-1: Chain Initiation Cl 2 2 Cl Step-2 & 3: Chain Propagation CH 4 + Cl CH 3 + H-Cl CH 3 + Cl 2 CH 3 Cl + Cl Step-4: Chain Termination CH 3 + Cl CH 3 Cl CH 3 + CH 3 CH 3 -CH 3 Cl + Cl Cl-Cl Heat light Chain Reaction of Free radicals

11 Types of Organic reactions Organic reactions are classified into 4 groups: 1. Substitution reaction 2. Addition reaction 3. Elimination reaction & 4. Rearrangement or isomerization reaction Substitution reaction: The reaction in which one group of molecules is replaced by more reactive groups of molecules and forms a new compound is called substitution reaction.e.g. C 2 H 5 -Cl + OH - C 2 H 5 -OH + Cl -

12 Addition reaction: The reaction in which two different molecules are added to produce an added compound is the addition reaction. e.g. H 2 C=C 2 H + Br-Br H 2 C-CH 2 Unsaturation test: Addition reaction is used to identify the unsaturation in an organic compound. In the previous reaction we can see the alkene contains a pie bond and a sigma bond. The bromine solution in CCl 4 is red and when reacts with the alkene the pie bond is broken to give the addition product and red color of the solution disappears. This is also a 1,2- addition reaction. 1,2 addition reaction occurs in unsaturated organic comp. Br CCl 4 1,2- dibromo alkane

13 Markinov’s Rule Addition of hydrogen halides to alkenes: The addition of HX to an asymmetric alkene could conceivably occur in 2 ways. In practice, however, one product usually predominate. The addition of HBr to propene, for example, could conceivably lead to either 1-bromopropane or 2- bromopropane. The main product is 2-bromopropane.

14 Markinov’s Rule One way to state this rule is to say that in the addition of HX to alkene, the hydrogen atom adds to the carbon atom of the double bond that already has the greater number of hydrogen atoms. Modern statement of Markonikov’s rule: In the ionic addition of an unsymmetrical reagent to a double bond, the positive protion of the adding reagent attaches itself to a carbon atom of the double bond so as to yield the more stable carbocation as an intermediate.

15 Markinov’s Rule Markonikov’s rule can define the regioselevtivity of the addition of hydorgen halide or other reactants to the alkenes. Regioselective reactions: When a reaction that can potentially yield two or more constitutional isomers actually produces only one (or a predominance of one), the reaction is said to be regioslelective.

16 Antimarkonikov’s rule

17 SUBSTITUTION REACTION Nucleophilic substitution reactions: General types of nucleophilic substitution (S N ) Because of the substitution is initiated by a neucleophile, it is called a nucleophilic substitution or S N reaction. The R-X bond can be broken by two ways- Thus 2 types: S N 1 & S N 2

18 S N 2 REACTION: Bimolecular substitution Order of the reaction is 2, thus rate of the reaction depends on the concentration of two reactants e.g both alkyl halide & base. The nucleophile approaches the carbon bearing the leaving group from the back side, opposite to the leaving group.

19 MECHANISM OF S N 2 REACTION The negative OH - ion pushes a pair of electrons into the partially positive carbon from the back side. The chlorine begins to move away with the pair of electrons that may bonded it to the carbon Transition state A bond between oxygen and carbon in partially formed and the bond between carbon and chlorine is partially broken. The configuration of the carbon atom begins to change Bond between the oxygen and carbon has formed and the chloride ion has departed. Configuration of the carbon has inverted. Walden Inversion Configuration: The particular arrangement of groups around that atom in space.

20 S N 2.. Characteristics of SN2 reaction: 1. C-Nu bond provides energy to break the C-L bond 2. Involves only one step 3. No intermediate compound 4. Reaction proceeds through the formation of an unstable arrangement of atoms that is transition state which exist for an extremely brief period of time 5. Always lead to inversion of configuration 6. 3D factor is the rate determining factor

21 Stereochemistry of SN2 Walden inversion- in acyclic and cyclic carbon skeleton

22 Unimolecular substitution reaction in which reaction rate depends on one reactants concentration. S N 1 REACTION:

23 MECHANISM OF S N 1 REACTION Multi-step reaction Intermediate products are produced in the steps but no transition state


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