umapathi reddy nalla ISOMERISM IN ORGANIC COMPOUNDS Isomerism is the phenomenon of exhibiting two or more compounds with same

ame molecular formula but different physical and chemical properties. Isomers are the compounds showing different physical and chemical properties but same molecular formula. The isomerism in organic compounds can be classified broadly into: 1. Structural isomerism (constitutional isomerism) 2. Stereo isomerism STRUCTURAL ISOMERISM The structural isomerism or constitutional isomerism arises when atoms within a molecule are arranged in different orders. The structural isomers have the same molecular formula but different structural formulae. The structural isomers usually show different physical and chemical properties. The structural isomerism is further divided into: 1. Chain isomerism 2. Positional isomerism 3. Functional isomerism 4. Metamerism CHAIN ISOMERISM The chain isomerism arises due to different arrangements of carbon atoms leading to linear and branched chains. The chain isomers have same molecular formula but different types of chains i.e., linear and branched. The chain isomers have almost similar chemical properties but different physical properties. For example, the branched chain isomers have lower boiling points than that of their linear counterparts. It is because, the linear ones have more surface area of contact and hence the intermolecular forces of attraction are maximum. E.g. two chain isomers possible with the molecular formula, C4H12. i.e., n-butane: a linear chain isomer. Isobutane (or 2-methylpropane): a branched isomer

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POSITIONAL ISOMERISM The positional isomerism arises due to different positions of side chains, substituents, functional groups, double bonds, triple bonds etc., on the parent chain. E.g. 1) Propyl chloride and isopropyl chloride are the positional isomers with the molecular formula, C3H7Cl. These isomers arise due to difference in the position of the chloro group on the main chain.

2) In the following positional isomers i.e., but-1-ene and but-2-ene the position of double is different but they have same molecular formula, C4H8.

3) The functional group, -OH is at different positions on the main chain of the following alcohols. They have the same molecular formula, C3H7OH.

4) In the following positional isomers i.e., ortho xylene, meta xylene and para xylene, the relative positions of methyl groups on the benzene ring are different.

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FUNCTIONAL ISOMERISM The functional isomerism arises due to presence of different functional groups. The functional isomers have the same molecular formula but possess different functional groups. The functional isomers show different physical as well as chemical properties.

E.g. 1) the dimethyl ether is the functional isomer of ethyl alcohol. Both have the same molecular formula, C2H6O. However they have different functional groups.

2) Acetaldehyde is a functional isomer of acetone. They have the same molecular formula, C3H6O but different functional groups. Acetaldehyde contains aldehyde, -CHO functional group, whereas acetone has ketone, >C=O functional group.

3) Both Acetic acid and methyl formate are also functional isomers. They have the same molecular formula, C2H4O2. Acetic acid is a carboxylic acid with -COOH group whereas methyl formate is an ester with -COOCH3 group.

umapathi reddy nalla METAMERISM The metamerism arises when different alkyl groups are attached to same functional group. E.g.1) The following metamers contain the ether functional group. However they differ by the nature of alkyl groups attached to the oxygen atom.

2) The metamerism is also possible in amines as shown below.

STEREOISOMERISM The isomerism which arises due to different spatial arrangements of atoms or groups is called stereo isomerism. It is broadly divided into: 1. Geometrical isomerism 2. Optical isomerism 3. Conformational isomerism The stereo isomers have same structural formula i.e., same connectivity order between atoms. However the atoms or groups are arranged differently in space.

Bond polarization in covalent compounds The development of charges due to the movement of electrons towards more electro negative atom in a polar covalent bond is known as polarization or electron displacement. The effects that cause polarization are called as polarization effects. The 4 important polarization effects are

umapathi reddy nalla 1. Inductive effect 2. Mesomeric or resonance effect 3. Hyper conjugation 4. Electromeric effect INDUCTIVE EFFECT Partial displacement of electrons forming sigma bonds towards more electronegative atoms is called as inductive effect. (or) The polarization of a bond due to electron withdrawing or electron donating effect of adjacent groups or atoms is called inductive effect.

Salient features of inductive effect 1. It is a permanent effect 2. It involves sigma bonds 3. It is operated in saturated compounds. 4. It involves partial displacement of electrons 5. It arises due to electro negativity difference between two atoms forming a sigma bond. 6. It is transmitted through the sigma bonds. 7. It is denoted by arrow mark.

8. It depends on length of the carbon chain. 9. The effect of inductive effect decreases with increase in length of the carbon chain. For practical purposes it is considered up to 3 0r 4 carbon atoms. After 4th carbon atom its effect is zero. 10. It influences the chemical and physical properties of compounds. 11. Based on the nature of functional groups inductive effect groups are classified into 2 types. a. +I.E. groups: which can donate electron density are called as +I.E. groups. ex: - C(CH3)3 , -CH(CH3)2 , -CH2CH3 , -CH3 , -H .

umapathi reddy nalla b. -I.E. groups: which are withdrawing the electron density is called as I.E. groups. ex: -NO2 , -CN , -SO3H ,-CHO , -CO , -COOH , -COCl >, -CONH2 , -F , -Cl , -Br , -I , -OH , -OR ,- NH2 , -C6H5

ILLUSTRATION OF INDUCTIVE EFFECT The C-Cl bond in the butyl chloride, CH3-CH2-CH2-CH2-Cl is polarized due to electro negativity difference. The electrons are withdrawn by the chlorine atom. Thus the first carbon atom gets partial positive charge. In turn, this carbon atom drags electron density partially from the next carbon, which also gets partial positive charge. Thus the inductive effect is transmitted through the carbon chain. TYPES OF INDUCTIVE EFFECT The inductive effect is divided into two types depending on their strength of electron withdrawing or electron releasing nature with respect to hydrogen. 1) Negative inductive effect (-I): The electron withdrawing nature of groups or atoms is called as negative inductive effect. It is indicated by -I. Following are the examples of groups in the decreasing order of their -I effect: 2) Positive inductive effect (+I): It refers to the electron releasing nature of the groups or atoms and is denoted by +I. Following are the examples of groups in the decreasing order of their +I effect. APPLICATIONS OF INDUCTIVE EFFECT Stability of Carbonium ions: The stability of carbonium ions increases with increase in number of alkyl groups due to their +I effect. The alkyl groups release electrons to carbon, bearing positive charge and thus stabilize the ion. The order of stability of carbonium ions is:

umapathi reddy nalla 2. MESOMERIC EFFECT OR RESONANCE EFFECT 1. It is permanent effect 2. It is defined as pi electrons from a multiple bond transferred to a sigma or an atom or non bonding electrons from an atom transferred to a sigma bond or an atom is called as mesomeric effect or resonance effect. Ex: CH2=CH- CH=CH2 CH2-CH=CH-C H2

CH2=CH-CH=O 3. 4. 5. 6. 7. 8. 9.

CH2-CH-CH-O

It is operated in unsaturated compounds especially in conjugated double bond systems. It is denoted by arrow mark. It involves complete displacement of electrons. It involves pi and non bonding electrons. It is transmitted along the chain to any length if the conjugation is provided. It is symbolized by M or R. Based on the nature of functional groups this effect groups are also divided into two types. a. +M.E groups: which can donate electrons by delocalization are called +M.E groups. ex.: -OH, -OR, -SH, -SR, -NH2, -NR2 etc. b. -M.E groups: which withdraw electron density by delocalization are called M.E groups. ex.: -NO2, Carbonyl group (C=O), -CN, -COOH, -SO3H etc. 10. As the no. of resonance structures increases stability of the molecule increases. 11. Types of mesomeric effect: 2 Types. a. Positive mesomeric effect (+M or +R) : the effect that is caused due to the presence of electron donating group like NH2, -OH,-SH ,-Cl etc.

b. Negative mesomeric effect (-R or -M) : the effect that is caused due to the presence of electron with drawing groups like -NO2, Carbonyl group (C=O), -CN, -COOH, -SO3H etc.

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3.HYPERCONJUGATION

1. It is a permanent effect. 2. Both resonance effect and hyperconjugation are similar effects on bond polarization.but in resonance effect pi and non bonding electrons are involved in delocalization whereas in hyperconjugation sigma and pi bonded electrons are involved. 3. it is defined as delocalization of alpha electrons between alpha carbon and alpha hydrogen atom to sigma bond or an atom is called as hyperconjugation. 4. it is operated in unsaturated compounds. 5. it involves sigma and pi electrons. 6. it is operated in the molecule having at least one alpha hydrogen or one hydrogen with rspect to an unsaturation or carbocation or free radical. 7. it is also called as NO BOND RESONANCE. In the contributing structures: (II), (III) & (IV) of propene, there is NO bond between an -carbon and one of the hydrogen atom. Hence the hyperconjugation is also known as "no bond resonance". 8. Stability of alkenes: A general rule is that, the stability of alkenes increases with increase in the number of alkyl groups (containing hydrogens) on the double bond. It is due to increase in the number of contributing no bond resonance structures.

umapathi reddy nalla For example, 2-butene is more stable than 1-butene. This is because in 2-butene, there are six hydrogens involved in hyperconjugation whereas there are only two hydrogens involved in case of 1butene. Hence the contributing structures in 2-butene are more and is more stable than 1-butene. 4.ELETROMERIC EFFECT (E effect) 1.Is is temperary effect. 2. it is defined as the complete trasfer of a shared pair of a pi electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. 3.it is denoted by E and the the shifting of the electrons is shown by a curved arrow mark. 4. it is operated in the presence of a reagent only. 5.it occurs in unsaturated compounds. 6.it is classified into two types. a.Positive eletromeric effect: In this effect the pi electrons of the multiple bond are trasferred to that atom to which the reagent gets attached. C=C + H+ C-C

b.Negatibe eletromeric effect: In this effect the pi electorns of the multiple bond are trasferred to that atom to which the attacking reagent dies not get attached. C=C + CN C-C