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    Chapter 6: Organohalogens: Alkyl Halide Vinyl Halide Aryl Halide

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    Organohalogens are a class of compounds containing halogens as a functional group. There are five major classes of organohalogens: alkyl halides, vinyl halides, aryl halides, geminal dibromides, and vicinal dibromides. Alkyl halides can be prepared through several methods including free radical halogenation of alkanes, halogenation of alkenes and alkynes, from alcohols, and from other halides. Their physical properties depend on factors like molecular weight, halogen atom, and chain length. Nomenclature involves both IUPAC and common names.

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    Chapter 6: Organohalogens: Alkyl Halide Vinyl Halide Aryl Halide

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    cikguhafidzuddin
    244 views13 pages
    Organohalogens are a class of compounds containing halogens as a functional group. There are five major classes of organohalogens: alkyl halides, vinyl halides, aryl halides, geminal dibromides, and vicinal dibromides. Alkyl halides can be prepared through several methods including free radical halogenation of alkanes, halogenation of alkenes and alkynes, from alcohols, and from other halides. Their physical properties depend on factors like molecular weight, halogen atom, and chain length. Nomenclature involves both IUPAC and common names.

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    Organohalogens are a class of compounds containing halogens as a functional group. There are five major classes of organohalogens: alkyl halides, vinyl halides, aryl halides, geminal dibromides, and vicinal dibromides. Alkyl halides can be prepared through several methods including free radical halogenation of alkanes, halogenation of alkenes and alkynes, from alcohols, and from other halides. Their physical properties depend on factors like molecular weight, halogen atom, and chain length. Nomenclature involves both IUPAC and common names.

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    244 views13 pages

    Chapter 6: Organohalogens: Alkyl Halide Vinyl Halide Aryl Halide

    Uploaded by

    cikguhafidzuddin
    Organohalogens are a class of compounds containing halogens as a functional group. There are five major classes of organohalogens: alkyl halides, vinyl halides, aryl halides, geminal dibromides, and vicinal dibromides. Alkyl halides can be prepared through several methods including free radical halogenation of alkanes, halogenation of alkenes and alkynes, from alcohols, and from other halides. Their physical properties depend on factors like molecular weight, halogen atom, and chain length. Nomenclature involves both IUPAC and common names.

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    Chapter 6: Organohalogens

    -Organohalogens are a class of compounds which has


    halogens as the functional group.
    -General formula: CnH2n+1X
    There are 5 major classes:
    1. Alkyl halide: compound which has an X atom bonded
    to one of the sp3 hybrid C atoms of an alkyl grp.
    2. Vinyl halide: compound which has an X atom bonded
    to one of the sp2 hybrid C atoms of an alkene.
    3. Aryl halide: compound which has a X atom bonded to
    one of the sp2 hybrid C atoms of an aromatic ring
    Examples:

    H H I
    H H
    H C C Br C C
    H H H Cl
    alkyl halide vinyl halide aryl halide

    Chloroethane chloroethene p-dichlorobenzene

    Iodomethane benzyl chloride 1-chloro-2-butene


    More Examples:

    Alkyl Halide
    H
    CH3I CH3CH2Cl
    R-C-X iodomethane chloromethane

    Vinyl Halide Br
    H H
    CH2=CHCl CH3CH=CCH3
    C=C
    H H chloroethene 2-bromo-2-butene

    Aryl Halide

    Br Cl Cl
    x bromobenzene
    p-dichlorobenzene

    Nomenclature

    A. Common Name and Trivial Names


     constructed by naming the alkyl grp followed by the
    halide, i.e isopropyl bromide. (origin of term alkyl
    halide).
     suitable for simple alkyl halides.
     trivial names are also similar to common names. Trivial
    names are names which are not clearly related to their
    structures. Examples:

     CH2Cl2 is methylene chloride (IUPAC: dichloromethane)


     CHCl3 is chloroform (IUPAC: trichloromethane)
     CCl4 is carbon tetrachloride (IUPAC:
    tetrachloromethane)

    B. IUPAC
     Named as haloalkane
     Choose the longest carbon chain, even if the halogen is
    not bonded to any of those C’s
     Use lowest possible C atom numbers for the position of
    halide.
     Examples:
    CH3 CH CH2CH3 CH3
    Cl CH3 CH CH2F
    Common: sec-butyl chloride isobutyl fluoride
    IUPAC : 2-chlorobutane 1-fluoro-2-methylpropane

    Common: cyclohexyl iodide Common: n-butyl chloride


    IUPAC: iodocylohexane IUPAC: 1-chlorobutane
    Classes of Alkyl Halides

    There are 4 classes according to the nature of the C atom


    bonded to the halogen:
    1. Methyl halides: only one C, CH3X
    2. Primary: C to which X is bonded has only one C-C
    bond [R-CH2-X]
    3. Secondary: C to which X is bonded has two C-C
    bonds [R2CH-X]
    4. Tertiary: C to which X is bonded has three C-C
    bonds [R3C-X]

    Examples:

    CH3I (1oC) CH3CH2CH2F (2oC)


    IUPAC: Iodomethane 1-fluoropropane
    Common: methyl bromide n-propyl fluoride

    I
    CH3CHCH2CH3 (CH3)3CCl

    IUPAC: 2-iodobutane 2-chloro-2-methylpropane


    Common: sec-butyl iodide t-butyl chloride

    -There is another class of halides whereby 2 halogen


    atoms attached to the molecule.

    Br
    Br Br
    R-C-R H C C H
    Br H H
    geminal dibromide vicinal dibromide
    PHYSICAL PROPERTIES

    a. Boiling Point
    -There are 2 intermolecular forces which influence b/pt,
    VdW forces and dipole-dipole attractions.
    -VdW are surface attractions in which molecules with
    large surface area have larger VdW forces, hence higher
    b/pt.
    -Dipole-dipole attraction arise from polar C-X bond also
    affect b/pt but only very little.

    -B/pt. is proportional to the increase of MW. ( MW, B/pt)


    -B/pt increase by the order of F < Cl < Br < I.
    -B/pt of alkyl halides with one halogen atom increase with
    increasing length of parent C chain. Examples:
    CH3Cl < CH3CH2Cl < CH3CH2CH2Cl
    B/pt -24oC 12oC 47oC

    - Increase in branching is inversely proportional to b/pt.


    ( branching, B/pt).

    b. Density & Solubility


    -All alkyl fluoride and alkyl chloride (R with only one
    atom) are less dense than water.
    -alkyl chloride with more than 2 atoms of Cl, alkyl
    bromide and alkyl iodide are more dense than water.
    -All alkyl halide are not miscible in aqueous but
    dissolve/miscible in non-polar organic solvent i.e ether,
    benzene, chloroform.
    Preparation Of Alkyl Halides

    -There are 4 main methods to prepare alkyl halides;


    1. Free-radical halogenation of alkanes
    2. Halogenation of Alkenes & Alkynes
    3. Alkyl Halide from Alcohol
    4. From Other Halides

    A. Free-radical Halogenation of Alkanes


    -General eqn:
    hv
    RH X2 RX HX
    alkyl halide
    -It is a rarely effective method of alkyl halide synthesis
    cause produces too many mixtures of products. Example:
    hv
    CH4 X2 CH3Cl CH2Cl2 CHCl3

    CCl4 HCl
    -In laboratory, this rxn can be performed to only
    specialized compounds that give a single major product.
    Examples:

    H H
    H Cl
    hv
    Cl2

    chlorocyclohexane

    CH3 CH3
    hv
    H 3C H Cl2 H3C Br
    CH3 CH3
    t-butyl bromide
    -The above rxns are possible for both starting material
    cause all the H in cyclohexane are equivalent and there is
    only one 3o C atom in isobutane.

    B. Halogenation of Alkenes
    I. Addition of acids of halogens to alkenes
    General Eqn.:

    -This rxn follows the Markonikov rule.


    Example:

    II. Addition of halogens to Alkenes


    General Eqn:

    CCl4

    Example:

    CCl4
    - This rxn produce vicinal alkyl halides.
    III. Allylic Bromination (by using NBS)
    -In 1942, Karl Ziegler found that alkenes react with N-
    bromosuccinimide (NBS) to give allyl halide with the X
    atom bonded to the C adjacent to C of C=C.

    General Eqn:

    -The result is that the rxn is highly selective, with only the
    most stable radical being formed.
    Example:
    O

    H H N Br Br
    O
    O
    N H
    hv, CCl4
    H 3-bromocyclohexene O
    (85%)
    -Allylic halogenation can also occur under high
    temperature. Example:
    Cl

    400oC HCl
    Cl2

    allylic
    hydrogens
    H H H Br
    allylic
    positions hv
    Br2 HBr

    H H

    3-bromocyclohexene

    Mechanism of Rxn:

    H H H H
    H Br
    H
    Br Br-Br
    Br-H Br
    H H H

    -Abstraction of the allylic hydrogen by halogen radical will


    give an allylic radical which is stabilized by resonance.
    C. Alkyl Halide From Alcohol
    -This is the most common and easiest method to prepare
    alkyl halide.
    -Involves rxn of tertiary alcohol with acid of halogens.
    -Reactivity of rxn by different alcohols are as below:

    3o > 2 o > 1o
    General Eqn:
    HX (X = Cl, Br or I)
    ROH R-X H2O
    H2SO4
    Example:

    HO CH3 Cl CH3
    HCl (gas)
    H2O
    Ether, 0oC

    1-methylcyclohexanol 1-chloro-1-methylcyclohexane
    90%
    -Alkyl halides synthesized from 2oC and 3oC alcohol via
    reagents thionyl chloride (SOCl2) or phosphorus
    tribromide (PBr3).
    Examples:
    a. O P(OH)3
    PBR3
    ether, 35oC CH2Br
    O 2-(bromomethyl)-tetrahydrofuran

    SOCl 2
    CH2OH
    O HCl SO2

    CH2Cl
    b.
    OH 2-(chloromethyl)-tetrahydrofuran
    OH
    PBr3
    CH3CH 2CHCH3 CH3CH2CHCH3 P(OH)3
    ether, 35oC
    2-bromobutane (86%)
    Questions:
    Give the reaction equation for the formation of each alkyl
    halide below by free-radical halogenation.
    1. 1-chloro-2,2-dimethylpropane
    2. 2-bromo-2-methylbutane
    3. 1-bromo-1-phenylbutane

    Answers

    1. CH3 CH3
    hv
    H3 C C CH3 Cl2 H3C C CH2Cl
    CCl 4
    CH3 CH3

    2. CH3 CH3
    hv
    Br2 H3C C Br
    H3C C H
    CCl4
    CH2CH3 CH2 CH3
    O
    3. N-Br
    Br
    O
    CH2CH2CH2CH3 CHCH 2CH2CH3
    hv, CCl4
    D. From Other Alkyl Halides
    General Eqn
    acetone
    R-X -
    I R-I X-
    Example:
    acetone
    H2C=CHCH2Cl NaI H2C=CHCH2Cl
    allyl chloride allyl iodide

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