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    Lecture-1 Alkyl Halide Dinusha

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    NadunKodikara
    Alkyl halides are organic compounds containing one or more carbon-halogen bonds. They can be classified as primary, secondary, or tertiary depending on the number of carbons bonded to the halogenated carbon. Alkyl halides undergo nucleophilic substitution reactions by two mechanisms: SN1 and SN2. The SN1 reaction involves the formation of a carbocation intermediate and results in the loss of stereochemistry. The SN2 reaction is a single concerted step with inversion of stereochemistry. The reactivity depends on factors like the stability of carbocation intermediates, the nature of the nucleophile and leaving group, and steric hindrance around the reaction center. Tertiary alkyl halides favor

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    Lecture-1 Alkyl Halide Dinusha

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    NadunKodikara
    134 views44 pages
    Alkyl halides are organic compounds containing one or more carbon-halogen bonds. They can be classified as primary, secondary, or tertiary depending on the number of carbons bonded to the halogenated carbon. Alkyl halides undergo nucleophilic substitution reactions by two mechanisms: SN1 and SN2. The SN1 reaction involves the formation of a carbocation intermediate and results in the loss of stereochemistry. The SN2 reaction is a single concerted step with inversion of stereochemistry. The reactivity depends on factors like the stability of carbocation intermediates, the nature of the nucleophile and leaving group, and steric hindrance around the reaction center. Tertiary alkyl halides favor

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    Alkyl halides are organic compounds containing one or more carbon-halogen bonds. They can be classified as primary, secondary, or tertiary depending on the number of carbons bonded to the halogenated carbon. Alkyl halides undergo nucleophilic substitution reactions by two mechanisms: SN1 and SN2. The SN1 reaction involves the formation of a carbocation intermediate and results in the loss of stereochemistry. The SN2 reaction is a single concerted step with inversion of stereochemistry. The reactivity depends on factors like the stability of carbocation intermediates, the nature of the nucleophile and leaving group, and steric hindrance around the reaction center. Tertiary alkyl halides favor

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    © All Rights Reserved
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    134 views44 pages

    Lecture-1 Alkyl Halide Dinusha

    Uploaded by

    NadunKodikara
    Alkyl halides are organic compounds containing one or more carbon-halogen bonds. They can be classified as primary, secondary, or tertiary depending on the number of carbons bonded to the halogenated carbon. Alkyl halides undergo nucleophilic substitution reactions by two mechanisms: SN1 and SN2. The SN1 reaction involves the formation of a carbocation intermediate and results in the loss of stereochemistry. The SN2 reaction is a single concerted step with inversion of stereochemistry. The reactivity depends on factors like the stability of carbocation intermediates, the nature of the nucleophile and leaving group, and steric hindrance around the reaction center. Tertiary alkyl halides favor

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    of 44

    Alkyl Halides

    What Is an Alkyl Halide?


    An organic compound containing at least one carbonhalogen bond (C-X)
    o X (F, Cl, Br, I) replaces H

    Can contain many C-X bonds

    Some uses
    Solvent
    Refrigerants
    Pharmaceuticals and precursors

    Alkyl halides
    Alkyl halides are organic molecules containing a halogen
    atom directly bonded to an sp3 hybridized carbon atom.
    Alkyl halides are classified as primary (1), secondary
    (2), or tertiary (3), depending on the number of
    carbons bonded to the carbon with the halogen atom.
    H

    H
    H

    Methyl halide

    One R group
    1

    C
    R

    Two R groups Three R groups


    2
    3

    The halogen atom in halides is often denoted by the symbol X.

    Types of halides
    CH2CH3
    CH3CH2CH2

    Cl

    Cl

    3 chloride

    2 chloride

    CH2CH3

    CH3
    CH3

    C CH2Cl

    H
    1 chloride

    CH 3

    CH 3

    2 chloride

    Cl

    CH3

    There are other types of organic halides. These include vinyl halides, aryl halides,
    allylic halides and benzylic halides.

    Vinyl halides
    alkene.

    halogen atom (X) bonded to sp2 carbon of


    H

    H
    C

    C
    X

    Types of halides
    Aryl halides

    X directly bonded to a benzene ring.


    X

    Allylic halides
    X bonded to the carbon atom
    adjacent to a C=C double bond.
    H
    H
    C
    H

    C
    CH2

    Benzylic halides
    X bonded to the carbon atom
    CH2X
    adjacent to a benzene ring.

    Naming Alkyl Halides


    Name is based on longest carbon chain
    o (Contains double or triple bond if present)
    o Number from end nearest any substituent (alkyl or
    halogen)

    Naming with Multiple


    Halides
    If more than one of the
    same kind of halogen is
    present, use prefix di, tri,
    tetra

    If there are several


    different halogens,
    number them and list
    them in alphabetical
    order

    Naming if Two Halides or Alkyl Are Equally Distant


    from Ends of Chain
    Begin at the end nearer the substituent whose
    name comes first in the alphabet

    Many Alkyl Halides That Are Widely Used Have

    Common Names

    Chloroform
    Carbon tetrachloride
    Methylene chloride
    Methyl iodide
    Trichloroethylene

    Cl

    Cl

    H
    Dichloromethane

    Cl

    Cl
    H

    Cl

    Cl

    D
    Deuterated chloroform

    Structure of Alkyl Halides


    C-X bond is longer as you go down periodic table
    C-X bond is weaker as you go down periodic table
    C-X bond is polarized with slight positive on carbon
    and slight negative on halogen

    11

    Quick Review Questions

    Preparing Alkyl Halides


    Alkyl halide is from addition of HCl, HBr, HI to
    alkenes to give Markovnikov product
    Alkyl dihalide from anti addition of bromine or
    chlorine

    14

    It is usually not a good idea to plan a synthesis that


    uses this method

    Why?

    Reaction of Alkanes with


    Halogens

    16

    Preparing Alkyl Halides from Alcohols


    Reaction of tertiary C-OH with HX is fast and effective
    o Add HCl or HBr gas into ether solution of tertiary alcohol

    Primary and secondary alcohols react very slowly and


    often rearrange, so alternative methods are used

    17

    Preparation of Alkyl Halides from Primary and

    Secondary Alcohols
    Specific reagents avoid rearrangements of
    carbon skeleton
    Thionyl chloride converts alcohols into alkyl
    chlorides (SOCl2 : ROH RCl)
    Phosphorus tribromide converts alcohols into
    alkyl bromides (PBr3: ROH RBr)

    18

    Reactions of Alkyl Halides: Grignard

    Reagents
    Reaction of RX with Mg in ether or THF
    Product is RMgX an organometallic compound
    (alkyl-metal bond)
    o R is alkyl 1, 2, 3, aryl, alkenyl
    o X = Cl, Br, I

    19

    Reactions of Grignard
    Reagents
    Many useful reactions
    o RMgX behaves as R- (adds to C=O)
    o RMgX + H3O+ R-H

    20

    Alkyl Halides React with Nucleophiles and Bases


    Alkyl halides are polarized at the carbon-halide bond,
    making the carbon electrophilic
    Nucleophiles will replace the halide in C-X bonds of many
    alkyl halides(reaction as Lewis base)
    Nucleophiles that are Brnsted bases produce elimination

    21

    Good Base

    Quick Review Questions

    The Nature of
    Substitution

    Substitution, by definition, requires that a "leaving group",


    which is also a Lewis base, departs from the reacting
    molecule.
    A nucleophile is a reactant that can be expected to
    participate effectively in a substitution reaction.

    24

    Substitution Mechanisms

    SN1
    o Two steps with carbocation intermediate
    o Occurs in 3, allyl, benzyl

    SN2
    o Two steps combine - without intermediate
    o Occurs in primary, secondary

    25

    Two Stereochemical
    Modes of Substitution
    Substitution with inversion:

    Substitution with retention:

    26

    The SN2 Reaction

    Reaction is with inversion at reacting center


    Follows second order reaction kinetics
    Nomenclature to describe characteristic step:
    o S=substitution
    o N (subscript) = nucleophilic
    o 2 = both nucleophile and substrate in characteristic
    step (bimolecular)

    27

    SN2 Process

    The reaction involves a transition state in which


    both reactants are together

    28

    SN2 Transition State

    The transition state of an SN2 reaction has a


    planar arrangement of the carbon atom and
    the remaining three groups

    29

    Characteristics of the SN2 Reaction

    Sensitive to steric effects


    Methyl halides are most reactive
    Primary are next most reactive
    Secondary might react
    Tertiary are unreactive by this path
    No reaction at C=C (vinyl halides)

    30

    Steric Effects on SN2


    Reactions

    The carbon atom in (a) bromomethane is readily accessible


    resulting in a fast SN2 reaction. The carbon atoms in (b) bromoethane
    (primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-methylpropane
    (tertiary) are successively more hindered, resulting in successively slower SN2
    reactions.
    31

    Order of Reactivity in SN2


    The more alkyl groups connected to the reacting carbon,
    the slower the reaction
    o Difficult for nucleophile to approach, steric strain in T.S.

    32

    The Nucleophile
    Neutral or negatively charged Lewis base
    Reaction increases coordination at nucleophile
    o Neutral nucleophile acquires positive charge
    o Anionic nucleophile becomes neutral
    o See Table 7-1 for an illustrative list

    33

    Relative Reactivity of Nucleophiles


    Depends on reaction and conditions
    More basic nucleophiles react faster
    Anions are usually more reactive than neutrals

    34

    The Leaving Group


    A good leaving group reduces the barrier to a reaction
    Stable anions that are weak bases are usually excellent
    leaving groups and can delocalize charge

    35

    Poor Leaving Groups


    If a group is very basic or very small, it is prevents
    reaction

    36

    The SN1 Reaction

    Tertiary alkyl halides react rapidly in protic solvents by


    a mechanism that involves departure of the leaving
    group prior to addition of the nucleophile
    Called an SN1 reaction occurs in two distinct steps
    while SN2 occurs with both events in same step
    If nucleophile is present in reasonable concentration
    (or it is the solvent), then ionization is the slowest step

    37

    SN1 Energy Diagram


    k1

    k-1

    k2

    Rate-determining step is
    formation of carbocation

    38

    Step through highest


    energy point is ratelimiting (k1 in forward
    direction)
    V = k[RX]

    Rate-Limiting Step
    The overall rate of a reaction is controlled by the
    rate of the slowest step
    The rate depends on the concentration of the
    species and the rate constant of the step
    The highest energy transition state point on the
    diagram is that for the rate determining step
    (which is not always the highest barrier)
    This is the not the greatest difference but the
    absolute highest point

    39

    Stereochemistry of SN1
    Reaction
    The planar
    intermediate
    leads to loss of
    chirality
    o A free
    carbocation
    is achiral

    Product is
    racemic or has
    some inversion

    40

    Delocalized Carbocations
    Delocalization of cationic charge enhances
    stability
    Primary allyl is more stable than primary alkyl
    Primary benzyl is more stable than allyl

    41

    Characteristics of the SN1 Reaction


    Tertiary alkyl halide is most reactive by this
    mechanism

    o Controlled by stability of
    carbocation

    42

    Allylic and Benzylic Halides


    Allylic and benzylic intermediates stabilized by
    delocalization of charge
    o Primary allylic and benzylic are also more reactive in
    the SN2 mechanism

    43

    Effect of Leaving Group on SN1


    Critically dependent on leaving group
    o Reactivity: the larger halides ions are better leaving groups

    In acid, OH of an alcohol is protonated and leaving group


    is H2O, which is still less reactive than halide
    p-Toluensulfonate (TosO-) is excellent leaving group

    44

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