Revision of isomerism

1.Structural isomerism 2. Geometrical isomerism 3.Optical isomerism 4. Conformational isomerism

By

Ajnish Kumar Gupta (AKG) Lecturer of Organic Chemistry Ajnish@OrganicChemistry.co.in

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Isomers
Two or more molecules with same molecular formula but have different physical & chemical properties

Isomers

Structural i.e Compounds have different IUPAC name

Stereo i.e. Compounds having same IUPAC name

Chain

Positional

Functional

Metamer

Tautomer

Configuration

Conformation

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Structural isomerism
Chain isomerism :
Isomers which differ in main chain or side chain of carbon keeping no change in nature of chemical reaction, functional groups, multiple bonds or substituents. substituents.

Position isomerism :
Isomers which differ in position of functional groups, multiple bonds or substituents keeping no change in main skeleton or side skeleton of carbon, functional groups or multiple bonds.

Functional isomerism :
Isomers which differ in nature of chemical reactions i.e. mainly functional groups.

Metamerism :
Isomers which have any type of difference in carbon along the polyvalent atom containing functional groups which have carbon in both sides.

Tautomerism :
Isomers which differ in position of protons when two structures are in dynamic equilibrium with each others www.OrganicChemistry.co.in

Geometrical isomerism
Isomers which are formed by restriction in rotation in a molecule.

Conditions:
1. Molecules must have restriction in rotation 2. Restricted atoms must have different substituents attach to them

General cases of Geometrical isomerism :

1. Along C=C bond 2. Along C=N bond 3. Along N=N bond 4. Along cycloalkanes 5. Along cycloalkenes with carbon 8 or greater than 8

Some molecules have restriction in rotation but due to absence of different substituents they dont show GI
1. Along C=O bond 2. Along O=O bond 3. Along N=O bond 4. Along S=O bond 5. Along C C bond 6. Along C N bond www.OrganicChemistry.co.in

Nomenclature used in GI
CisCis-Trans:
Mainly used for C=C bonds & Cycloalkanes Cis : when 2 similar groups are on the same side of restricted atoms Trans : when 2 similar groups are on the same side of restricted atoms

SynSyn-Anti:
Mainly used for C=N & N=N bonds Syn : When H & groups are on the same side of restricted atoms when derived from aldehydes. aldehydes. When both lone pairs of electrons are on the same side of restricted atoms in N=N bonded compounds. Anti : When H & groups are on the opposite side of restricted atoms when derived from aldehydes. aldehydes. When both lone pairs of electrons are on the opposite side of restricted atoms in N=N bonded compounds. In case of molecules with C=N we have to specify the group on which we are saying about syn or anti.

E-Z :
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E-Z :
IUPAC recommended nomenclature used for all geometrical isomers Given by Cahn-Ingold-Prelog therefore priority rule for deciding Cahn-Ingoldconfiguration as E or Z is called as CIP Rule. If two high priority groups are on the same side of restricted atoms than such configuration is called as Z. If two high priority groups are on the opposite side of restricted atoms than such configuration is called as E.

CIP Rule :
1. Group with the first atom having high atomic number directly attach to restricted atom in case of GI is given higher priority. 2. If the first atom is identical then second atom is observed for deciding the priority. If second is also same then go on up to that place from where we get the difference. 3. If the group has unsaturation, then a hypothetical equivalent sigma unsaturation, bond is drawn for it and then compare with other group for seniority. 4. Only in case of isotopes where atomic number is same but have different atomic mass, atomic mass is given higher priority. Never correlate Cis-Trans with E-Z because both have different CisEconcepts for naming configurations. CIP Rule is also used to decide R-S nomenclatue in optical isomerism. Rwww.OrganicChemistry.co.in

Optical isomerism:
Experimental background : Those compounds which can rotate the plane polarized light to certain angle is called optically active compounds and the isomers are called as optical isomers. Theeoratical background : Chirality is one & sufficient condition for a molecule to be optically active. active. Chirality means dissymmetry or nonsuperimposability of an object on its mirror image i.e. absence of plane of symmetry (POS) & Centre of symmetry (COS) .

Dont confuse with chiral molecule and chiral carbon, both are different
Chiral carbon is that carbon whose all the four valencies are different but chiral molecule is that one which do not have POS & COS. Symmetric molecules are some times called as achiral molecules so if a carbon have atleast 2 similar groups then it is achiral carbon. Plane of Symmetry (POS): An imaginary plane that bisects a molecule in such a way that the two halves of the molecule are mirror images of each other Centre of Symmetry (COS): It is the point in the centre of molecule from which if we move in equal and opposite direction, we get the same atoms or groups on other side. www.OrganicChemistry.co.in

Basic concepts & pictures

Chiral molecule - has the property of handedness i.e Not superposable on its mirror image They can exist as a pair of enantiomers which are individually a chiral molecule. Achiral molecule has property of Superposable on its mirror image.

Mirror images = handedness

Mirror image = Left hand cannot be superimposed converts right hand into left on the right hand

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Some terms used in optical isomerism

Enantiomers : Two stereo isomers which are non superimposable but are mirror images of one another. They have same physical properties so have 1 fraction on distilation. distilation. Diastereomers : Two stereo isomers which are non superimposable and non mirror images of one another. They have different physical properties so have 2 fractions on distilation. distilation. Racemic mixture : Mixture of pair of enantiomers in equal amounts. Compound is optically inactive due to external compansation. compansation. Meso compound : Indivisual compound which have plane of symmetry along with chiral centre. Compound is optically inactive due to internal compansation. compansation. Specific rotation : Observed rotation/Concentration lenght Optical purity (OP): Observed optical rotation/Optical rotation of pure enatiomer 100 Enantiomeric excess (EE): Excess of one enantiomer over other/Entire mixture 100 Mathematically optical purity (OP) =enantiomeric excess (EE) =enantiomeric Resolution : It is a chemical method to separate pair of enantiomers. enantiomers. In this method enantiomers ore first converted into diastereomers by reacting with a compound which have chiral carbon and then distill them. www.OrganicChemistry.co.in

Some chiral molecules without chiral carbon

1. Allenes with even no of double bonds & end cabon have different substituents. substituents. 2. Spiranes with even no of rings & end cabon have different substituents 3. Cycloalkylidines with some of double bonds & rings are even in no and end cabon have different substituents. substituents. 4. Ortho-ortho tetra substituted biphenyl with two different substituent Orthoat ortho position of one phenyl group. 5. Quaternary ammonium salt with all the four valancies are different. 6. Tetravalent phosphorus compounds in which all its four valancies are different. 7. Tetravalent sulphur compounds in which all its four valancies are different. 8. Tetravalent silicon compounds in which all its four valancies are different. 9. Tetravalent germanium compounds in which all its four valancies are different. 10. Any tetravalent compounds in which all its four valancies are different.

Basic for a compound to show optical activity is nonsuperimposability i.e. absence of Plane of symmetry & Centre of symmetry.
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Calculation for number of sterioisomers

Case 1 : For unsymmertical molecules with n stereocentres No. of stereo isomers = 2n Case 2 : For Symmertical molecules with n even stereocentres No. of stereo isomers = 2n 1 + 2n/2 1 Case 3 : For Symmertical molecules with n odd stereocentres Case a : Central stereo centre is optical in nature : No. of stereo isomers = 2n 1 + 2n 1/2 Case b : Central stereo centre is geometrical in nature : No. of stereo isomers =

2n 1

It is important to remember that stereocentres means any centre along which we can see stereo isomerism i.e. Optical or geometrical both.
It may be along C=C,C=N,N=N,Cycloalkanes, Cycloalkenes with C=C,C=N,N=N,Cycloalkanes, 8 of geometrical or along chiral carbon, pseudo chiral carbon or along special case of allenes, spiranes, cycloalkylidine or orthoallenes, spiranes, orthoortho tetra substituted biphenyl.
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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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Some compounds showing either GI,OI,both or none

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