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    CHAPTER 11 :

    INTRODUCTIONTO

    ORGANIC CHEMISTRY

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    CHAPTER 11 :CHAPTER 11 :

    INTRODUCTION TOINTRODUCTION TOORGANIC CHEMISTRYORGANIC CHEMISTRY

    11.1 Introduction

    11.2 Empirical molecular and structural formulas

    11.3 Functional groups and homologous series

    11.4 Classification of carbon atoms in organic molecules

    11.5 Isomerism

    11.6 Reactions in organic compound

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    11.1 INTRODUCTION

    Organic chemistry is the study ofcarbon compounds

    Generally, the components of organic compound are :

    C, H, O, N, S, X (halogen) and P

    Carbon compounds constitute the central chemicals of

    all things on this planet. Carbon compounds include

    deoxyribonuicleic acids (DNAs) the giant molecules

    that contain the genetic information for all living species

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    Organic and Inorganic Compound

    Organic compound Inorganic compound

    were defined as

    compounds that

    could be obtained

    from living

    organisms

    were those that

    came from

    nonliving sources

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    Examples of organic compounds :-

    CH4

    methane

    (a component of natural gas)

    OCOCH3

    COOH

    CH3 CHCOOH

    NH2

    Methyl salicylic acid

    (aspirin-a drug)

    alanine

    (amino acid-a protein component)

    NCH3

    CO2CH3

    OCO

    cocaine

    (a pain killer)

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    CH2 C

    O

    NH

    O

    S

    N

    COOH

    penicillin (an antibiotic)

    Cl CH Cl

    CCl3

    dichlorodiphenyltrichloroetane(DDT- a pesticide component)

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    N OHN

    4-hydroxyphenylazobenzene(a kind of dye)

    Caffeine(found in coffee and tea)

    N

    N

    O

    CH3

    C H3

    N

    N

    C H3

    O

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    C NH2NH2

    O

    Urea(a component in urine,

    also used as fertilizer)

    Deoxyribonucleic acid (DNA)(carries genetic informationof living organisms)

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    11.2 EMPIRICAL, MOLECULAR AND

    STRUCTURAL FORMULAE

    Empirical formula is the formula that shows the

    simplest ratio of number ofelements present in a

    molecule

    Molecular formula is a formula that shows the

    actual number ofatoms of each element in a

    molecule. Example : C2H4 , C2H4O2

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    Molecular formula = (empirical formula)n

    where n is a whole number

    therefore,

    massformulaempiricalmassmolecularrelative

    n =

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    Example 1 :

    If the relative molecular mass of a substance with empiricalformula CH2O is 60.0, what is the molecular formula of the

    substance?

    Solution :-

    massformulaempiricalmassmolecularrelative

    n =

    0.160.20.12

    0.60

    = = 2

    Molecular ormula = (empirical ormula)n

    = (CH2

    )2

    = C2H

    4

    O2

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    A sample of hydrocarbon contains 85.7 % carbon and

    14.3 % hydrogen by mass. Its molar mass is 56.

    Determine the empirical formula and molecular formula

    of the compound.

    Example 2 :

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    Solution :-

    Element C H

    Mass (g) 85.7 14.3

    Moles (n) 85.7

    12.0

    14.3

    1.0

    Smallest ratio 7.1427.142

    = 1

    14.437.142

    = 2

    = 7.142 = 14.3

    @ Empirical formula = CH2n (empirical molar mass)= molar massn ( 12 x 1 + 1 x 2 ) = 56

    n = 4Molecular formula = C4H8

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    Structural formula is a formula that shows

    how the atoms of a molecule are bonded to

    one another

    Representation of structural formula :-

    a) CondensedStructure

    b) ExpandedStructure

    c) SkeletalStructure

    d) 3-Dimensional formula

    e) Ficher Projection

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    The structural theory of organic chemistry

    Two central premises are fundamental :

    1.The atoms of the elements in organic compoundscan form a fixed number of bonds. The measureof this ability is called valence.

    Carbon tetravalent (C atoms form 4 bonds)

    Oxygen divalent

    Hydrogen & halogens monovalent

    C

    Carbon atoms aretetrahedral

    O

    Oxygen atoms aredivalent

    H Cl

    Hydrogen and halogenatoms are monovalent

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    2.A carbon atom can use one or more of itsvalences to form bonds to other carbon atoms

    Carbon-carbon bonds

    C C

    Single bond

    C C

    Double bond

    C C

    Triple bond

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    a) Condensed Structure

    In condensed formulae all the hydrogen atoms

    that are attached to a particular carbon are

    usually written immediately after that carbon

    In fully condensed formulae all atoms that are

    attached to a carbon are written immediately

    after that carbon

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    Example :

    C4H9ClCH3CHCH2CH3 or CH3CH(Cl)CH2CH3

    Condensed structure

    Cl

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    b) Expanded Structure

    Expanded structures indicate the way in which

    the atoms are attached to each other and are not

    representations of the actual shapes of the

    molecules.

    Example :

    C4H9ClC C C C

    H H

    H H HCl

    H H H H

    Expanded structure

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    c) Skeletal Structure

    This structure shows only the carbon skeleton

    The hydrogen atoms that are assumed to bepresent, are not written.

    Other atoms such as O, Cl, N and etc. are shown

    Example :

    CH3CH(Cl)CH2CH3

    Cl

    =1.

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    H2C CH 2

    H2C CH 2

    2.

    =

    CH2=CHCH2OH3. =OH

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    Practice Exercise :

    Rewrite each of the following structures using skeletalformula :-

    O

    CH3CH

    2CH

    2C CH

    3

    (CH3)

    2CHCH

    2CH

    2CH(CH

    3)CH

    2CH

    3

    CH2= CHCH2CH2CH = CHCH3

    O

    CH3CH

    2CH ( CH

    3) CH

    2C OH

    1.

    2.

    3.

    4.

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    d) 3 - Dimensional formula(wedge - dashed wedge - wedge)

    Describes how the atoms of a molecule are arrangedin space

    Example :

    C

    Br

    H

    H

    H(Bromoethane)

    C

    Br

    H

    H

    H

    C

    H

    BrH

    H

    C

    H

    H

    B rH

    Indication :-

    bonds that lie in theplane of the pagebonds that lie behindthe plane

    bonds that project out

    of the plane of thepaper

    OR OR

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    e) Fischer Projection

    Vertical lines represent bonds that project behindthe plane of paper

    Horizontal lines represent bonds that project out of

    the plane of paper

    The intersection of vertical and horizontal linesrepresent a carbon atom, that is stereocentre

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    Example :

    2 butanol , CH3CH(OH)CH2CH3

    CH3

    HO

    CH2

    CH3

    H

    CH3

    H

    CH2

    CH3

    OHOR

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    11.3 FUNCTIONAL GROUPS AND

    HOMOLOGOUS SERIES

    A functional group is an atom or group of

    atoms in an organic molecule which characterizedthe molecule and enables the molecule to react

    in specific ways (determines its chemical properties)

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    Functional groups are important for three reasons :

    1. They are the units by which we divide organiccompounds into classes

    2.They are sites of chemical reaction; a particularfunctional group, in whatever compound it is found,undergoes the same types of chemical reactions

    3.Functional groups serve as a basic for namingorganic compounds

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    Homologous series is series of compoundswhere each member differs from the next member

    by a constant CH2 unit (14 mass unit)

    Members of a homologous series are calledhomologs

    A homologous series has four features:

    1. All the members of a particular homologous serieshave the same general formula.

    Example : General formula of alcohol is CnH2n+1OH,where n=1, 2, 3 etc

    For n=1 CH3OH (methanol)

    For n=2 C2H5OH (ethanol)

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    2. All the members of a particular homologous serieshave the same functional group. Thus, they have

    the same chemical reactions and can be made bythe same general methods

    Example : All alcohols contain OH group

    they react with carboxylic acids to give esters

    they can be prepared, for instance, by heatingdilute sodium hydroxide solution with an

    appropriate alkyl halide

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    3. The successive members of any homologous seriesdiffer by CH2

    Example : For alcohol group.

    The first few alcohols are :

    CH3OH (methanol)

    CH3CH2OH (ethanol)

    CH3CH

    2CH

    2OH (propanol)

    } The different by CH2} The different by CH2

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    4. There is a trend in the physical properties of themembers of any homologous series.

    As the molecules increase in size, there is agradual change in physical properties, e.g. theirboiling points increase

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    Some important functional groups in organiccompounds :-

    HomologousHomologous

    SeriesSeries

    FunctionalFunctional

    GroupGroup

    GeneralGeneral

    FormulaFormula

    IUPACIUPAC

    nomenclaturenomenclature

    PrefixPrefix-- --suffixsuffix

    ExampleExample

    alkanealkane nonenone CCnnHH2n+22n+2 --aneane CHCH44

    methanemethane

    alkenealkene C = CC = C

    (double(double

    bond)bond)

    CCnnHH2n2n --eneene CHCH22=CH=CH22

    etheneethene

    alkynesalkynes CC || CC

    (triple(triple

    bond)bond)

    CCnnHH2n2n--22 --yneyne CHCH || CHCH

    ethyneethyne

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    HomologousHomologous

    SeriesSeries

    FunctionalFunctional

    GroupGroup

    GeneralGeneral

    FormulaFormula

    IUPACIUPAC

    nomenclaturenomenclature

    PrefixPrefix-- --suffixsuffix

    ExampleExample

    arenearene CCnnHH2n2n--66 --benzenebenzene

    alcoholalcohol OHOH

    (hydroxyl)(hydroxyl)

    CCnnHH2n+12n+1OHOH alkanolalkanol CHCH33CHCH22OHOH

    ethanolethanol

    etherether OROR(alkoxy)(alkoxy)

    CCnnHH2n+22n+2OO alkoxyalkanealkoxyalkane CHCH33OCHOCH33methoxymethanemethoxymethane

    haloalkanehaloalkane XX

    (halogen)(halogen)

    CCnnHH2n+12n+1XX haloalkanehaloalkane CHCH33CHCH22ClCl

    chloroethanechloroethane

    aromatic

    ring

    CH3

    methylbenzene

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    HomologousHomologous

    SeriesSeries

    FunctionalFunctional

    GroupGroup

    GeneralGeneral

    FormulaFormula

    IUPACIUPAC

    nomenclaturenomenclature

    PrefixPrefix-- --suffixsuffix

    ExampleExample

    aldehydealdehyde CCnnHH2n2nOO alkanalalkanal CHCH33C=OC=O

    ketoneketone CCnnHH2n2nOO alkanonealkanone CHCH33C=OC=O

    carboxyliccarboxylicacidacid

    CnHCnH2n2nOO22 alkanoic acidalkanoic acid CHCH33C=OC=O

    C

    O

    H

    carbonylH

    ethanal

    C

    O

    carbonylCH3

    propanone

    C OH

    O

    carboxyl

    OHethanoic

    acid

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    HomologousHomologous

    SeriesSeries

    FunctionalFunctional

    GroupGroup

    GeneralGeneral

    FormulaFormula

    IUPACIUPAC

    nomenclaturenomenclature

    PrefixPrefix-- --suffixsuffix

    ExampleExample

    acylacyl

    chloridechloride

    CCnnHH2n+12n+1

    COClCOCl

    alkanoylalkanoyl

    chloridechloride

    CHCH33C=OC=O

    esterester CCnnHH2n2nOO22 alkylalkyl

    alkanoatealkanoate

    CHCH33COOCHCOOCH33

    amideamide CCnnHH2n+12n+1

    CONHCONH22

    --amideamide CHCH33CONHCONH22

    amineamine --NHNH22 CCnnHH2n+12n+1

    NHNH22

    --amineamine CHCH33NHNH22

    C

    O

    Cl

    acylCl

    ethanoyl

    chloride

    C

    O

    O C

    ester

    C

    O

    NH2

    ethyl

    ethanoate

    amideethanamide

    amino methanamine

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    11.4 CLASSIFICATION OF CARBON ANDHYDROGEN ATOMS IN ORGANIC

    MOLECULES

    Carbon atom classified primary (1o)

    secondary (2o)

    tertiary (3o)

    quarternary (4o)

    depending on the

    number of carbonatoms bonded to it

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    A primary carbon directly bonded to one other

    carbon atom(has 1 adjacent carbon atom)

    C

    H

    H

    CH3

    H

    Example :

    1o carbon

    1oH

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    A secondary carbon directly bonded to two other

    carbon atoms(has 2 adjacent carbon atoms)

    C

    H

    CH3

    H CH3

    Example :

    2o carbon

    2o H

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    A tertiary carbon directly bonded to three other

    carbon atoms(has 3 adjacent carbon atoms)

    C

    CH3

    CH3

    H CH3

    Example :

    3o carbon

    3o H

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    A quarternary carbon directly bonded to four other

    carbon atoms(has 4 adjacent carbon atoms)

    CCH3

    CH3

    CH3

    CH3

    Example :

    4o carbon

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    Similarly, a hydrogen atom is also classified as

    primary, secondary or tertiary depending on the

    type of carbon to which it is bonded.

    1 hydrogen atom bonded to a 1 C atom

    2 hydrogen atom bonded to a 2 C atom

    3 hydrogen atom bonded to a 3 C atom

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    Classification of haloalkanes (alkyl halides)

    Alkyl halides are classified based on the carbon atom

    to which the halogen is directly attached.

    1 alkyl halide the halogen atom is bonded to a

    primary carbon atom

    2 alkyl halide the halogen atom is bonded to asecondary carbon atom

    3 alkyl halide the halogen atom is bonded to atertiary carbon atom

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    H C

    H

    H

    C

    H

    H

    Cl

    H C

    H

    H

    C

    H

    C

    H

    H

    HCl

    H C

    H

    H

    C C

    H

    H

    HCl

    CH3

    1 alkyl chloride

    1 C

    2 alkyl chloride

    2 C

    3 alkyl chloride

    3 C

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    Classification of alcohols

    Alcohols are classified based on the carbon atom

    to which the hydroxyl group is directly attached.

    1 alcohol the hydroxyl group is attached to a

    1 carbon atom

    2 alcohol the hydroxyl group is attached to a2 carbon atom

    3 alcohol the hydroxyl group is attached to a3 carbon atom

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    H C

    H

    H

    C

    H

    H

    OH

    H C

    H

    H

    C

    H

    C

    H

    H

    HOH

    H C

    H

    H

    C C

    H

    H

    HOH

    CH3

    1 alcohol

    1 C

    2 C

    2 alcohol

    3 alcohol

    3 C

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    Classification of amines

    Amines are classified based on the number of alkylgroups or carbon atoms that are directly attached

    to the nitrogen atom

    1 amine N is bonded to one alkyl group

    2 amine N is bonded to two alkyl groups

    3

    amine N is bonded to three alkyl groups

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    H3

    C N

    H

    H

    H3

    C N H

    CH3

    H3C N

    CH3

    CH3

    N bonded toone alkyl group

    A primary (1)amine

    N bonded totwo alkyl group

    A secondary (2)amine

    N bonded to three

    alkyl group

    A tertiary (3)amine

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    ISOMERISM

    Structural/Constitutional Isomerism Stereoisomerism

    Isomerism

    Chainisomerism

    Positionalisomerism

    Functionalgroup

    isomerism

    Geometricisomerism

    Opticalisomerism

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    Isomerism is the existence of different compounds

    with the same molecular formula but different

    structural formulae

    Isomers different compounds that have same

    molecular formula

    Two types ofisomerism

    structural isomerism

    stereoisomerism

    different order of attachmentof atoms

    different spatial arrangement of

    atoms in molecules

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    Structural isomerism

    Chain/skeletal

    isomerism

    Structural isomers are different compounds with

    the same molecular formula but differ in the order

    of attachment of atoms

    Positional

    isomerism

    Functional

    groupisomerism

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    The isomers differ in the carbon skeleton(different carbon chain)

    a) Chain/skeletal isomerism

    They possess the same functional group andbelong to the same homologous series

    Example :

    C5H12 :

    CH3CH2CH2CH2CH3

    CH3CHCH2CH3

    CH3

    CH3-C-CH3

    CH3

    CH3

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    1,2-dimethylbenzene

    iii) C8H10 CH3CH3

    CH3

    CH3

    1,3-dimethylbenzene

    CH3

    CH3

    1,4-dimethylbenzene

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    c) Functional group isomerism

    These isomers have different functional groups

    and belong to different homologous series withthe same general formula

    Different classes of compounds that exhibit

    functional group isomerism :-

    General formulaGeneral formula Classes of compoundsClasses of compounds

    CnH2n+2O alcohol and ether

    CnH2nO aldehyde and ketone

    CnH2n alkene and cycloalkane

    CnH2nO2 carboxylic acid and ester

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    Example :

    i) C2H6O CH3CH2OH

    ethanol

    CH3OCH3

    dimethyl ether

    ii) C3H6O CH3CH2C-H

    O

    propanal

    CH3C-CH3

    O

    propanone

    iii) C3H6O2 CH3CH2C-OH

    O

    propanoic acid

    CH3C-O-CH3

    O

    methyl ethanoate

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    Stereoisomerism

    Geometric Isomerism Optical Isomerism

    a) Geometric isomerism

    occurs only in two classes of compounds :

    Alkenes & cyclic compound

    (because of rigidity in molecules)

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    Geometric isomers (also called cis-trans isomers)

    are stereoisomers that differ by groups being

    on the same side (cis-isomer) or opposite

    sides (trans-isomer) of a site of rigidity in a molecule

    The requirements for geometric isomerism :

    i) restricted rotation about a C=C,double bond, inalkenes or a C-C single bond in cyclic compounds

    ii) each carbon atom of a site of restricted rotation hastwo different groups attached to it

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    Examples :

    H3C CH3

    H H

    C C=

    i)

    cis-2-butene

    H3C

    C=C

    CH3

    H

    H

    trans-2-butene

    ii) H3C CH2CH3

    C= C

    H CH3

    trans-3-methyl-2-pentene

    H3C CH3

    C= CH CH2CH3

    cis-3-methyl-2-pentene

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    iii)

    HH

    CH3 CH3

    cis-1,2-dimethylcyclohexane

    H

    HCH3

    CH3

    trans-1,2-dimethylcyclohexane

    Cl

    Cl

    H

    H

    iv)

    Cl

    Cl

    H

    H

    cis-1,3-dichlorocyclopentane trans-1,3-dichlorocyclopentane

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    If one of the doubly bonded carbons has 2 identical

    groups, geometric isomerism is not possible.

    Examples :

    CH3CH2i)

    C = C

    H

    HH3C

    2-methyl-2-butene

    Hii)

    C= C

    CH3

    CH3Cl

    1-chloro-2-methylpropene

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    cis-trans isomers have similar chemical properties

    but different physical properties

    They differ in melting and boiling points and

    solubility due to different polarity of the molecules

    cis-isomers polar molecules

    trans-isomers non-polar

    Melting point: trans- isomer > cis-isomer Boiling point: cis-isomer > trans- isomer

    Stability: trans-isomer > cis-isomer

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    b) Optical isomerism

    If a beam of light is passed through a piece of

    polarizer prism, the emergent light vibrates in a

    single plane, hence it is called aplane-polarized

    light

    Opticallyactive compounds have the ability to

    rotate plane-polarized light

    The angle of rotation can be measured with an

    instrument called polarimeter

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    Schematic representation of a polarimeter containingan optically active sample :

    clockwise rotation plus sign (+) / dextrorotarory

    anticlockwise rotation minus sign (-) / levorotorary

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    The requirements for optical isomerism :-

    i) molecule contains a chiral carbon or chiral centre(carbon atom with 4 different groups attached to it)

    ii) molecule is not superimposable with its mirror image

    A representation of a chiral molecule with

    3-dimensional formula :-

    P

    CQ

    R

    S* P{Q{R{S

    *designates chiral centre

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    Enantiomers are apair of mirror-image molecules

    that are notsuperimposable (must have one or more

    chiral carbons)

    Examples :

    i) 2-butanol, CH3CHCH2CH3

    OH

    C*

    CH2CH3

    H3C

    OHH

    C

    CH2CH3

    CH3HOH

    enantiomers

    :-

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    A racemic mixture or racemate is an equimolar

    mixture of enantiomers which is optically inactive

    because the two components rotate plane-polarized

    light equally (same degree of rotation but in opposite

    direction so they can cancel each others rotation)

    A pair of enantiomers have identical chemical and

    physical properties but differ in the direction of

    rotation of plane-polarized light

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    A compound with n chiral centers can have a

    maximum of2n stereoisomers

    If a molecule contains two or more chiral centers,

    diastereomers may exist

    Diastereomers are stereoisomers that are not

    mirror images of each other

    All physical properties of diastereomers are usually

    different from one another

    Example :

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    Example :

    The 4 stereoisomers of 2-amino-3-hydroxybutanoicacid CH3CH-CHCOOH are shown below using

    OH NH2Fischer projection formula:-

    COOH COOH

    CH3 CH3

    HH

    HH

    NH2 H2NOH HO

    enantiomers

    COOH

    NH2H

    H

    HO

    CH3

    COOH

    H

    H

    OH

    H2N

    enantiomers

    CH3

    A B

    C D

    Four pairs ofdiastereomersare identified :

    A and C;A and D ;B and C;B and D

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    Meso compoundis a stereoisomer that has more

    than one chiral centres and that issuperimposableon its mirror image because of the presence of an

    internal plane ofsymmetry, hence it is optically

    inactive (does not cause a rotation of plane-polarizedlight)

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    Example : Tartaric acid , HOOCCH(OH)CH(OH)COOH

    COOH

    OH

    OH

    H

    H

    COOH

    COOH

    COOH

    HO

    HO

    H

    H

    COOH

    COOH

    H

    H

    OH

    OH

    plane of symmetry

    plane of symmetry

    rotate 180o

    P Q

    identical

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    At first glance, Pand Q are assumed to be enantiomers

    But if compound Q is rotated 180o in the plane ofthe paper, it is actually identical to compound P,therefore Pand Q are superimposable mirror images

    Pand Q are thesame compound

    It is a meso compound

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    COOH

    OH

    OH

    H

    H

    COOH

    COOH

    COOH

    R S

    COOH

    COOH

    HHO

    H OH*not a plane of symmetry

    *not a plane of symmetry

    rotate 180o

    different

    H OH

    HHO

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    R and S are related as mirror images and are notsuperimposable even if rotated 180o

    Thus R and Sconstitute an enantiomeric pair

    There are 2 pairs of diastereomers :

    Pand R & Pand S

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    Further examples of meso compounds:

    CH3

    CH3

    Cl

    Cl

    H

    H

    CHO

    CHO

    HO

    HO

    H

    HH OH plane of symmetry

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    11.6 REACTIONS OF ORGANIC COMPOUNDS

    11.6.1 Types of CovalentBond Cleavage/Fission

    All chemical reactions involved bond breaking andbond making

    Two types of covalent bond cleavage :-

    Homolytic cleavage

    Heterolytic cleavage

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    a) Homolytic Cleavage

    Occurs in a non-polar bond involving two atoms of

    similar electronegativity

    A single bond breaks symmetrically into two equal

    parts, leaving each atom with one unpaired electron

    Free radicals are formed in homolytic cleavage

    X X X + X 2X

    free radicals

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    b) Heterolytic Cleavage

    Occurs in a polar bond involving unequal sharingof electron pair between two atoms of differentelectronegativities

    A single bond breaks unsymmetrically and both the

    bonding electrons are transferred to the moreelectronegative atom

    Cation and anion are formed in heterolytic cleavage

    A BA

    -

    + B+

    A is moreelectronegative

    A+ + B- B is more

    electronegative

    cationanion

    anioncation

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    Carbocations and free radicals are intermediates inorganic reactions.

    They are unstable and highly reactive

    11 6 2 R ti I t di t

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    11.6.2 Reaction Intermediates

    a) Carbocation

    Also called carbonium ion

    A very reactive species with apositive charge

    on a carbon atom

    Carbocation is formed in heterolytic cleavage

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    Example :

    (CH3)3C ClH H

    (CH3)3C+

    carbocation

    + Cl-

    anion

    Chlorine is more electronegative than carbon andthe CCl bond is polar

    The CCl bond breaks heterolitically and both thebonding electrons are transferred to chlorine atomto form anion and carbocation

    b) F R di l

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    b) Free Radical

    A very reactive species with an unpaired electron

    Formed in homolytic cleavage

    Cl Cl

    Example :

    uv Cl

    free radicals

    + Cl

    C C C + C

    H3C H CH3 + H

    11 6 3 R l ti St biliti f

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    11.6.3 Relative Stabilities ofCarbocations and Free Radicals

    Carbocation and free radical primary

    secondary

    tertiary

    depending on the number of carbon atoms directlybonded to the :-

    positively charged carbon atom (for carbocation)

    carbon atom with unpaired electron (for free radical)

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    The stability of carbocation increases with thenumber of alkyl groups present

    The alkyl groups are electron-releasing relative tohydrogen, thus help to stabilize the positive chargeon the carbocation

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    Lik i h bili f f di l i

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    Likewise, the stability of free radical increases asmore alkyl groups are attached to the carbon atomwith unpaired electron

    Free RadicalStability :

    H C H < R C H < R C H < R C R

    H H RR

    methylradical primary(1) secondary(2) tertiary(3)

    Increasing stability

    11 6 4 Reagents and Sites of Organic Reactions

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    11.6.4 Reagents andSites of OrganicReactions

    a) Elec trophile (E+

    )

    Means electron loving

    An electron-deficientspecies and electron-pair

    acceptorthat attacks a part of a molecule wherethe electron density is high

    An electrophile can be either neutralorpositivelycharged

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    Examples of electrophiles :-

    1.cations such as H+, H3

    O+, NO2+, Br+ etc.2.carbocations.3.Lewis acids such as AlCl3, BF3 etc.4.oxidizing agents such as Cl2, Br2 and etc

    Examples of electrophilic sites in organic molecules :-

    molecules with low electron density around apolar bond such as :-

    H+ H- H+ H- H+ H-C = O C X C OH

    carbonyl haloalkanes hydroxyl

    compound

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    b) Nucleophile (Nu-)

    Means nucleus loving

    An electron-rich species and electron-pair donorthat attacks a part of a molecule where the electron

    density is low

    A nucleophile can be either neutralor negativelycharged

    E l f l hil

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    Examples of nucleophiles :-

    1. anions such as OH-

    , RO-

    , Cl-

    , Cn-

    etc.2. carbanions. (species with ve charge on C atoms)3. Lewis bases which can donate lone pair electrons

    such as NH3, H2O etc.

    Examples of nucleophilic sites in organic molecules :-

    molecules with high electron densityaround thecarbon-carbon multiple bond such as :-

    -C=C- (alkenes) , -C|C-(alkynes),

    (benzene ring) and etc.

    11 6 5 T f O i R ti

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    11.6.5 Types of OrganicReactions

    The four main types of organic reactions are:

    Addition

    Substitution

    Elimination

    Rearrangement

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    a) ElectrophilicAddition

    Initiated by an electrophile, which attacks anucleophilic site of a molecule

    Typical reaction of unsaturated compounds suchas alkenes and alkynes

    Example :

    CH3

    CH=CH2

    + Br2

    CH3

    CHBrCH2

    Brroom

    temperature

    electrophile

    b) l hili ddi i

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    b) NucleophilicAddition

    Initiated by a nucleophile, which attacks anelectrophilic site of a molecule

    Typical reaction ofcarbonyl compounds

    Example :

    CH3 C CH 3 + HCN

    O

    CH3 C CH3

    OH

    CN

    H

    H+

    H+ CN-

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    2. Substitution Reaction

    A reaction in which an atom orgroup in a molecule is replacedby

    another atom or group

    a) Free-radicalSubstitution

    b) ElectrophilicSubstitution

    c) NucleophilicSubstitution

    ) F di l S b tit ti

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    a) Free-radicalSubstitution

    Substitution which involves free radicals asintermediate species

    Example :

    CH3CH3 + Cl2 CH3CH2Cl + HCluv light

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    b) ElectrophilicSubstitution

    Typical reaction ofaromatic compounds

    The aromatic nucleus has high electron density,thus it is nucleophilic and is tend to electrophilic

    attack

    Example :

    + Br2Fe

    catalystBr + HBr

    electrophile

    BrH

    BrH

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    c) NucleophilicSubstitution

    Typical reaction of saturated organic compoundsbearing polar bond as functional group, such ashaloalkane and alchohol

    Example :

    CH3CH2Br + OH-(aq) CH3CH2OH + Br

    -(aq)

    nucleophile

    HH

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    3. Elimination Reaction

    A reaction in which atoms or groups are removedfrom adjacent carbon atoms of a molecule to forma multiple bond(double or triple bond)

    E

    limination reaction results in the formation ofunsaturated molecules

    CH3CH2OH CH2= CH2 + H2OConc. H2SO4

    (

    Example :

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