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    Chapter 7 - Alkylhalides

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    عبدالرجمن عكاشة

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    Chapter 7 - Alkylhalides

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    عبدالرجمن عكاشة
    2 views42 pages

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    Chapter 7- Alkylhalides

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    2 views42 pages

    Chapter 7 - Alkylhalides

    Uploaded by

    عبدالرجمن عكاشة

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 42

     An organic compound containing at least one carbon-

    halogen bond (C-X)


     X (F, Cl, Br, I) replaces H
     Can contain many C-X bonds
     Properties and some uses
     Fire-resistant solvents
     Refrigerants
     Pharmaceuticals and precursors
     Find longest chain, name it as parent chain
     (Contains double or triple bond if present)
     Number from end nearest any substituent (alkyl or
    halogen)
     Begin at the end nearer the substituent having its name first in
    the alphabet
     Name halide as a substituent
     Two best ways:
     Alkyl halide from addition of HCl, HBr, HI to alkenes to give
    Markovnikov product

     Alkyl dihalide from anti addition of bromine or chlorine


     Alkane + Cl2 or Br2, heat or light replaces C-H with C-X but
    gives mixtures
     Hard to control
     Occurs via free radical mechanism
     It is usually not a good idea to plan a synthesis that uses this
    method
     If there is more than one type of hydrogen in an alkane,
    reactions favor replacing the hydrogen at the most highly
    substituted carbons (not absolute)
     Based on quantitative analysis of reaction products, relative reactivity
    is estimated
     Order parallels stability of radicals
     Reaction selectivity is greater with bromine than chlorine
     i.e. 3o > 2o > 1o
     Addition reactions of X2 and HX with alkenes (Chapter 4)

     Reaction of an alkane with Cl2 (Chapter 2)


     Reaction of tertiary C-OH with HX is fast and effective
     Add HCl or HBr gas into ether solution of tertiary alcohol
    (ether is solvent)
     Primary and secondary alcohols react very slowly and often
    rearrange under acidic conditions (with HX), so alternative
    methods are used usually thionyl chloride (SOCl2) or
    phosphorus tribromide (PBr3)
     Reaction of RX with Mg in ether or THF
     Product is RMgX – an organometallic compound (alkyl-metal
    bond)
     R is alkyl 1° ,alkyl 2° , alkyl 3°, aryl, alkenyl
     X = Cl, Br, I
     Grignard reagent – magnesium salt of a carbon-based acid
     Carbon atom is a carbon anion, or carbanion
     This carbon atom is both nucleophilic and basic
     Water or protic solvents (eg. ROH) must be excluded
     Aklyl halides (RX) when they react with nucleophiles/bases can undergo
     Substitution of the X group by the nucleophile
     Elimination of HX to yield an alkene by the base
     In 1896, Walden showed that (-)-malic acid could be converted to
    (+)-malic acid by a series of chemical steps with achiral reagents
     This established that optical rotation was directly related to
    chirality and that it changes with inversion of chirality
     Reaction of (-)-malic acid with PCl5 gives (+)-chlorosuccinic acid
     Further reaction with wet silver oxide gives (+)-malic acid
     The reaction series starting with (+) malic acid gives (-) acid
    inversion

    retention retention

    inversion
     The PCl5 reactions invert the stereochemistry at the chirality
    center
     The reactions involve substitution at that center
     Therefore, nucleophilic substitution can invert the configuration
    at a chirality center
     The Ag2O reactions occur with retention (without inverting the
    stereochemistry at the chirality center)
     Regardless of mechanism, the overall changes during a
    nucleophilic substitution reaction are the same
     Nucleophile (Nu: or Nu:– ) reacts with a substrate R— X
     Substitutes for the leaving group X:–
     To yield a new product R— Nu
     Reaction occurs with inversion at reacting center
     Takes place in a single step
     Without intermediates
     Entering nucleophile is 180˚ from the leaving group
     Reaction is bimolecular
     The rate of the reaction depends on the concentration of both the nucleophile
    and the substrate
     The reaction involves a transition state in which both reactants
    are together
     The transition state of an S 2 reaction has a roughly planar arrangement of the carbon atom and the
    N
    remaining three groups
     Rate = k [Nu][RX] (bimolecular)
     Alkyl Halide: 1°> 2°>> 3°
     Backside attack
     One step
    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 S N2 reactions.
     The more alkyl groups connected to the reacting carbon, the
    slower the reaction
     A good leaving group reduces the energy barrier to a
    reaction
     Stable anions that are weak bases are usually excellent
    leaving groups and can delocalize charge

    Best leaving groups


     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
     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
    this step
     SN1 reactions are unimolecular

     The rate depends on the concentration of the substrate (Rate


    = k[RX])
     The substrate must undergo a reaction without involvement of the nucleophile
     The planar intermediate leads to loss of chirality
     A free carbocation is achiral
     Product is racemic or has some inversion
     Critically dependent on leaving group
     The best leaving groups are those that give the most stable anions
     Elimination is an alternative pathway to substitution
     Opposite of addition
     Generates an alkene
     Can compete with substitution and decrease yield, especially for
    SN1 processes
     In the elimination of HX from an alkyl halide, the more highly substituted
    alkene product predominates
     Eliminations can take place by several different mechanisms
    differing in the time of C—H and C—X bond breaking
     E1 Reaction: elimination, unimolecular
     Involves a carbocation intermediate
     E1cB Reaction: elimination, unimolecular
     Involves a carbanion intermediate
     Both substitution reactions occur in biological pathways
     Among the most common is methylation
     All three elimination reactions occur in biological pathways
     E1cB very common
     Typical example occurs during biosynthesis of fats when 3-
    hydroxybutyryl thioester is dehydrated to corresponding
    thioester

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