Nomenclature and Isomerism

Chapter Objectives
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Introduction to organic chemistry Hybridisation of carbon in organic compounds Representation of organic compounds Nomenclature of organic compounds Isomerism Effects operating in organic systems. Fission of a covalent bond: homolysis and heterolysis Reaction intermediates: carbocations, carbanions and free radicals Different reagents: electrophiles, nucleophiles and carbene Types of organic reactions

Chemistry / Nomenclature and Isomerism

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Concept Notes
Introduction to Organic Chemistry
Organic chemistry is a new branch of chemistry. It mainly deals with compounds made up of carbon. Other than carbon some elements like H, O, N, and halogen etc. are also involved. Starting from living beings to cooking gas, all belong to this new branch of chemistry. Let us see how it is important for coming examinations. Why are there so many carbon compounds This is because a single carbon atom is capable of combining with up to four other atoms. The unique property of carbon atom is that it can combine with other carbon atoms. The ability of carbon to form a long chain bonding with other carbon atom is called catenation. Therefore carbon atoms can form chains- and rings-type compounds. The simplest organic compounds are made up of only carbon and hydrogen atoms, e.g.

CH4 , CH3 — CH3 , CH3 — CH2 — CH3 and
Methane Ethane Propane

etc.

These properties of carbon can be explained by hybridization.

2p 2p 2s E lectron P rom otion 2s sp
3

H ybridization

sp3 hybrid orbitals

1s C (ground state)

E nergy

Tetravalency of carbon
Since the 2s and 2p orbitals are very close in energy, one electron from the 2s orbital jumps to the 2pz orbital. The one 2s and three 2p orbitals mix together and give rise to four new different types of orbitals. This is called hybridization and is seen only in carbon atom. sp3 hybridization in carbon: The one 2s and three 2p orbitals mix together and give rise to four sp3 hybrid orbitals, e.g. CH4. Carbon in methane molecule forms four sigma bonds. The carbon here is sp3 hybrid carbon. The methane molecule has a tetrahedral shape. The C atom is at the centre of the tetragon (three-dimensional equilateral triangle) and the four H in the four corners of the tetragon. Each C — H bond in methane makes an angle of 109° 28’ with the other. Chemistry / Nomenclature and Isomerism ... 2

2p 2p E nergy 2s E lectron P rom otion 2s sp
3

H ybridization

sp3 hybrid orbita ls

1s C (ground state)
H 1s H sp 3 sp 3 sp 3 H 1s sp 3 H 1s H
Orientation of sp3 hybridised orbitals and overlapping with 1s orbitals of H. sp2 hybridization in carbon: Carbon also exhibits sp2 and sp hybridization. In sp2 hybridization one s and two p orbitals participate. The sp2 hybrid orbital is planar triangular in shape and the bond angle is 120°. Here the the unhybrid pz orbitals or adjacent carbons overlap to form pi bond, e.g. ethylene molecule.

σ 109 ° 28 ´ H 1s H σ C σ σ H

2p E lectron P rom otion

2p sp 2 H ybridization

U nhybridized p-orbita l

En ergy

2s

2s

sp2 hybrid orb itals

1s C (ground state)

Chemistry / Nomenclature and Isomerism

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Here three of the bonds lie parallel to each other CH CH . In acetylene in all there are three sigma bonds and two pi bonds. The angle between the direction of the bonds is 1800.There are five sigma bonds and one pi bond in ethylene as shown below.. only 1 s and 1 p orbital take part. 2p E lectron P rom otion 2p 2p 2s 2s sp unh yb ridized orbita ls sp hybrid orbita ls σ C π σ H H ybridization 1s C (ground state) 1s C (excited state) E nergy sp hybridization in acetylene For sp hybridization the molecule of acetylene is an example. π-bond 2p y H sp 1s σ 2p z sp 2p y 2p z H H π — σ — σ σ H — C —— C — H —π — σ sp sp H σ 1s π-bond Chemistry / Nomenclature and Isomerism . The rest two unhybrid p orbitals form 2 pi bonds. The shape is linear and the bond angle is 180°. 4 .. H -atom 1s sp 2 sp 2 sp 2 1s H -atom H 120 ° C C 120 ° O R 120 ° σ pz sp 2 sp 2 pz pz pz sp 2 H -atom 1s 1s H -atom H H σ 120 ° C 120 ° σ H H H H sp hybridization in carbon: In sp hybridization.

it always forms covalent bonds.g. 5 .Sigma and pi bonds When a carbon atom forms a compound. H H C H H Four electrons of carbons (x) One electron of four hydrogen atoms each ( ) (x ) represents a C — H bond. Structural representation should clearly portray the structure. s-s overlap s-p overlap p-p overlap Whereas sidewise overlap leads to pi bond as shown below + + + + + + Inte rn uclear axis p-orbitals S idew ay overla pping + + + or Final ele ctron cloud picture + + + + Structural representations of organic compounds Organic compounds and their formulae are represented using many structures. bonding and orientation of different atoms in the molecule. When the covalent bonds are linear or aligned along the plane containing the atoms. or xx e. H H H H H H—C—C—C—C—C—H H H H H H Chemistry / Nomenclature and Isomerism . Complete structural formula: Here the two atoms are represented by a dash (—).. There are various representations. Lewis structure: Here the bond C — H or C — C is represented by . the bond is known as sigma (σ) bond. There are two types of covalent bonds: sigma and pi.. Sigma bond is stronger than pi bond.. C — C (—) represents the bond.

6 . In these structures it is understood that there is a carbon atom at each ‘bend’ and that each carbon atom is attached to as many hydrogen atoms as are needed to complete its valence of four. Wedged bonds are understood to be coming out of the plane of the paper towards the reader. This is shown for methane. These structures are drawn with the longest carbon chain vertically and it is understood that all horizontal bonds are coming towards the reader. Bonds that drawn as plain lines in one of these structures are in the plane of the paper. Here only the skeleton is shown. This type of drawing is commonly used for carbohydrates. Only those atoms other than carbon and hydrogen are represented. all vertical bonds are going away from the reader and that there is a carbon atom at the intersection of four bonds. Wedge and Dash Representation This reprentation actually represents the bond projections from the plane. This is a simplified version of complete formula. This is further simplified to CH3 — CH2 — CH2 — CH2 — CH3 or CH3 (CH2)3CH3 Bond line structure: This is further simplification of the condensed formula. whereas dashed bonds are understood to be going away from the reader.. Here only the atoms are shown.. The three-dimensional structure of a molecule can be shown through the use of wedged and dashed bonds. H C H H H Fischer projections These are also used to show three-dimensions. A zig-zag structure is used for linear compounds. Cl H Br OH H Cl – – – – – – – C – – – – – – – – Br OH Chemistry / Nomenclature and Isomerism .Condensed structural formulae: In this formula the bonds are also not shown. O OH P e n ta n e B utan – 1 – 01 E th y lm e th y l e th e r Representing three-dimensional organic structures on a two-dimensional surface (such as a piece of paper) presents some challenges.

• Place the groups or atoms that are attached to each of the carbon atoms that make up the bond whose rotation is being shown on the appropriate carbon. In each pair of structures below.Newman and Sawhorse Projections Rotation around a bond in a linear structure is shown through the use of sawhorse structures or Newman projections. The structures below show only two of the many possible conformations. Draw three lines that intersect at their ends and are at 120° angles to each other so that the intersection is in the middle of the circle.. Newman projection (think of them as a head-on views of sawhorse structures) is drawn as follows: • • • • Draw a circle. H H CH3 C H3 H C H3 C H3 H CH3 H H H H H H C H3 H3 C H H H H H C H3 H Sawhorse structures are drawn as follows: • Draw three lines that intersect at their ends and are at 120° angles to each other. 7 . Draw a second set of intersecting three lines “behind the circle.. The front and back groups are drawn slightly offset in the Newman projection of the eclipsed structure so that they don’t overlap.” Place the groups or atoms that are attached to each of the carbon atoms that make up the bond whose rotation is being shown on the appropriate carbon. the conformation on the left is referred to as staggered and the conformation on the right is referred to as eclipsed. • Draw a slanted line from the intersection of the three original lines to a second set of three lines. Chemistry / Nomenclature and Isomerism . The intersection represents the carbon atom at one end of the bond around which the rotation is being shown.

The second member’s name in the derived system would be ‘Ethyl Alcohol’ because the formula of this alcohol CH3-CH2-OH shows the ethyl group attached to an OH group. Coupled with the observation that each carbon atom forms four bonds to other atoms this leads to incomprehensibly large numbers of possible molecules. These are now called common or trivial names and some are still in use today. Chemistry / Nomenclature and Isomerism . the simplest alcohol has a common or trivial name of ‘wood alcohol’. of which the IUPAC name may not be the one most commonly used. The IUPAC nomenclature system is such a set of rules used widely by organic chemists and this introduction to nomenclature will outline the rules in this system for the simpler organic compounds. The same simplest member of the alcohol family would be called ‘Methyl Alcohol’ because the formula CH3OH shows a methyl group attached to the functional group for the alcohol family. carbon atom has unique ability to form stable molecules consisting of chains of carbon atoms of any length. In the derived system. For example. Analysis of this mixture will result in a large part of this alcohol.. 8 . Another alcohol. a second nomenclature system was developed called as derived system. To name such vast numbers of possible molecules requires a systematic approach consisting of a set of arbitrary rules which are readily learned and applied to each molecule individually to generate the name. the major hydrocarbon portion of the molecule was named as an alkyl group followed by the family name. This compound was given this name because the chief source of this alcohol was the destructive distillation of wood chips. there were other attempts to produce a systematic nomenclature system before the IUPAC system and sometimes compounds have several different names.. Usually they were named reflecting the source of the compound. Wood chips can be distilled in this manner and will yield a very complex mixture. The International Union of Pure and Applied Chemists (IUPAC) developed a systematic approach to organic nomenclature. Note that in addition to names invented for compounds because of their origin. Later in the century. the second member of the alcohol family is called ‘grain alcohol’. Earlier Methods of Naming Organic Compounds Organic compounds were named prior to the end of the 19th century by those that synthesized them. This trivial name came from the fact that one of the principle sources of this alcohol is from the fermentation of grains and fruits.Nomenclature Why we need nomenclature specially for organic compounds? As we have already discussed. IUPAC came up with a set of rules to name organic compounds. Nomenclature System for Organic Compounds — IUPAC Nomenclature The use of common names and derived names did not work because large number of molecules were discovered and synthesized.

2 : Names of Representative Groups Group Name Methyl Ethyl Propyl Group −C ≡ CH Name Ethynyl Allyl CH3 — CH2CH3 — CH3 CH2 CH2 — CH3 CH CH3 −CH2 CH = CH2 Isopropyl Phenyl CH3 CH2CH2CH2 — CH 3 CH CH3 CH3 CH 2 CH CH3 n-Butyl O Phenoxy CH 2 Isobutyl CH 2 Benzyl O sec butyl C Benzoyl – CN Cyano.. Amino Hydroxyamino Hydroxy Methoxy Formyl Keto or Oxo CH3 CH 3 C CH 3 −CH2CH2CH2CH2CH3 Pentyl tert butyl – NH2 – NH2OH – OH – OCH3 – CHO O C O CH3 CH3 C CH3 CH2 Neopentyl Acetoxy C CH3 CH2 Methylene –COOH –CH2OH –SO3H Carboxy Hydroxymethyl Sulphonyl .. 9 CH2 = CH — Vinyl Chemistry / Nomenclature and Isomerism .Table 1.

A prefix and/or suffix to indicate the family to which the compound belongs. This system of nomenclature is designed to closely associate the name the compound with the structure since structure is so important in establishing the physical and chemical behaviour of organic molecules. 10 .This number will be the prefix to the molecule name. 2. the name pentanol indicates a carbon chain of length five (pent-). Longest chain rule: The first step in naming compounds is identification of the longest chain of carbons. 8-carbon chain So the largest is 8 carbon chain. A root indicating how many carbon atoms are in the longest continuous chain of carbon atoms. General rules established for all of the families: 1. 2 4 3 IV (iv) III (v) 5 VI (vi) (v) II I 6 VII VIII 7 2 1 3 4 5 1 (i) (ii) Longest chain here is 5-carbon chain The only possibility The carbon chains are of 3 different lengths 6-carbon chain. For example.Naming organic compounds using IUPAC rules At its simplest. the longest chain with functional group has to be considered. the IUPAC name for an organic compound contains these two parts: 1. If the compound has functional group. So prefix will be oct Do You Know? Greek prefixes o di for 2 o tri for three o tetra for four o penta for five o hexa for six o hepta for seven o octa for eight Chemistry / Nomenclature and Isomerism . an alkane derivative (-an-) and an OH functional group (-ol).. 7-carbon chain..

5 4 6 3 2 1 8 7 Only one branch . 5 7 4 5 8 2 1 8 6 3 2 1 3 6 7 Branch is on C-4 carbon 4. Branch is on C-5 carbon Identify the suffix — the family name. First number the longest carbon chain you have identified from one end to the other.. 11 .2 carbon .The branch always gets the lowest possible position.length branch 3. Do You Know? Do you know names of carbon chains o Meth for one carbon o Eth for a two carbon continuous chain o Prop for a three carbon chain o But for a four carbon chain o Pent for a five carbon chain o Hex for a six carbon chain o Hept for a seven carbon chain o Oct for an eight carbon chain o Non for a nine carbon chain o Dec for a ten carbon chain Chemistry / Nomenclature and Isomerism . Lowest number rule: Fix the position of branches.. Remember to number them from both the ends. To do this make sure you follow the lowest number rule. Whichever has the lowest number that is the final postion. Identify the various branches and groups attached to the following compound. To do this check out the functional group in your carbon chain.2.

depending on how many times the substituent is getting repeated. Substituents are same: If the substituents are same. 12 . tri etc. Let us take each of the special structures and learn the specific rule to name them. Special rules: There are many compounds with complicated and branched structures. Name is 3. But the position of the substituent needs to be repeated as many times. a.4-ethyl-octane These rules are adequate to name simple carbon compounds. The substituents should get the lowest possible numbers. Remember to place a hyphen between a position number and the name. multiple branch compounds some special rules are required.. 2 1 3 5 7 7 5 3 1 4 6 6 4 2 Name is 3-ethyl-5-methyl heptane Chemistry / Nomenclature and Isomerism Order of substituents is written in alphabetical order. then name them in alphabetical order. 1. with a comma in-between... then the name need not be repeated. 5-diethyl-heptane b. So either way we can assign the number. . Naming a compound with more than one substituent: When there are more than one substituent or branch they can be of various types. Indicate the carbon number of each group is attached.5 4 6 3 2 1 7 8 Saturated compound so suffix is (-ane) Name . 2 1 4 VII VI V 3 IV III 5 II 6 7 I The position of branches are same. Substituents are different: If more than one kind of substituents are present in the parent chain. But when it comes to multiple functional group compounds. Just name the branch once and add prefix di. followed by the substitute name as a series separated by commas.

Cl O –C– – one Oxo – CN – nitrile Cyano Chemistry / Nomenclature and Isomerism . Such groups are: – COOH.atom is always assigned number 1 and its position is not mentioned while writing the name of the compound.C .3 : Suffixes for groups. – CONH2 and – COCl O 2. 2 3 7 8 6 5 4 2 1 2-ethyl-4..Similar and different sets of substituents are present. Exceptions are: C = C. – CHO. C ≡ C and — C — Table 1. 3. – COO R. The name of a functional group containing compound is obtained by adding a suffix to the ‘root’ derived from the name of the hydrocarbon of longest carbon chain. 13 ..5-dimethyl octane Naming of Compounds Containing One Functional Group Additional rules are desired for naming compounds containing functional groups. 3. – CN. The suffix replaces the ending ane in most cases. The chain is numbered so that the functional group gets the lowest number. Group C=C C ≡C – OH – CHO Suffix – ene – yne – ol – al Prefix Alkenyl Alkynyl Hydroxy Formyl Group – COOH – COOR – NH2 Suffix – oic acid – oate – amine –oyl chloride Prefix Carboxyalkyl Alkoxycarbonyl Amino Chloroformyl O . Rules 1. A functional group containing a C . The suffixes for various groups are listed in Table 1.

bromo. 3.CH . 2. Priority order of functional groups Carboxylic acid > Sulphonic acid > Acid anhydride > Esters > Acid chlorides > Amides > Nitriles > Aldehydes > Ketones > Alcohols > Amines > Ethers All the remaining groups such as halo (fluoro.2) .CONH2 Cl CH3 C H3 − C H − C H2 − C OOH | OH 3.Chloro-5.Naming of Compounds Containing Two Functional Groups : Similar rules as discussed in naming of compounds containing one functional group are applied for naming compounds with two functional groups with slight modifications. For compunds with both double and triple bonds. When there is a choice in numbering. nitro (–NO2). The name of the compound ends with the suffix of the principal functional group.CH2 .COOH 1.Ethanediol CH2 . All other groups including the functional groups are used as prefixes (Table 1.4 . numbers as low as possible are given to double and triple bonds even though this may at times give “-yne” a lower number than “-ene”.CH2 .Hydroxybutanoic acid 4 3 2 1 6.CH2 .. iodo). nitroso (–NO) and alkoxy (–OR) are always treated as substituents group. then the letter ‘e’ is omitted in writing the name of the compound.CH2 .4-Butanedioic acid 6 5 4 3 2 1 HO C H2 − C H2OH 1. The following examples will illustrate these rules.CH2 . 14 . 4 HOOC .Buten -1-ol Note if the ending does not occupy the terminal position.. 4 3 2 1 CH2 = CH . Rules 1.CH2 . 2 .CH2 .methylhexanamide Chemistry / Nomenclature and Isomerism . chloro.Pentadiyne 2 1 Note here letter ‘e’ is retained because it occupies a terminal position. the double bonds are given the lowest numbers.OH (-OH is the principal functional group) 3 . Double and triple bonds are not used as prefixes. 1 2 3 4 5 HC C CH2 3 2 C CH 1 1.

2.CH . 4-dioic acid Same rules apply to compounds containing three functional groups.CH2CN NO2 5 O 4 || 3 2 1 CH3 − C − CH2 − CH2 − CHO 4. 5-diethyl-6-methylnon-5-en-1-ol 1 N.Methylhexan .CH2 . 4-dioic acid 3 HOOC trans-but-2-ene-1.6 5 4 3 2 1 CH3 . 2.CH .ene 6 5 4 3 2 C H3 − C ≡ C− C H2 − C H3 2 .Pentyne 1 2 3 4 5 CH3 1 4 3 2 1 CH3 .Oxopentanal 8 9 4.CH2 .CH3 CH3 4 .CH . 3 .CH2 . 1 2 3 4 5 6 CH2 = CH .Dimethyl-2-pentenamine H 4 1 2 3 H H 2 COOH 4 COOH H COOH cis-But-2-ene-1.Methylhex -1 .COOH CH3 3 .CH .N OH 1 CH3 CH3 4 3 4.CH2 .ol CH3 CH3 .CH2 .1.CH2 .CH2 .Propanetriol propane .Methylbutanoic acid Chemistry / Nomenclature and Isomerism . N .3 .CH . 15 .CH = CH . 3-tricarboxylic acids These rules can be illustrated by the following examples.. 4 3 2 1 3 2 CH2 — CH — CH2 COOH COOH COOH 5 1 CH2 OH CH OH CH2 OH 1.CH OH 2 ..Nitrohexanenitrile 5 6 7 2 5 4 3 2 1 CH3 .CH2 .

. Ethylcyclohexane Numbering is needed if two or more groups are present on the ring.CH2 .dimethylbutanoate 3 2 1 2 . 3 3 2 CH3 C 2H 5 4 5 6 2 CH3 4 1 1 CH3 4. The difference being the word cyclo is prefixed before the name of the parent straight chain hydrocarbons. 3 . N .CH3 1 CHO Ethyl 3.C -CH2 ..Methylpentanal CH3 CH3 CH3 .COOC2H5 CH3 CH3 .N N. Cyclopentene Chemistry / Nomenclature and Isomerism Cyclohexene . For naming monocyclic compounds same rules apply as for naming straight chain hydrocarbons.CH . Cyclopropane 2. C H 2C H 3 CH 3 Methylcyclopentane 3. 1-Ethyl-2 methylcyclobutane 1. 2-dimethylcyclohexane If a single double bond present in the ring.propanamine Naming of Monocyclic Compounds Rules 1.CH2 .CH2 . no numbering is needed.CH3 4 3 2 1 5 4 3 2 CH3 . Cyclobutane Cyclopentane Cyclohexane If a single substituent is present on the ring. 16 . then no numbering is needed.Dimethyl -1.CH2 .

then the principal functional group gets the lowest number O OH 1 6 5 4 2 1 6 2 5 3 4 C CH 3 CH 3 4. 3-Dimethylcyclobut-1-ene If two functional groups are present on the ring. 1. These are of three main types and named differently. 17 .Dimethylcyclohex 2-ene-1-one CH 3 2-Ethynylcyclohex-1-ol The following cyclic compounds have special nomenclature.5. Chemistry / Nomenclature and Isomerism . COOH O Cyclopentanone CO OCH 3 Cyclohexanecarboxylic acid COCl CONH2 Carbomethoxycyclopentane Cyclobutanecarbonitrile Cyclohexane carbonyl chloride Naming of Bicyclic Compounds Compounds containing more than one ring and close rings have two or more of the same carbon atoms called polycyclic. CH3 3 4 5 6 2 1 CH3 3 2 4 1 CH3 3 . numbering is needed and the lowest number is assigned to the carbon atoms linked with the double bond.. A compound containing rings with an adjacent carbon atom in common is called a condensed ring system. If one or more double bonds and a group or groups are present on the ring. 4.Methylcyclohexa -1. 4 -diene 6.. A compound containing rings with one common carbon atom is called spiro cyclic. The numbers to the groups are assigned by going around the ring.

Chemistry / Nomenclature and Isomerism . For substituted bicyclic ring systems.2. 1] octane Note that the right hand ring is larger. Numbering of the remaining carbons proceeds around each ring in turn beginning with the largest ring. In doing this the lowest number is assigned to groups and double bonds.1] heptane. the number 1 position is assigned to the bridgehead carbon. 2. these carbon are called bridgehead carbons.cyclic rings). therefore. The compound’s name is derived from heptane and is called bicycloheptane(2 . 7-Trimethylbicyclo [2.. Spirocyclic Condensed Bridgehead In order to name a bridgehead hydrocarbon. 2. we must identify the carbons to which the rings are joined. the compound is named bicyclo [ 2. In the above case there are seven.. B ridge head carbon 1-C arbo n 2-C arbo n 2-C arbo n Bridgehead carbon The total number of carbon atoms are counted. 7 1 6 4 2 3 6 4 7 1 2 3 5 5 Bicyclo [2. The numbers are written in parenthesis and in decreasing order. 18 .ene 8 7 7 6 4 1 1 2 O 2 6 3 5 4 3 CH3 5 1. 1] heptane Bicyclo [2. 2. 7. 1] hept -2. 1] hept-2-one 3-Methylbicyclo [3. There are two carbons on each side and one above.A compound containing more than two atoms is called a bridgehead ring system. 2.

8 7 1 2 4 5 3 6 Bicyclo [2. 3. 2.. structural and stereoisomerism which are further subdivided as shown in the diagram. These characteristic endings are as follows: o ‘ane’ for the alkane family o ‘ene’ for the alkene family o ‘yne’ for the alkyne family o ‘ol’ for the alcohol family o ‘al’ for the aldehyde family o ‘one’ for the ketone family o ‘oic acid’ for the carboxylic acid family Isomerism The existence of different compounds with the same molecular formula but different structural formula is called isomerism. Isom erism Structrual Isom erism C hain Isom erism Functional Isom erism P ositional Isom erism R ing C hain Isom erism M etam erism Tautom erism Stereoisom erism C onform ational Isom erism C onfigurational isom erism G eom etrical isom erism O ptical isom erism Chemistry / Nomenclature and Isomerism .. The two chloropropanes are isomers. Isomerism has been classified into two types. 2 ] octane Bicyclo [1. Compounds which have the same molecular formula but differ in physical and chemical properties are called isomers. 19 . 1. 0] nonane Do You Know? End the name by attaching the characteristic ending that has been established for each family. 0] butane Bicyclo [4. Thus 1-chloropropane and 2-chloro propane depict the relationship of isomerism.

CH3OCH3 CH3 CH2 OH Note: Alcohols and ethers are always functional isomers.5 ° C CH — CH3 CH3 Isobu tane m . . so are carboxylic acids and their esters.p. 2 7 ° CH 3 Iso -p entane CH3 C CH 3 CH3 N eo-pen tane CH3 CH2 CH2 CH2 OH 1-Butanol CH3 CH CH2 OH CH3 2-Methyl propanol Functional Isomerism It is the type of isomerism in which the compounds possess the same molecular formulae but differ in the functional groups. 3 6 ° CH3 n-penta ne C 5 H 12 P entane CH C H 2 CH 3 CH3 m . CH3 CH2 CH2 CH2 CH3 m . CH3 CH3 − CH2 −CH 2 − CH3 B utane m .p.p . CH3 CH2 CH2COOH O || CH3 CH2 C OCH3 Ask Yourself What other compounds would show functional isomerism? Chemistry / Nomenclature and Isomerism ..p.Chain Isomerism In this type of isomerism the compounds possess same molecular formula but differ in the arrangement of carbon chains. -12 ° C Pentane has the following three chain isomers. 20 ..0.

g.Chloropentane CH3 — CH2 — CH 1-butene CH2 2-butene A disubstituted benzene has three positional isomers..M eth oxypropane O CH3 — CH2 — C — OCH2 — CH3 E thyl propanoate CH 3 — CH 2 — N H — C H 2 — C H 3 N -E thyl ethanam ine Chemistry / Nomenclature and Isomerism O CH3 — C — OCH2 — CH2 — CH3 P ropyl e than oate C H 3 — N H — CH 2 — CH 2 — C H 3 N -M ethyl propylam ine . e. CH 3 C H 2 O C H 2 C H 3 E thox ye thane C H 3O C H 2 C H 2 C H 3 1 . 21 .. ketones. CH3 — CH2 — CH2 — CH2 — OH 1 .Butanol CH3 — CH2 — CH — CH2 — CH3 Cl 3 .Butanol CH3 — CH — CH2 — CH2 — CH3 Cl 2 . Metamerism occurs in amines.Positional Isomerism It is the type of isomerism in which the compounds possess the same molecular formula but differ in the position of the same functional group. OH OH NO2 NO2 NO2 p-nitrophenol o-nitrophenol m-nitrophenol OH Metamerism It is the type of isomerism in which the compounds possess the same molecular formula but the distribution of alkyl groups on either side of the functional group is dissimilar.Chloropentane CH3 — CH CH — CH3 CH3 — CH2 — CH — CH3 OH 2 . ethers and esters.

in the presence of an acidic or basic catalyst a rapid equilibrium is established between an aldehyde or ketone and its isomeric (tautomeric) forms. 22 .. O OH C C CH C Keto-form Enol-form CH2 Cyclopropane Presence of at least one hydrogen atom is essential adjacent to the carbonyl group for a compound to exhibit keto-enol tautomerism. O O OH CH3 C CH 3 CH3 C CH2 Does not show keto enol tautomerism Shows keto-enol tautomerism Chemistry / Nomenclature and Isomerism .e. i. It is due to the presence of labile hydrogen atom. Keto-enol Tautomerism In the particular case of keto-enol tautomerism.. This is dynamic isomerism because the structures are in equilibrium with each other. C3H6. Some common type of tautomerism are (i) keto-enol tautomerism (ii) nitro-aci tautomerism (iii) nitrite-nitro tautomerism.Ask Yourself How many isomers are possible by compound having formula C4H10O? Ring chain isomerism This type of isomerism is due to the difference in linkage of carbon atoms in the form of ring or open chain structure. CH3 — CH CH2 propene CH2 CH2 Tautomerism It is the phenomenon of existing of single compound in two readily interconvertible structures called as tautomers which appears in acid catalysed or base catalysed conditions. For example. the isomers or the tautomers contain a keto and an enol form.

H-bond formation results in appreciable stability of the enol-form and sometime. H O O CH3 O C CH O C CH3 CH3 C CH2 C CH3 Keto enol tautomerism is also exhibited by cyclic compounds. Chemistry / Nomenclature and Isomerism . (i) If the enolic double bond is in conjugation with other double bond: For example. 23 . Generally. In the following compound.. These exist in solution simultaneously unlike the resonance structures. Phenols > β-diketones with phenyl group > β-diketones > β-ketoesters > normal aldehyde and ketones. resonance also stabilises enol form..These tautomeric forms are two different molecules. O CH3 C CH2COO C2H5 CH3 OH C CHCOOC2H5 Percentage of enol form decreases in the following order. the keto form is of lower energy than the enol form and thus more stable. An important example of this type of tautomerism is acetoacetic ester. O OH OH OH There are certain cases when enol forms are more stable. O O O — H O H 3C — C — C H 2 — C — O E t 36% +O — H O – H 3C — C CH — C — OEt 64% H 3C — C — C H C — OEt Enol form is stabilized by resonance and intramolecular H-bonding. One form can be more stable than the other.

Chemistry / Nomenclature and Isomerism . generally a H-atom. 2. Ph Ph CH Ph sp 3 C O R Ph C sp 2 C OH R In keto form. Resonating structures are arbitrary and do not exist. Resonance involves a shift in the position of electrons only. Difference between resonance and keto-enol tautomerism Resonance 1. 24 . 3.(ii) Enols with strongly electron-withdrawing groups are stable at room temperature as the tautomerization becomes slow. Tautomers exist in solution as they are different compounds. Resonating structures lower the potential energy and thus stabilize the molecule. These structures do not exist in equilibrium. Keto-enol tautomerism Tautomerism involves a change in the position of an atom. O F3C — C — CF2H OH F3C — C CF2 (iii) Aromaticity can stabilize the enol forms in ring compounds. O H H O H (iv) H H O H OH OH OH Presence of bulky groups can destabilise keto compounds. In resonance structures. 5. The tautomeric structures have no stabilization effect on the molecule. They exist in dynamic equilibrium. sp3 hybridised carbon atom cannot arrange two bulky groups (bond angle : 109°28 ' ) while in enol form sp2 carbon atom (bond angle 120°) can arrange the bulky groups at greater distance and hence stabilises it.g.. the functional group does not change. e.. 4. The tautomeric forms possess different functional groups.

. O Example 2: O + O – O S o on Answer: (b) Keto-enol tautomerism is observed in O O H (a) P h C O (b) P h C O CH3 CH3 C CH3 Ph (c) P h C Ph (d) P h C O Solution: OH CH3 Ph C CH2 Ph C Only this compound has α-H atom which can involve in tautomerism. Hence. it will not tautomerize.. Answer: (b) Nitro-aci tautomerism O CH3 N O CH2 O N OH (N itroform ) (A ci form ) Chemistry / Nomenclature and Isomerism . benzoquinone is very stable through conjugation. 25 .Illustrative Examples Example 1: Which of the following compounds does not show tautomerism? (a) (b) O O O O O (c) Solution: (d) CH CH OH O Among the given options.

. which gives few products having same molecular formula. There are two extreme forms.Nitrite-nitro tautomerism O H O N O H N O N itro fo rm N itrite fo rm Introduction to Stereoisomerism There are some reactions. CH3 — CH3. Their compounds differ in arrangement of atoms or groups in 2-D or 3-D space. Their products can only be distinguished on further analysis. Stereoisomerism and Its Classification This has the same structural formulae but different spatial arrangements. the carbon-carbon bond is formed by the axial or head on overlapping sp3 hybrid orbitals of the adjacent carbon atoms. Conformations of Ethane In ethane. allows freedom of the free rotation about the C — C bond because of axial symmetry. Chemistry / Nomenclature and Isomerism . The different arrangements of a molecule can be obtained by rotation around C — C single bonds are called conformers or conformational isomers. but their physical and chemical properties are different. They can be represented by Sawhorse or Newman projections. Definition: It is the study of spatial arrangement (arrangement of atoms or groups in two-dimensional or three-dimensional space) of atoms in any given compound. The staggered and eclipsed conformations. The electron distribution in the bond is symmetrical around the internuclear axis (molecular axis). the molecule can have different spatial arrangements of atoms or groups attached to the carbon atoms. As a result of rotation about the C — C single bond. 26 . Ste re oisom ers C onfigu rational isom erism C onform ational isom erism G e om etrical isom erism Conformations O p tical isom erism In alkanes.. The carbon-carbon single bond. As a result. The molecular geometry corresponding to a conformer is known as conformation. Such compounds are known as isomers and the chemistry which deals with these compounds is called stereochemistry. therefore. the methyl groups can rotate about the C — C bond. an infinite number of spatial arrangements of ethane are possible.

The reverse is true with the eclipsed conformations due to the minimum distance between hydrogen atoms.H H H H H H eclipsed form H stagge re d form Conformations of ethane (Sawhorse model) H H H H H H H repulsion H H H H H H H H H H eclipsed form stagge re d form Conformations of ethane (Newman projection) The staggered conformation is associated with minimum energy because the repulsive interactions between the hydrogen atoms attached to the two carbon atoms are minimum due to the maximum distance between them.6 kJ m ol – 1 stagge red R otatio n ab out C – C b ond of ethane However. the energy difference between the staggered and eclipsed conformations is only 12. staggered conformation is more stable than the eclipsed form. However. At any given time. eclipsed P otential energy 12.. it is usually not possible to separate them from one another. at room temperature. we would expect a greater percentage of ethane molecules to be in staggered conformation because of its lower energy. Chemistry / Nomenclature and Isomerism .6 kJ mol–1. Thus. 27 ..

In the boat form. H H H H H H C hair form H H H H H H H H H H H H B oat form H H H H H H The energy difference between the boat and chair conformations is 44 kJ mol–1. two strainless ring conformations are possible. Cyclopropane and cyclobutane are planar molecules. Consequently they are called strainless rings. there are large differences between the tetrahedral angle (109° 28´) and the actual bond angles. They are called chair and boat form.Conformations of Cycloalkanes In cyclopropane and cyclobutane. In the case of cyclohexane. Cyclohexane exists in chair conformation at room temperature.4 kJ m ol– 1 –1 chair form Relative energies of the conformations of cyclohexane molecule Chemistry / Nomenclature and Isomerism . the normal bond angle (109° 28’) is retained and they are free from any strain. So these molecules have considerable strain and hence they are less stable and highly reactive.. the bond angle is 60° while in cyclobutane it is 90°. The chair form does not have these unfavourable interactions and all the hydrogen atoms are fully staggered. half chair Tw ist boat half chair P otential ene rg y 44 kJ m ol – 1 22 kJ m ol chair form 28. The chair form is more stable than the boat form and has the lower energy. 28 . In cyclopropane.. Thus. Higher cycloalkanes are not planar they are puckered. any hydrogen atoms on the adjacent carbon atoms correspond to the unfavourable eclipsed conformation.

p.Geometrical isomerism Geometrical isomerism or the cis-trans isomerism is a consequence of restriction to rotation about a C = C bond. Another example is H C C H H C C CH3 H H3C cis-2-butene CH3 H 3C trans-2-butene Chemistry / Nomenclature and Isomerism . H C HOOC C COOH H H C HOOC C COOH H cis – butenedioic acid Maleic acid m. H H C H C H H C H C H H H H Rotation about C – C bond possible Rotation about C = C bond not possible Let us consider two different compounds which contain the same atomic pattern: one is maleic acid and the other fumaric acid. then it is called cis and if on opposite side then it is trans isomer. 29 .89 µD = 0 Chemically.p.69 trans – butenedioicacid Fumaric acid m... these isomers also behave differently. Maleic acid on heating to 150° C is converted to maleic anhydride while fumaric acid is recovered unchanged.0 These two acids thus show geometric or cis-trans isomerism. The trans-isomer being symmetrical has zero dipole moment while the cis-form has appreciable value of dipole moment H C Cl C Cl Cl H H C C Cl H µD = 1. 287° µD = 0. The geometric isomers differ in their physical and chemical properties. The two groups around the C = = C bond can be arranged in two different ways to give two types of isomers. If similar groups are placed on the same side. 130° C µD = 1.

30 H 5C 2 H H C H H C C 2H 5 H H C H C C H CH3 H cis-trans tra ns-trans tran s-cis Chemistry / Nomenclature and Isomerism . In such compounds the rotation about a C – C bond is not possible due to rigidity of the ring. e. but presence of a double bond is not enough. 4-heptadiene has four geometrical isomers. the two groups attached to a carbon atom should be dissimilar. H C C H CH 3 C C H Cl C C H C2H5 C2H5 CH3 C 2H 5 Cl H (Shows geometrical isomerism) (No geometrical isomerism) (No geometrical isomerism) Other compounds containing a C = N. (i) If an unsaturated compound has two or more double bonds and at least two of the end groups are different. N = N also show geometrical isomerism. In addition. 2.. H 3C — C H H C C H C C H C 2H 5 CH — CH C H — C 2H 5 H C H 5C 2 C H C C H C C C CH3 H 3C H H 3C cis-cis . where x = Number of double bonds.. the following idea will help. H H H COOH COOH COOH cis-isomer H COOH H trans-isomer H H OH OH OH cis-isomer OH H trans-isomer To find out the number of geometrical isomers. Compounds containing a C – C bond also exhibit geometrical isomerism as the cyclic compounds.It is stated that the geometric isomerism is due to the presence of a C = C bond. then number of geometrical isomers are 2x.g.

. Again for 2.g. H 3C — CH CH — CH CH — CH CH — CH 3 C 2H 5 tra ns-trans H C 2H 5 H 5C 2 H tra ns-cis 3 −1 2−1 Number of geometrical isomers = 2x −1 + 2y −1 = 2( ) + 2( ) = 22 + 21 = 6 Since the number of double bonds are 3. In plane polarised light. 6-octatriene. the vibration takes place only in one plane. This activity is referred as optical activity. where 2 x +1 y= when odd number of double bonds are present. let us find out the number of geometrical isomers.(ii) If the compound consists of two or more double bonds and when two end groups are same. the number of geometrical isomers is 2x −1 + 2y −1 . Light is propagated by a vibratory motion of the particles present in the atmosphere. They can only be distinguished by their ‘action on plane-polarized light’. 3. 31 . vibration occur in all planes at right angles to the line of propagation. 4. in ordinary light. vibration in other plane being cut off by passing it through nicol prism. ∴ x = 3. x y = when even number of double bonds are present. e. H 5C 2 — C H C H — C 2H 5 CH — CH H C C H C 2H 5 H 5C 2 C H H C H C H C 2H 5 H 5C 2 C H H C C H C C C H C C H C C C H H 5C 2 H H cis-cis cis-trans Here cis-trans and trans-cis are same isomers. Now a question arises: What is optical activity? So let us seek the answer to this question. Chemistry / Nomenclature and Isomerism . Thus. 2 x = Number of double bonds.. y = 3 +1 =2 2 Optical Isomerism The optical isomers have the same chemical reactions and will be alike in all physical properties. 5-octadiene has three isomers.

4. the plane having been rotated through the angle ‘α‘. 2. have the property of rotating its plane through certain angle which may be either to the left or to the right. The amount of substance in tube. αobs → Observed angle of rotation. It is defined as the number of degrees of rotation observed when light is passed through one decimetre of its solution having concentration 1 g per millilitre. Wavelength of light used. Chemistry / Nomenclature and Isomerism . It is so made that light moves vibrating in all directions except one cut off by refraction to one side of the prism. Length of solution examined. C → Concentration of the active compound in grams per millilitre. 1.O rdinary light w aves vibrating in all directio ns N icol prism P lane po larized lig ht w aves vibrating in one dire ction Do You Know? A nicol prism is constructed of iceland spar. Temperature of the experiment. The observed rotation of the plane of polarised light produced by a solution depends on the following. l×C where α → Specific rotation. l → Length of the solution in decimetre. a substance which is doubly refracting. Specific rotation It is used for the measurement of optical rotations. 3.. Certain organic compounds. t °C α [α ]D = obs . If the polarised light has its vibration in the plane XY before entering such a solution. when their solutions are placed in the path of a plane polarised light. X X' X X' α S olution Y Y' Y' Y This property of a substance of rotating the plane of polarised light is called optical activity and the substance possessing it is said to be optically active. 32 . the direction on leaving it will be changed to say X’Y’..

Such forms of the same compounds which differ only in their optical properties are called optical isomers and the phenomenon is termed as optical isomerism. P lane rotated to the left (Laevo rotato ry) P lane po larised light P lane rotated to the right (D extro rotatory) The organic compound showing optical activity may exist in following three forms..Latic acid ( ± ) Lactic acid Melting point (°C) 26 26 26 Density 1. 33 . melting point..g.It is customary to denote the temperature and wavelength of light used as a subscript.. etc. It is a mixture of equal amounts of (+) and (–) forms. [α ] → stands for D specific rotation at temperature t degrees celsius and using D-line of sodium light. Chemical properties of optical isomers are same towards achiral reagents.248 [α]D 25° +2.7 The positive sign indicates the direction of rotation towards right. The specific rotation may be different in different solvents and different concentration. solvents and catalysts. etc. Physical properties of lactic acids Name (+) .248 1. Laevorotatory — rotating the plane of polarised light to the left [(–) form] 2. solubility. but towards chiral reagents they reacts at different rates. For example: Lactic acid may exist as: (i) (+) — Lactic acid (ii) (–) — Lactic acid (iii) ( ± ) — Lactic acid Optical isomers have identical physical properties like boiling point. t °C [α]D 25° = 24.248 1. e. and the negative sign indicates the direction of rotation towards left.Lactic acid (–) . Racemic mixture — an inactive form which does not rotate the plane of polarised light at all. Dextrorotatory — rotating the plane of polarised light to the right [(+) form] 3.00° Chemistry / Nomenclature and Isomerism .24° 0.24° –2. 1.

P lane of sym m etry Centre of symmetry: The centre of symmetry is defined as that point (atom) in a molecule from which if a straight line is drawn from any part of the molecule through that point (atom) and extended to an equal distance by a straight line on the other side. a like point (atom) is encountered. 34 . The necessary condition for a molecule to exhibit optical isomerism is dissymmetry or chirality. It is represented by ‘σ’. For example: F C C F F HOOC HO H COOH OH H P lane of sym m etry F 2. Any molecule or compound is said to be chiral or dissymmetric if: (i) It is non superimposable on its mirror image. For example benzene C C C C C C entre of sym m etry C Chemistry / Nomenclature and Isomerism . A molecule as a whole is asymmetric if it does not possess any element of symmetry such as: 1. Plane of symmetry: The plane of symmetry of a molecule represents a plane bisecting the molecule such that each half of the molecule is the mirror images of the other half. For example: M irror plane CH3 CH3 Cl Cl C H M irror p lane F Br Br C I Cl C H 2C H 3 (a) H 3C H 2C C H F (b) Cl C I (ii) It does not contain any element of symmetry. It is symbolised as C.Chirality A compound of carbon is said to be asymmetric or chiral if four different atoms or groups are bonded to it. and is also called centre of inversion...

e. i. (2) The asymmetric carbon atom is in the paper plane and is represented at the intersection of crossed lines. CH3 C H C C CH3 H CH3 C H C C CH3 H 1. (4) Horizontal lines represent bonds coming toward the observer. To overcome this difficulty we use Fischer projections.dim ethylallene H H C H The shaded and unshaded orbitals are at right angles to each other. i. 35 . groups attached to the horizontal lines are understood to be present above the planes of the paper.. C C H Fischer Projections When we attempt to depict configuration. but there are certain compounds such as: Allenes (R — CH == C == CH — R). we face the problem of representing three-dimensional structures on a two-dimensional surface. The following points are followed in writing the Fischer formula. For example: COOH COOH (1) COOH NH2 C CH3 H NH2 C CH3 H C H 3C H NH2 Chemistry / Nomenclature and Isomerism .. and thus lie in different planes. with the most oxidized carbon at the top. the presence of a chiral centre is considered as the cause of optical activity.e.These stereoisomerism which are related to each other as non superimposable mirror images and do not contain any element of symmetry are called as enantiomers. (3) Vertical lines are used to represent bonds going away from the observer. which are chiral or dissymmetric but do not contain any asymmetric carbon and show optical activity. (1) The carbon chain of the compound is arranged vertically. 3 . groups attached to the vertical lines are understood to be present behind the plane of the paper. In general.

CHO H OH CH2OH (I) First in t e rch an ge H OHC OH CH2OH (II) S e co nd in t e rch an ge H OHC OH C H 2O H (III) Structres (I) and (III) are identical.CHO CHO (2) CHO Visua lise the structure such tha t th e m ain s C arbo n cha in is vertical H C OH H OH C H 2O H H OH C C H 2O H C H 2O H In order to convert one Fischer projection to another identical form. A Fischer projection may be rotated by 180 ° in the plane of the paper (around a point) but not 90° or 270° to obtain an identical structure.. One interchange leads to an enantiomeric structure. CHO H OH C H 2O H (I) 180° HO C H 2O H H CH O (II) Structures (I) and (II) are identical. any two pairs of substituents (even interchanges) linked to the chiral carbon need to be interchanged. A 90° rotation results in an enantiomeric form. 36 . Structures (I) and (II) are enantiomers.. Chemistry / Nomenclature and Isomerism .

But we have no knowledge of the absolute configuration of the either isomer.. D and L system This system has been used to specify the configuration at the asymmetric carbon atom. i. Before we discuss about any type of absolute configuration. about the asymmetric carbon atoms.g lucose OH H OH OH OH H OH OH CHO H HO H H C H 2O H L . 37 Chemistry / Nomenclature and Isomerism .glucose . say (+) and (–) lactic acid. we cannot tell as to which of the two possible configurations corresponds to (+) acid and which is the (–) acid. CHO H C OH OH CHO C H C H 2O H (+) . it belongs to D-series and if it can be related to L(–) glyceraldehyde.glyceralodehyde D C onfiguration C H 2O H ( – ) . we must distinguish between relative and absolute configurations. it should be remembered that there is no relation between configuration and sign of rotation.( – ) . Let us consider a pair of enantiomers. COOH H C CH3 (+) – Lactic acid COOH OH C CH3 (–) – Lactic acid OH H We know that they differ from one another in the direction in which they rotate the plane of polarised light. the compounds belong to L-series.(+) . In this system.e. the configuration of an enantiomer is related to the two forms of glyceraldehyde were arbitrarily assigned the absolute configuration.glyceralodehyde L C onfiguration If the configuration at the asymmetric carbon atom of a compound is related to D(+) glyceraldehyde.Absolute Configuration While discussing optical isomerism. For example: CHO H HO H H C H 2O H D ..

CHClCH3 C3 has CH3 .Br. Diastereomers have different physical properties and differ in specific rotation.. the configuration in the dotted bracket is similar to that of L-glyceraldehyde.e. These two pairs of enantiomers will give rise to two possible racemic modifications.S erin e In this example.H. II and IV are also not enantiomers but optically active isomers.. can give four possible stereoisomeric forms. it belongs to L-serine Optical Isomerism in Compounds with More Than One Asymmetric Carbon Atoms An organic compound which contains two dissimilar asymmetric carbons. Thus. 2-bromo-3-chlorobutane may be written CH3 1 *H C 2 *H C 3 CH3 4 Br Cl The two asymmetric carbons in its molecule are dissimilar in the sense that the groups attached to each of these are different. the positions of H. i. Chemistry / Nomenclature and Isomerism . Similarly.Cl. They may have same or opposite signs of rotations. CH3 CH3 CH3 CH3 H H C C CH3 (I) Br Cl Br Cl C C CH3 (II) H H Br H C C CH3 (III) H Cl H Cl C C CH3 (IV ) Br H The forms I and II are optical enantiomers and so are forms III and IV. if we replace .NH2 by OH.Compare the dotted brackets of glyceraldehyde and glucose. Such stereoisomers which are optically active isomers. For example: COOH H 2N H C H 2O H L . 38 . C2 has CH3 . Thus.( – ) .CHBr CH3 Such a substance can be represented in four configurational forms. OH and CH2OH are similar in both cases and hence we can assign D and L configuration to glucose. are called diastereoisomers or diastereomers. but not mirror images.H. the other two forms. The I and III are not mirror images or enantiomers and yet they are optically active isomers.

666 [∝]2 +12° –12° 0° 0° Chemistry / Nomenclature and Isomerism .760 1. II and III arrangements. if the force which rotates the plane of polarized light is directed from H to OH.760 1... since the rotatory power of the upper left half of the molecules is balanced by that of the lower half.Isomerism in Tartaric Acid The two asymmetric carbon atoms in tartaric acid are * C H (O H )C O O H * C H (O H )C O O H The possible arrangements are COOH H HO C C OH H HO H COOH C C H OH HO HO COOH C C H H H H COOH C C OH OH COOH COOH COOH COOH (I) (II) (III) (IV ) Of these. Now.697 1. 39 . (I) (II) (III) Structure I will rotate the plane of polarized light to the right and will represent (+) – tartaric acid. Name (+) – tartaric acid (–) – tartaric acid (±) – tartaric acid meso – tartaric acid Melting point (°C) 179 170 206 140 Density 1. The physical properties of the four tartaric acids are tabulated below. for tartaric acid we use only I. COOH P lane of sym m e try H C OH H C OH COOH Such arrangement is also termed as meso forms. Therefore. Structure II will rotate the plane of polarized light to the left and will represent (–) – tartaric acid. Structure III will represent optically inactive tartaric acid. formula IV when rotated through 180° in the plane of the paper becomes identical with formula III.

n −1 . When the molecule can be divided into equal halves. then The number of d. m = n   −1 2 2  . In all the above cases. The number of meso.forms. Since the optical isomers have identical physical properties. then the number of d. the molecule has symmetry and the number of asymmetric carbon atoms is even. a The number of racemic forms will be .forms. 2.forms. a solution of lactic acid may be treated with an optically active base such as the alkaloid (–) – Brucine. Biochemical methods 4. Total number of optical isomers = a + m = 2n−1 + 2 2 3. Total number of optical isomers = a + m = 2n. 1. m = 2 n 1 − 2 2 n 1 − 2.. then the number of d. The number of meso. a = 2n–1. Selective adsorbtion In general. Kinetic methods 5. 40 Chemistry / Nomenclature and Isomerism .and l. When the molecule can be divided into two equal halves and the number (n) of asymmetric carbon atom is odd.and l.and l. i. Mechanical methods 3. The following methods can be used for resolution.forms. For example.e. a = 2n.e.forms. 2 Resolution of Racemic Mixture The separation of a racemic mixture into its (+) or (–) components is termed resolution. m = 0. i. we use chemical method of resolution in which ± mixture is mixed with another suitable optically active isomer when the products are no longer mirror image isomers and may be separated by crystallization. (+) – Acid (–) – Base (–) – Acid (–) – Base . Chemical methods 2. The resulting product will consist of two salts: 1. . the molecule has no symmetry and (n) is the number of asymmetric carbons atoms. Total number of optical isomers = a + m = 2n−1 . they cannot be separated by ordinary methods such as fractional crystallization or fractional distillation.Number of Possible Stereoisomers in Compounds Containing Different Number of Asymmetric Atoms 1. 2..forms. When the molecule cannot be divided into two equal halves. a = 2n−1 − 2 2 The number of meso.

Inspection of the configuration of the two salts shows that they are not enantiomorphic. Therefore, they have different solubility in water and can be separated by fractional crystallization.

Chemical Reaction and Stereochemistry
Stereoselective reaction: A stereoselective reaction is one in which the reactant is not necessarily chiral (as in the case of alkyne), but in which the reaction produces predominantly or exclusively one stereoisomeric form of the product. Stereospecific reaction: A stereospecific reaction is one that produces predominantly or exclusively one stereoisomers of the product when a specific stereoisomeric form of the reactant is used. It should be noted that all stereoisomeric reaction are stereoelective, but the reverse is not necessarily true. For example synthesis of trans-2-butene from 2-butyne.

CH3

C

C

CH3

(1) L i, E tN H 2 (2) N H 4 C l

CH3 C H C

H

2-B utyne

CH3 Trans - 2 - bu tene

Here the possible products can be trans-2-butene as well as cis-2-butene. But trans-2-butene is formed predominantly thus showing that it is a stereo selective reaction. Example of stereospecific reaction Reaction of cis- and trans-2-butene with Br2. One stereoisomeric form of the reactant, say trans-2-butene, gives one product, i.e. meso compound. Whereas the other stereoisomeric form of cis-2-butene gives racemic mixture.

H 3C C C H

H B r2 C C l4 CH3

CH3 Br C C H CH3 2, 3 - D ibrom obuta ne (m eso com pou nd) Br H

tra ns - 2 - butene

Chemistry / Nomenclature and Isomerism

... 41

H 3C C C

H B r2 C C l4

CH3 Br C + C Br Br CH3 Br H H

CH3 Br C C H CH3

H 3C H cis - 2 - bu ten e

(R acem ic m ixture)
Regioselective Reactions: When a certain 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 regioselective, e.g. alkynes react with HCl and HBr to form haloalkenes or geminal dihalides following Markownikoff’s rule.

R

1

C

C

R

2

HX

H C R
1

R C X

2

H HX R
1

X C X R
2

C H

Asymmetric synthesis When a compound containing an asymmetric carbon atom is synthesized by ordinary laboratory methods from a symmetric compound, the product is a racemic mixture. If, however, such a synthesis is carried under the ‘asymmetric influence’ of a suitable optically active reagent, one of the optically active isomers is produced in preference. This kind of process in which an asymmetric compound is synthesized from a symmetric compound to yield the (+) – or (–) – isomer directly, is termed as asymmetric synthesis. For example, when pyruvic acid is reduced as such, it yields (±) – lactic acid. However, when pyruvic acid is first combined with an optically active alcohol, e.g. methanol (R OH) to form an ester, which is then reduced the product upon hydrolysis yields (–) – lactic acid in exess.

CH3 — CO — COOH + CH3 P yru vic acid CH H 2C H 2C CH C H (C H 3 ) 2 (M enthol) CH2 CHOH

CH3 — CO — COOR M enthyl p yru va te +H 2 O H CH3 — C — COOH + ROH OH ( – ) – lactic acid (exce ss)

Chemistry / Nomenclature and Isomerism

... 42

Where

CH3 CH CH2
R=

CH2 CH — O — CH C H (C H 3 ) 2

CH2

Importance of Stereochemistry
1. Biological importance Chirality is a phenomenon that pervades the universe. (a) The human body is structurally chiral with the heart lying the left of the centre and the lever to the right. (b) Helical seashells are chiral. (c) All but one of the 20 amino acids that make up naturally occurring protein are chiral and have L-configuration. The synthesized D-protein is resistant to break down by enzymes. Chemical importance Stereochemistry plays an important role in deciding the physiological properties of compounds, e.g. (a) (–) – nicotine is much more toxic than (+) – Nicotine. (b) (+) – adrenaline is very active in construction of blood vessels than (–) – adrenaline. Chiral drugs Chirality is crucial for the effect of drugs. In a majority of cases only one enantiomers is found to have the desired effect, e.g. (a) (+) – thalimide has the intented effect of curing morning sickyness. (b) (s) – enantiomers of ibuprofen has the pain-relieving action. There are several factors that influence the behaviour of organic molecules. Many of the properties such as acidic and basic strengths, boiling point, solubility in water, rates of chemical reactions and stability of intermediates can be predicted on the basis of the following effects. (i) Resonance (ii) Inductive effect (iii) Electromeric effect (iv) Hydrogen bond (v) Steric efftect (vi) Hyperconjugation

2.

3.

Chemistry / Nomenclature and Isomerism

... 43

The negative charge must preferably lie on the most electronegative atom. CO3 2 Different structures of a molecule which differ in the position of electrons are called resonance contributing structures or canonical structures. this mode of stabilizing substances is called as resonance.. The resonance structures are only arbitrary or imaginary. Dispersal (or delocalization) of electrons decreases the potential energy of a molecule and enhances its stability. The resonance hybrid is more stable than the contributing structures. 44 – –O C O Resonance hybrid structure Chemistry / Nomenclature and Isomerism . Two or more structures must then be combined to provide a good description of the molecule. It is represented by a double headed arrow (↔ ) . 2− the charge is equally distributed on all the atoms. many molecules cannot be represented adequately by a single Lewis structure.g. This distribution is called In case of an ion CO3 dispersal of charge and it leads to greater stability. the more stable is the molecule. One can draw different resonance structures of a molecule by using the following rules. . The following structure is for benzene. The larger is this energy. The resonance energy is a measure of the stability of the molecule. The resonance energy of a system is the difference in energy between the actual energy of the hybrid and the energy of the most stable contributing structure. etc. Examples are (C6H6).. tautomerism). The resonance energy is measured by taking a model molecule. Benzene has resonance energy of 36 K cal per mole. It contains an alternating system of single and double bonds (a conjugated system). 2− ion and SO .Resonance Ethylene can be represented by a single Lewis structure. O– O– O ( ) O – C O – O – C O – O O C – O Resonance is also called mesomerism. The relative positions of nuclei should remain unchanged (e. Therefore. The actual structure of the molecule is the resonance hybrid of all the possible resonance structures. The charge needs to be preserved in all the resonating structures. (i) (ii) (iii) (iv) (v) The molecule should be planar. However.

+R effect of –NH2 group. –CONH2. while the substituent with partial or complete positive charge exhibits –M effect.g. (B) If atoms or groups withdraw electrons through resonance. C C CH O —C—C CH — O – (–R effect of –CHO group) Other groups showing –R effect are –NO2. –CO2R. O N O O N O O N etc. Arrows should be drawn to indicate the direction of the movement of electrons. O + + –R effect of –NO2 group. NH2 + NH2 + NH2 etc. –OR. –COCl. Chemistry / Nomenclature and Isomerism . e. C C OH – —C—C OH (+M or +R effect of –OH group) Groups showing +R effect are –NHR. For substituted benzene. etc. –COOH. Resonance (mesomeric) effect is of two types: (A) If an atom or group of atoms donates electrons through resonance. –NH2. e. 45 . –X (halogens) etc.g. –SO3H.(vi) (vii) The electrons always move away from a negative charge. e. –NR2.. then it is known as –R or –M effect. –NHCOR. it shows +M effect. it is considered to exhibit +R or +M effect.g.. if the substituent bears at least one lone pair of electrons. –CN. –COR.

C + O H + -I O CH3-C OH Ka = 1.Inductive Effect The electron shift takes place by resonance in a conjugated system. Group showing +I effect: Group showing –I effect: CH3. Cl2CHCOOH Cl3CCOOH Ka 2. CH(CH3)2. i. –C6H5 Chloroacetic acid is a stronger acid than acetic acid because O Cl . Features of inductive effect The extent of inductive effect can be predicted by noting the following points. Br CH2 COOH F CH2 COOH Ka 2. 46 Chemistry / Nomenclature and Isomerism .32 × 10 −4 3.02 × 10 −5 . the group attached to the chain is electron-withdrawing). C(CH3)3. the group attached to the chain is electron-donating) and – I (i. It takes place in a saturated carbon chain unlike resonance..e. inductively an electron-withdrawing (– I) group has an acid strengthening effect and an electron-donating group (+ I) has an acid weakening effect. –CN. C2H5.3 × 10 −1 5.4 × 10 −2 (iii) Since this effect is transmitted through a chain it becomes less effective with distance ClCH2CH2CH2COOH ClCH2CH2COOH Ka 8. –OH. This effect takes place when a group attached to the carbon chain has the tendency to release or withdraw electrons through the chain. larger is the –I effect. more the electron-withdrawing groups attached to the chain.3 × 10 −3 Inductive effect is additive.. –Br. In short. There is an additional way for similar transmission of electrons and this is done through the inductive effect (I). –OCH3. The reverse is true for bases. It is of two types: + I (i.CH2 C OH Ka = 1. O–.e.5 × 10 −3 (ii) 1.e. (i) The larger is the electron-withdrawing effect of a group. –NO2. the greater is the –I (inductive) effect. –I. –N+(CH3)3.4 × 10-3 O Cl-CH2 . –Cl.75 × 10-5 O CH3-C + O H + +I The chloro-acetate ion is more stable than the acetate ion because of – I effect of the Cl group. –F.

R 1 2 H H Br – R HBr H R C—C + – H H H C H R — CH — CH3 Br C + C — CH3 + H C1-atom is having positive charge as it has been neutralized by +I effect of R group and has been attacked by Br – to give the addition product. i.e.e. solubility in water. Chemistry / Nomenclature and Isomerism . Hydrogen bond effects the properties of a molecule such as boiling points. i. in presence of reagent X Y in absence of reagent + X Y The common example of electromeric effect is the partial charge development in an alkene during addition reaction. The Hydrogen Bond A hydrogen bond is formed when a hydrogen atom lies between two electronegative atoms. within the same molecule. The force of attraction between a hydrogen atom attached by a covalent bond in one molecule and an electronegative atom attached in the same or different molecule is called the hydrogen bond..Electromeric Effect It is a temporary or time-variable effect which is observed in presence of reagents involving transfering of electrons in an unsaturated system. etc. basic strength. It is a weak bond and the bond energy is of the order of 2-10 Kcal per mole. (ii) Intramolecular. There are two types of H-bonds. (i) Intermolecular.. 47 . F H H F H F The bond is formed due to electrostatic attraction and is represented by a dotted line. among different molecules. acidic strength.

Alcohols are soluble in water because they form hydrogen bond with water. boiling points of alcohols are higher since they are hydrogen bonded. Similarly.. proteins. etc. H O H O H O H H H O H H H-bond formation in water Such an association does not exist in H2S as the sulphur atom has a poor electronegativity and large size. OH δ – H δ + O O N+ O δ O o -N itro phenol H – δ H + N + O – O p -N itro phenol (interm olecular H -bo nding) Hydrogen bonds exist in primary amines.The boiling point of H2S is 40° C while that of water is much 100° C.. 48 . This large difference is explained on the basis of intermolecular H-bonds in water leading to a large size cluster. Chemistry / Nomenclature and Isomerism . carboxylic acids. Do You Know? Any molecule which can form hydrogen bond with water will be soluble in it. o-nitrophenol has a lower boiling point than the p-isomer because the ortho isomer can form hydrogen bond intramolecularly and intramolecular H-bonding reduces the boiling point.

N N . 49 . Me N Me Me Me + N Me N –H Me + + Ph N N H N N Ph + N Chemistry / Nomenclature and Isomerism N Ph . This reduced acidity is explained in terms of steric effects.. . Illustrative Example Example 1: Solution: N. In this compound the two methyl groups twist the nitro group out of the plane of the benzene ring. between quinuclidine and triethylamine the former is more basic.6-dimethyl-4-nitrophenol has a value of ionization constant comparable to p-nitrophenol. OH CH3 OH CH3 CH3 OH CH3 NO2 NO2 NO2 2. Quinuclidine Triethylamine The presence of alkyl groups on the benzene ring also affects adversely the acidity of phenols. It is the result of the presence of bulky groups. In triethylamine the three ethyl groups offer interference for the donation of the electron pair but in quinuclidine these groups are pinned back and the electron-pair is available for donation. the phenoxide ion cannot be stabilized by resonance with the nitro group.. This effect is also termed as steric inhibition of resonance.. But the acidity of 3. which one is readily undergoing azo-coupling reaction? Explain. there are two –CH3 groups. The ionization constant of phenols is of the following order.5-dimethyl-4-nitrophenol is almost 10 times lower. N-dimethylaniline and its 2. The energy barrier to rotation in butane is more than that of ethane. as in the former.Steric Effects An energetically unfavourable effect on any physical or chemical property that results from van der Waal’s repulsion is generally termed as steric effect. Thus.. Steric effects result from interactions between atoms or groups that are non-bonded to each other. As a result.6-dimethyl derivative.

Hyperconjugation The relative magnitude of +I effect of alkyl groups follow the following order. particularly in case of conjugated double bond or benzene ring.. It can be explained by the extension of resonance.The lone pair on N-atom is available for electrophilic attack due to the presence of two electrons donating —CH3 groups. where delocalisation occurs in the follwing manner: H H — C — CH H CH2 H H—C H (3 similar structures) H H — C — CH CH3 CH2 H H—C CH3 (2 structures) H H3C — C — CH CH3 CH2 H H3C — C CH3 (only one structure) CH — CH2 CH — CH2 CH — CH2 Chemistry / Nomenclature and Isomerism . Me3C– > Me2CH– > MeCH2 – > CH3 – However. the reverse order can be found. 50 . Me N H3C Me Me + Me N CH3 H3C CH3 – Due to the presence of four bulky —CH3 groups —N(CH3)2 cannot be in the same plane with benzene ring. Hence. in certain cases. it is not capable of azocoupling reaction due to steric hindrance..

Relative strength of organic acids To determine whether a molecule is acidic or not. Alkyl groups containing C — H bonds if attached to benzene ring.CH3 H3C — C — CH CH3 CH2 No such extended structure possible which can explain the stability This type of delocalization involves σ− and π−bond orbitals and is given the name hyperconjugation or no bond resonance. 51 . Like resonance more is the hyperconjugative structures. non-terminal alkenes or more substituted alkenes have better stability compared to terminal alkenes. Then determine if the resultant ion can be stabilized by any means (resonance. The number of hyperconjugative structures in an alkene is obtained by the number of C — H bonds attached to the carbon bonded directly to the double bonded carbon atoms. increases electron density both at the ortho and para positions. Let us compare the stability of 1-butene and 2-butene. Significance of this effect a.. inductive effect. e. H3C — CH — CH CH — CH2 H3C — CH CH2 + H (2 hyperconjugative structures) H3C — CH CH — CH3 H3C — CH — CH CH2 H + (6 hyperconjugative structures) Hence. first ionize the molecule. If the ion can be stabilized then the parent molecule is always acidic. H-bonding.. etc). H H H H H—C—H H—C—H + + H—C H + H—C H b. Phenols are stronger acids than alcohols (the ion cannot be stabilized) but weaker than the carboxylic acids. more stable is the ion or molecule. the carboxylate anion is stabilized by resonance in which the negative charge remains on the oxygen atom unlike in phenol in which it is delocalized over the C-atoms as well. Chemistry / Nomenclature and Isomerism . This is so because after the carboxyl group loses a proton.g.

. It rather decreases the basicity of aromatic amines.O O R-C OH R-C O + H + O R-C O Resonance structures Electron-withdrawing groups (− NO 2 . OH O O O etc + + N O N O O N O O + N O O + O Resonance has opposite effect on the basicity of molecules. 52 . − CH3 ) do just the opposite.. Aniline for this reason is less basic than cyclohexylamine. then – O O O O O O N N N – O O O – o -nitrophe noxide io n O– N O O O N O O – Chemistry / Nomenclature and Isomerism . Electrondonating groups (− OCH3 . m. . NH2 N H2 – NH2 NH2 NH2 – – N o re sonance po ssible Now if we compare the acidic strength of o-.and p-nitrophenols. − CN) present on the ring in phenols help to delocalize the negative charge on the oxygen atom and stabilize the anion and hence increases the acidic strength. The electron-pair is resonated with the ring and is thus not available for donation. Basicity implies the capacity of a molecule to donate its electron pair..

Among ortho and para isomers.and p-nitrophenoxides are stabilised through –R effect of –NO2 group. it has less tendency to donate proton (H+). e. δ H O + Oδ N O − Aliphatic and aromatic carboxylicacids The strength of an organic acid RCOOH depends on the stability of RCOO– (carboxylic ion) as compared to RCOOH in aqueous solution. the stability of carboxylate ion determines the strength of the acid. O O CH3 — CH2 — C — OH H3C CH2 – + C—O+H Chemistry / Nomenclature and Isomerism .. it is clearly observed that o. While such kind of stabilisation is absent in m-nitrophenoxide. For an aliphatic acid.. 53 .g.O O O O NO2 m-nitrophenoxide NO2 NO2 NO2 O O O – NO2 p-nitrophenoxide NO2 O N O O O O NO2 NO2 N O O Hence. Hence. p-isomer is more acidic as ortho compound is stabilised through intramolecular H-bonding.

it will reduce the stability of carboxylate anion and hence acidic strength decreases. Electron-withdrawing groups substituted in benzene ring disperse the negative charge of –COO– group and increases the stability of the anion while electron-donating groups have the adverse effect on the acid strength. H—C—H H OH C H C—H H O H — C H+ H HO C O H — C H+ H HO C H+ C—H H H+ C—H H etc. which will increase the charge density on oxygen atom of –OH group and hence decreases acidic strength. CH3 — CF2 — C — OH H3C Ask Yourself What is the decreasing order of acid strength of following? H3C — CH2 — COOH H2C CH — COOH HC I II C — COOH III Acidic strength in aromatic acids depends on the stability of the benzoate anion. So the acid strength increases. But such kind of destabilising factor is absent in m-isomer. O O – + CF2 C—O+H Here CH3CF2 group is much less electron donating than previous one and hence stabilises carboxylate anion. OH HO HO O O O C C C etc. Chemistry / Nomenclature and Isomerism . the carbon atom attached to –COOH group gets additional negative charge due to hyperconjugation.. O In p-isomer.Since ethyl (CH3CH2) group is electron releasing.. e. 54 .and p-isomers of methyl benzoic acid. if we consider the m. m-isomer is a stronger acid than p-isomer.g.

o-hydroxy benzoic acid (salicylic acid) is more acidic than its two isomers because of intramolecular H-bonding as follows. p-isomer is more acidic. most of the o-substituted benzoic acid is stronger than benzoic acid.and p-nitro benzoic acids have different characteristics. O C O O H (Carboxylate ion is stabilised by H-bonding) Chemistry / Nomenclature and Isomerism . m. Again. HO HO C O C O etc. Hence. It can be explained by the fact that due to the presence of o.. we can explain the acidic strength as follows. the carbon of –COOH group has not carried positive charge in any resonating structure. N O H OH C O O N O OH C O etc. Irrespective of the nature of the group.. Here only –I effect is predominating. So the acid strength increases. 55 .On the other hand. Since –NO2 group is an electron-withdrawing group exerting –I as well as –R effect on the benzene ring. All the ortho-substituted benzoic acids show a special effect called ortho effect.substituent coplanarity of –COOH group with phenyl ring is being disturbed and resonance effect of phenyl ring does not increase the electron density on –COOH group. N O O N—O O In m-isomer.

56 . Due to +R effect its acidic strength decreases in o.Same effect is observed with phthalic acid.. COOH COOH COOH (a) OCH3 OCH3 OCH3 I COOH II III (b) HCOOH and Solution (a): –OCH3 group has –I effect as well as +R effect. HO C O HO C O etc. O C O H C—O O (Anion is stabilised by intramolecular H-bonding) Illustrative Example Example 1: Arrange the following compounds according to the decreasing order of acidic strength.. OCH3 + OCH3 Chemistry / Nomenclature and Isomerism .and p-isomers as compared to m-isomer where only –I effect predominates.

HO C O HO C O etc. 57 . COOH ∴ HCOOH > Relative Strength of Organic Bases Strength of organic bases increases as the ability to donate lone pairs of electrons increases for aliphatic and aromtic amines.and p-isomers. the decreasing order is II > I > III. the carboxylate ion is stabilised by equivalent resonating structure. – O O HCOOH H—C H+ + H — C – O O Whereas in benzoic acid. In formic acid. o-methoxy benzoic acid is more acidic due to ortho effect. due to the +R effect of phenyl ring more negative charge will be accumulated on oxygen atom of –COOH group and hence decreases the acid strength.. its energy distribution is very regular. Tertiary amine has minimum H-bonding stability. For aliphatic amines in aqueous solution. Therefore. the electron-donating groups increase the basic strength.. The decreasing order of basic strength of aliphatic amines should be R3N > R2NH > RNH2 > NH3 But the stability of the protonated base in aqueous solution through H-bonding is also important. Hence. OCH3 + OCH3 (b) Between o. Chemistry / Nomenclature and Isomerism . HO HO – C O C O etc.

58 . So in case of aromatic bases to find out the strength of bases it should be considered if the lone pair on N-atom is involved in resonance or not.H OH2 OH2 + R — NH H R + H OH2 OH2 R N H R—N—H R + OH2 R OH2 III II I Now the combined factor is highest for secondary-amine. R3N > R2NH > RNH2 > NH3. NH2 + NH2 etc. nitroaniline and methoxyaniline. OMe + OMe –OMe group (methoxy) has –I effect but stronger +R effect which increases the charge density on –NH2 group and increases the basic strength. Lone pair on N-atom involves in resonance. Hence. N O O N – O O –R effect of –NO2 group decreases the basic strength to a greater extent. then primary amine and then tertiary-amine. NH2 NH2 – etc. Electron-donating groups increase the basic strength and electron-withdrawing groups have adverse effect on basic strength. So the decreasing order of basic strength is II > I > III. Chemistry / Nomenclature and Isomerism .. In gaseous medium. Involvement in resonance decreases the basic strength and vice versa. NH2 + NH2 etc.. Consider the relative strength of aniline. it is less available for protonation.

Bond Cleavage A covalent bond is a pair of electrons shared by two atoms. and eventually their mechanisms. known as free radicals. NH2 NH2 NH2 OMe OMe OMe I Solution: II III –OMe group has –I effect and also +R effect when it is present to o. There is more than one way in which this can happen but all reactions involve electrons. 59 . → A ⋅ + B⋅ A :B  Chemistry / Nomenclature and Isomerism .. There are fundamentally two different modes of bond cleavage or bond fission. A : B → A + : B − A:B A– : B+ The species obtained after heterolytic cleavage or heterolysis are charged ions. Electrons are unit negative charges and the magnitude and disruption of charge are important consideration in the study of organic reactions. the shared pair of electrons is retained by one of the separating fragments. A reaction is said to have taken place when one compound has been converted to another compound so that it no longer shows its initial properties.and p-positions with respect to other substituent. 1. The carbon containing ions are of two types: (i) carbocations and (ii) carbanions. We are concerned with the manner a bond is broken and the nature of the resulting fragments. 2. Heterolytic Cleavage In this type of bond fission.. Again –I effect is least in p-isomer. Homolytic Cleavage In this type of bond fission the bond is broken in such a manner that the shared pair of electrons is divided equally between the two fragments. A reaction mechanism is simply a detailed description of the sequence of steps involved in going from reactants to products. the increasing order of basic strength is II < I < III.Illustrative Example Example 1: Arrange the following according to the increasing order of basic strength. Therefore. The organic compounds are bonded by covalent bonds and they can undergo reactions only by breaking some bonds and forming new bonds.

C H3 CH3 CH 3 C H3 > C + > C H3 > C H + > H C + C H3 2° 3° A tertiary (3°) carbocation is more stable than secondary (2°). Vinyl cation Inductive effect: Since a carbocation has a positive charge. Reactions involving heterolytic fission are known as ionic or polar reactions and those involving homolytic fission are called as non-ionic or non-polar reactions.. A carbocation can be stabilized by resonance or inductive effect or hyperconjugation. the bond angle is 120° and it is sp2 hybridized — it is planar. In a carbocation carbon atom has six electrons in the valence shell. H 1° Chemistry / Nomenclature and Isomerism . it is electron deficient. The species so produced above are called reaction intermediates. For example benzyl cation is stabilised through resonance as + CH2 CH2 CH 2 + Benzyl cation + etc CH2 + CH CH2 A llyl cation H2C CH + CH2 CH CH2 Stabilised through resonan ce no resonance hence unstable. The Carbocation or Carbonium ion An ion with a positive charge on the carbon atom is called a carbocation. i. 60 .Free radicals are uncharged.e. The resonance effect is always more predominant than the inductive effect in stabilizing an ion. all the bonds lie in one plane. an electron-releasing group with +I effect will stabilize it. which in turn is more stable than primary (1°)..

Do You Know? Carbocations are stabilised by hyperconjugation also. + H CH2 C CH3 CH3 Thus. Ask Yourself Is tertiary cation most stable cation always? Chemistry / Nomenclature and Isomerism . tertiary carbocation is more stable than secondary and so on.. Rearrangement of carbocations CH3 H 3C — C H — C H 2 O H C onc.. CH3 H 3C — C + CH3 H 3C — C C H 2H+ CH3 C H 2H H 3C — C + CH2 — H etc. 3° carbocation is the stable intermediate. 61 . H 2 SO 4 H + CH3 + H 3C — C H — C H 2 — O H 2 –H2O – ~C H 3 sh ift CH3 + H 3C — C — C H 2 H ~H – hydride shift 1 ° cation very le ss stable and w ill go for rearrangem ent for better sta bility A dition + H 3C — C H — C H 2C H 3 2° (less stab le than 3 ° ) CH3 H 3C — C — C H 3 + (3 ° m ost stable cation) Hence.

+ Solution: sp + s p2 The positive charge is present on electronegative sp carbon atom. Resonance : H H H Cyclopentadienyl carbanion Inductive Effect : C H3 C H3 C H3 C C H3 C H3 C H H C H3 C H 3° 2° 1° Electron-donating groups destabilize a carbanion while electron-withdrawing groups stabilize it. it is electron-rich. − CH2 CH− 2 > NO2 O C H3 Illustrative Examples Example 1: Which one is more stable. 62 .. phenyl carbocation is less stable. It is trigonal pyramidal like NH3. Hence. Chemistry / Nomenclature and Isomerism . While cyclohexyl cation is a secondary cation with sp2 hybridised carbon atom which is more stable than a phenyl cation. C6H5 + or C6H11+ ? Explain. Carbon atom is sp3 hybridized. Hence. In a carbanion the carbon atom has eight electrons.The Carbanion An ion with a negative charge on the carbon atom is called a carbanion.. A carbanion can be stabilized by resonance or inductively by electron-withdrawing groups.

− CN− . POCl3.g.e. (ii) Triplet carbene: Chemistry / Nomenclature and Isomerism .. Generally... Carbene is of two types (i) Singlet carbene: CH2 hybridisation sp2 it is v-shaped hybridisation sp it is linear shaped Triplet carbene is more stable than single carbene. Classification of Reagents Nucleophilic Reagents (Nucleophiles) A reagent which attacks the positive end of a polar bond or nucleus-loving is known as nucleophile. A tertiary (3°) radical is more stable than the other two.. OCH3 . etc. . FeCl3. Electrophilic Reagents (Electrophiles) . C 2 H 5 — O All nucleophiles are in general Lewis bases... ZnCl2 All electrophiles are in general Lewis acids. NO + . e. 63 CH2 . H 2O . N . NH3 . CH3 . A carbene is neutral and possesses two free electrons. . + H+ . SOCl2. negatively charged or electron rich species are nucleophilic. CH3 H2O. AlCl3. The stability of tertiary radical can be explained by hyperconjugation. A reagent which attacks a region of high electron density or electron-loving is known as electrophile. — C H 3 . a total of six electrons. . Here the carbon atom is linked to two adjacent groups by covalent bonding. C H 3 — O . CH3 COO − ..The Free Radical A species which contains an unpaired electron is called a free radical. All the factors that stabilize a carbocation also stabilize a free radical. Carbenes A carbene may be described as a divalent carbon compound. NH3 — NH2 Θ + .. NH2 . All positively charged or electron deficient species are electrophilic. It is also considered as electron deficient. Br + . It is considered electron deficient and neutral in nature. H . Cl+ . Ag+ 2 Neutral reagents which contain an electron-deficient atom are also electrophiles. N H 3 . Geometrically a free radical may be planar or pyramidal. BF3. i. A free radical has a total of seven electrons. OH− .. − −. SO3. − I− .

the reaction is called nucleophilic substitution reaction. Substitution 2.. 2-Methyl anion shift Fast OH CH3 — C — CH2CH3 CH — C — CH – CH CH3 — C — CH2 3 2 3 + OH CH3 In SN1 reaction.. SN2 is second order reaction. Types of organic reactions Organic compounds undergo a large number of interesting reactions. Isomerisation Substitution reaction: During substitution one atom or group of atoms is replaced by other group or atom. because substrate and nucleophile both are involved in the rate determining step. CH3 CH3 SN1 + CH3 — C — CH2Cl CH — C — CH2 3 – OH CH3 CH3 slow The carbonium ion formed can undergo rearrangement to give more stable carbonium ion before attack of the nucleophile. electrophile. It can be done by nucleophile. or free radical. there can be racemisation. R − X + OH −  → R OH + X − SN1 Reaction: Unimolecular nucleophilic substitution reaction. The rate of substitution depends on the concentration of the substrate. CH3 CH3 CH3 – + 1. Order of reactivity of RX as SN1 3° > 2° > 1° > CH3X SN2 Reaction: This is called bimolecular nucleophilic substitution and it is one-step process. These reactions are broadly classified into following: 1. CH3 – H — C — Br + OH slow C H 2C H 3 d– OH H C CH3 . CH3 F ast HO — C — H C H 2C H 3 d– Br C H 2C H 3 Transition state unsta ble Chemistry / Nomenclature and Isomerism . 64 . Nucleophilic substitution: When a substitution reaction is brought about by a nucleophile. Condensation 6. Elimination 4. Rearrangement 5. Addition 3. First step involved the formation of carbocation which is slow and rate determining step. It is a two-step process.Do You Know? Carbene is an electrophile.

There is complete stereochemical inversions during SN2.. Cl 2 → Cl CH 2 − CH 2 Cl CH 2 = CH 2  CCl 4 + H2 O H + OH (Hydration) Elimination Reactions In most elimination reactions. CH3 – CH – CH – CH3 OH H Conc. H2SO4 – H2O CH3 — CH CH – CH3 We divide elimination reactions into three classes. In first step. > C = O or − C ≡ N bond and the π bond is converted into σ bond. The higher the polarity of the solvent. two groups on adjacent atoms are lost as a double bond is formed. the order of reactivity is CH3X > 1° > 2° > 3° (Alkyl halide) High concentration of the nucleophile favours SN2 reaction while low concentration favours SN1 reaction. The reagent often adds to > C = C <. (i) E1 reaction. − C ≡ C−. First step L CH3 CH3 C—C H Second step Base + CH3 CH3 + C—C H CH3 CH3 –H Fast + CH3 CH3 – –L Slow CH3 CH3 C—C + CH3 CH3 H Carbocation CH3 CH3 C C CH3 CH3 Chemistry / Nomenclature and Isomerism . Addition Two molecules react to form one. the C – L bond is broken heterolytically to form a carbocation (as in SN1 reaction). carbocation loses a proton from an adjacent carbon atom to form a π bond in presence of base. It involves two steps. For SN2 reaction.. In second step. 65 . the greater is the tendency for SN1 reaction. It can be electrophilic addition and nucleophilic addition.

Evidence for E1 mechanism: (a) Follow the first order kinetics. we call it E1 CB reaction. δ– L L CH 3 CH3 slow – C C C—C B ase + CH 3 CH 3 H δ– B H Transition state CH3 CH3 C =C CH3 + H -B ase + L – CH3 It is a bimolecular since substrate and base are involved in the rate determining step. (ii) E1 CB This reaction is called unimolecular conjugate base elimination reaction. Hence. First step consists of the removal of a proton. leaving group releases from carbanion (II) to form alkene.The first step is slow and rate determining step E1 reaction is favoured in compounds in which one leaving group is at a secondary or tertiary position.. E 2 Chemistry / Nomenclature and Isomerism . 66 . the reaction rate is controlled by how fast the leaving group is lost from the carbanion (II) (conjugate base). Evidence for the E2 mechanism: (a) Follow the second order kinetics (b) These are not accompanied by rearrangement 3° > 2° > 1° The order of reactivity of alkyl halides in E1 and E2 are E 1. H+ by a base generating a carbanion (II). which includes breaking of 2 σ bonds and formation of one π bond simultaneously. E2 reaction does not proceed through an intermediate carbocation but through a transition state. The loss of L– from (II) is rate determining step and is unimolecular. In the second step. (iii) E2 Reaction This is one step process.. L L + CH Ph CH3 Ph – 3 –H Slow Ph CH3 + Base C—C C—C C = C – Fast H CH3 H CH3 – L H CH 3 H (II) Because step I (deprotonation) is fast and reversible. (b) Where the structure permits are accompanied by rearrangement.

3-trimethyl-1-propene (c) 3. 2 pi-bonds and 2 lone pairs (c) 10 sigma bonds. 67 . 5.3. (b) sp3 > sp > sp2 (d) sp > sp3 > sp (1989) (d) 6 sigma and 4 pi The number of sigma and pi-bonds in 1-buten-3-yne are: (a) 5 sigma and 5 pi (b) 7sigma and 3 pi (c) 8 sigma and 2 pi 3. they must have: (1987) (a) different percentage composition (b) different molecular weight (c) same velocity (d) same vapour density The IUPAC name of the compound having the formula is: (1984) 7.Take-off 1.2-dimethyl-3-butene CH3 Chemistry / Nomenclature and Isomerism . 8.1-trimethyl-2-propene (d) 2. CH3 H 3C C (a) 3.. 1 pi bond and 1 lone pair (d) 9 sigma bonds. The correct order of electronegativity of carbon atom in different hybrid orbitals is (a) sp > sp2 > sp3 (c) sp3 > sp2 > sp 2. (1999) If two compounds have the same empirical formula but different molecular formulae. Which of the following represent the given mode of hybridization sp2–sp2–sp–sp from left to right? (2003) (a) H 2 C CH C N (b) H C C C C C H (c) H 2 C C C C C H 2 (d) H 2 C CH2 The compound in which C uses its sp3-hybrid orbitals for bond formation is: (c) (CH3)3COH (d) CH3CHO (a) HCOOH (b) (H2N)2CO The enolic form of acetone contains: (a) 9 simga bonds.. Discuss the hybridization of carbon atoms in allene (C3H4) and show the π − orbital overlaps. 2 pi bonds and 1 lone pair (1989) 4.1. (1990) 6.3-dimethyl-1-butene CH CH2 (b) 1. 1 pi bond and 2 lone pairs (b) 8 sigma bonds.

68 ... The IUPAC name of C6H5COCl is : (a) benzoyl chloride (c) benzene carbonyl chloride (b) benzene chloro ketone (d) c hloro phenyl ketone 11.1-dimethyl-2-propene (c) 2-vinyl propane 10. The UPAC name of the compound (1987) (b) 3-methyl-1-butene (d) none of the above CH2 = CH – CH (CH3 )2 is : (a) 1. CH3 | (i) CH3 CH CH2 CH2 C CH2 CH3 | | CH2CH3 CH2CH3 CH2 CH2 CH3 (ii) (iii) C H 3 C H C H CH3 | CH CH3 C 2H 5 (iv) 13. Suggest an IUPAC names for the following compounds. (i) CH =CHCH CH CH N 2 2 2 2 O CH3 CH3 (ii) O CH2 CH2 OH (iii) CN (iv) CN Chemistry / Nomenclature and Isomerism . What will be the IUPAC name of the compound given below? C 6H 5 CH3 C CH O C CH3 CH3 CHCl CH3 12.9. Suggest an IUPAC name for each of the following.

69 . Only two isomeric monchloro derivatives are possible for: (a) n-butane (b) 2. An isomer of ethanol is: (a) methanol (b) diethyl ether The number of isomers of C6H14 is: (a) 4 (b) 5 (1986) (c) acetone (d) dimethyl ether (1987) (c) 6 (d) 7 (1986) 16..14.4 diemthyl pentane (c) benzene (d) 2-methyl propane How many monochloroderivatives are possible for the following? (i) CH3 — CH2 — CH2 — CH2 — CH2 — CH3 (ii) C H 3 CH CH3 CH3 18. CH2 CH2 CH3 CH3 CH2 CH3 (iii) C H 3 CH2 CH (iv) C H 3 C CH3 CH2 CH2 CH3 CH3 (v) C H 3 CH3 C H2 CH3 (vi) C H 3 C C H3 CH CH CH3 CH3 Chemistry / Nomenclature and Isomerism .. Write the IUPAC names of following compounds C H 2C l (i) B r — C H 2 — C H — (C H 2 )5 — C H C lB r (ii) CH2 — CH — CH2 OH OH OH NO2 HOOC (iii) *(iv) COOH NO2 (C H 3) 2C C O O C 2 H 5 (v) NO2 15. 17.

1-diphenyl-1-propene 23. H Br C2H5 The molecules represented by the above structures are (a) diastereomers (b) enantiomers (c) meso-compounds (d) None of these Chemistry / Nomenclature and Isomerism . Which of the following compounds will exhibit cis-trans (geometrical) isomerism? (a) 2-butene (b) 2-butyne (c) 2-butanol (d) butanal 22. Which of them will have zero dipole moment? (1985) The number of geometric isomers in case of the following compound CH3CH = CHCH = CHCH2CH3 is (a) 3 (b) 2 (c) 4 20. (b) optical isomerism (d) tautomerism Which one of the following compounds will show geometrical isomerism? (a) CH3 — CH = CH2 (b) CH3 (c) C CH3 CH3 N — OH (d) HO — N = N — OH CH3 OH H HO Br C2H5 H H 25. (d) 5 (1983) 21... 70 . Write the structure of all the possible isomers of dichloroethene.19. Which of the following compounds will exhibit geometrical isomerism? (2000) (a) 1-phenyl-2-butene (b) 3-phenyl-1-butene (c) 2-phenyl-1-butene (d) 1. H3C C H3C H3C C H H C COOH The above compound will exhibit (a) geometrical isomerism (c) geometrical and optical isomerism 24.

71 . O (a) (c) O H C 6H 5 (b) (d) C 6H 5 C O C 6H 5 C C 6H 5 C C H 3 O C 6H 5 C O CH2 C CH3 Chemistry / Nomenclature and Isomerism . Which of the following have asymmetric carbon atom? (1989) Cl Br (a) H C C H H H 27. F CH3 CH3 (a) (b) H H F CH3 (c) (d) H CH3 H COOH CH3 29. Write down the structures of the stereoisomers formed when cis-2-butene is reacted with bromine.26..3-diol ? (a) 1 (b) 2 (c) 3 (d) 4 Which of the following compound will be optically active? *28. (1995) Which one of the following has maximum enol content? (a) Acetaldehyde (b) Butanone (c) Propanone (d) Acetyl acetaldehyde Keto-enol tautomerism is observed in.. H Cl H Cl (c) H C C D H H H H (d) H C C C H 3 Br OH (1997) (b) H C C C l H H How many optically active stereoisomers are possible for butan-2. (1988) 30. 31.

(b) Non planar structure.32. 38.. The kind of delocalization involving σ -bond orbitals is called (a) inductive effect (b) resonance (c) hyperconjugation (d) None of these Phenol is more acidic than 37. 2-Bromopropan-1-ol has almost zero dipole moment whereas 2-fluoropropan-1-ol has a measurable dipole moment. (a) Non-bonding interaction of flagpole hydrogen. The compound exhibits (a) geometrical Isomerism (c) optical isomerism 33. H 3 2 CH3 H (2004) H C2 is rotated anticlockwise 120° C about C2—C3 bond. OH (a) C2H5OH (b) NO2 OH NO 2 (c) Chemistry / Nomenclature and Isomerism (d) CH3COOH . (b) tautomerism (d) conformational isomerism Isomers which can be interconverted through rotation around a single bond are: (1992) (a) conformers (b) diastereomers (c) enantiomers (d) positional isomers CH3 H 34. Boat structure of cyclohexane is unstable due to.. The resulting conformer is (a) partially eclipsed (b) eclipsed (c) gauche (d) staggered 35. 72 . *36. (c) Eclipsed conformation (d) Maximum van der Walls interaction. Explain.

39. CH3 (a) H3C — CH CH2 (b) H3C — C CH2 CH3 CH3 (c) H3C — C 41.. N. (b) (CH3 )2 CH (d) CH2CH2NO2 + + CH2 Which one of the following free radicals has the least bond angle? (a) •CF3 (c) •CH(CH3 )2 (b) •CH3 (d) •C(CH3 )3 (b) π-electron (d) None of these 43. p-toluidine. the resonance is possible? (a) CH2 = CH — CH2 — CHO (c) CH2 = CH — CHO (b) CH3COCH3 (d) CH2 = CH — CH2 — CH = CH2 45. H3C CH3 (d) H3C — C CH C — CH3 Which of the following is the most stable carbocation? + + (a) (CH3 )3 C (c) *42. aniline. In which of the following. Arrange the following in the order of their increasing basicity. p-nitroaniline.. will be (a) (b) (c) (d) Chemistry / Nomenclature and Isomerism . Which of the following species has the highest hyperconjugative stability? (1986) 40. Inductive effect involves (a) σ-electron (c) Both (a) and (b) 44. 73 . The most stable free radical. N-dimethyl-p-toluidine.

*46. 53. Which of the following is an electrophile? (a) RNH2 (c) CN– (b) condensation reaction (d) substitution reaction (b) : CH2 (d) H2O (d) CH3NH2 (d) BF3 52. NO 2 (i) (ii) NO2 (iii) . A nucleophile must possess (a) two lone pairs of electrons (c) an overall positive charge (b) an unpaired electron (d) tendency to donate electron pair 50. NH 2 N N 47. The molecule which behaves as electrophile as well as nucleophile is (b) CH3CN (c) CH3OH (a) CH3Cl Which of the following is not a nucleophile? (b) OH– (a) CN– (c) NH3 Chemistry / Nomenclature and Isomerism . OH N O2 . 49. Give the enol form of CH3 COCH2 COCH3 with intramolecular hydrogen bonding. H3C — CH CH2 Br2/H2O H3C — CH — CH2 OH Br The above reaction is an example of (a) addition reaction (c) elimination reaction 51... OH OH 48. H Arrange the following compounds in the increasing order of acidity. 74 . Account for the basicity order of the following compounds.

Which of the following has the highest nucleophilicity? (a) F− (b) OH− (c) CH3 − − (d) NH2 57. If it is isolated from a reaction with 30% racemisation and 70% retention. 63. The specific rotation of a pure enantiomer is +10°. (d) 16 Chemistry / Nomenclature and Isomerism .. Triplet carbene is more stable than singlet carbene. H2S. AlCl3 . RSH. – – C H 3 – C C . Why? 61. NO2 . C H 3 – C H 2 – C H 2 a nd C H 3– C H = C H – Which of the following compounds exhibit geometrical isomerism? (b) (CH)2(COOH)2 (a) C2H5Br (c) CH3CHO (d) (CH2)2(COOH)2 The lowest molecular weight alkane which is capable of showing enantiomorphism must have (a) four carbon atoms (b) five carbon atoms (c) six carbon atoms (d) seven carbon atoms Geometrical isomerism is possible in (a) Acetone-oxime (c) Acetophenone-oxime 62. Br + . Why? *60. 75 .54. is more stable carbocation than . Separate the following into electrophiles and nucleophiles. OH− . (c) carbene (d) carbonium ion 56. Vinyl carbocation is unstable while vinyl carbanion is more stable.. the observed rotation is (a) +10° (b) +14° (c) +7° (d) –7° The number of possible racemic form of glucose is (a) 4 (b) 8 (c) 12 66. Give the correct order of stability of the following anions. Which of the following bond will undergo heterolytic cleavage most readily? (a) C — C (b) C — H (c) C — O (d) O — H Carbanion is iso-structural with (a) free radical (b) ammonia 55. (b) Isobutane (d) Benzophenone-oxime *65. NH3 58. *59. Explain. + CH3 OH. 64.

(d) None of these Predict the number and kind of stereoisomers possible for each of the following compounds. trans (b) trans. Statement–II is not a correct explanation for Statement–I (c) Statement–I is True. cis (c) trans. but their rates of reaction with other optically active substances are usually different. (2007) (a) Statement–I is True. (2007) (a) Statement–I is True.. Statement–II is True. 3-Butane diol (d) Bromocyclohexane The geometrical isomerism shown by is (a) cis. Statement – I : p-hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoic acid. Which of the following statements is not correct? (a) Enantiomers are similar chemically. Statement–II is True. Statement–II is a correct explanation for Statement–I (b) Statement–I is True. 76 . Chemistry / Nomenclature and Isomerism . Statement–II is False (d) Statement–I is False. Statement–II is not a correct explanation for Statement–I (c) Statement–I is True. Statements – II : All chiral molecules have chiral centres. 2-Dimethyl cyclopentane (c) 2. (a) 2-Butenoic acid (b) 1. 70.. Statement–II is True 71. Statement–II is True. Statement–II is True Statement – I : Molecules that are not superimposable on their mirror images are chiral. 69. (c) Diastereomers differ in their physical properties.67. Statement – II : o-hydorxybenzoic acid has intramolecular hydrogen bonding. Statement–II is True. Statement–II is a correct for Statement–I (b) Statement–I is True. (b) A sample of sec-butyl chloride is optically inactive due to the absence of chiral carbon atom. cis (d) None of these 68. Statement–II is False (d) Statement–I is False.

d 5.4 . Br+.7.d 27. (a) two geometrical isomers (b) three stereosiomers (c) two enantiomers (d) two conformational isomers Chemistry / Nomenclature and Isomerism . AlCl3.Ethyl -3. b 55. c 38. c . (i) Three (ii) Five (iii) Four (iv) Four (v) Three (vi) Two 20. d 32. b 8. a 43.methyldecane (iii) 3 .3 . a 7. b 66. a 40. C H 3 – C C– > C H 3 – C H = CH – > C H 3 – C H – 2 CH 2 62.. 77 64. c 68. a 22. b 56. (i)1.Methyl propyl) nonane 13. (i) 3 . b 17. RSH. d 16.2’-dicarboxylic acid (v) Ethyl 2-methyl-2-(3-nitrophenyl) propanoate 15. a 45.(2 . b 69. Electrophiles: NO2+. OH–. Pyridine > Aniline > Pyrrole C H3 49. c. d 71. b 63. b 70. d 67. (i) N. b 3. H2S. Nucleophiles: CH3OH.10-tetraene (iv) 66’-Dinitrodiphenyl-2. 6 . d 25. b 47. a 23. d 50. d 41. a 26. d 31. b 10. III > I > II 48.d 18. d 51. c. a 2. b 9.Hexenenitrile 14. c 37. c 21.dimethyloctane (ii) 5. a 4.8 dibromo-1-chloro-7-(chloromethyl) octane (ii) Propane 1.Methyl . C H3 C O H CH C O 39. b 52. c 35.4. NH3 – 61. 4-Dimethyl-3-oxo-hexanenitrile (iv) 3 . b 33.N-Dimethyl-5-amino-1-pentene (ii) 2-Phenoxyethan-1-ol (iii) 4. 3-triol (iii) Cyclo-dodeca-1. b 24.Answer Key Nomenclature and Isomerism 1. 2. d 57. c 65. b 28.Diethyl . c 46. a.methylethyl) heptane (iv) 5 .(1 .. c 11. a 54. 6 . a 34. c 53. a. a 42. 4-methyl-4-phenyl-3-(1’-chloroethyl)-2-pentanone 12.

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