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    16 Hydroxyl compound-24-STD

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    Manh Doan Duc
    The document discusses hydroxyl compounds and alcohols. It defines hydroxyl groups and classifies alcohols as primary, secondary or tertiary. The document also describes production of alcohols, naming conventions, characteristic reactions including oxidation, dehydration, and esterification. Common tests for identifying alcohols like reaction with iodine to form triiodomethane are also covered.

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    16 Hydroxyl compound-24-STD

    Uploaded by

    Manh Doan Duc
    16 views38 pages
    The document discusses hydroxyl compounds and alcohols. It defines hydroxyl groups and classifies alcohols as primary, secondary or tertiary. The document also describes production of alcohols, naming conventions, characteristic reactions including oxidation, dehydration, and esterification. Common tests for identifying alcohols like reaction with iodine to form triiodomethane are also covered.

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    The document discusses hydroxyl compounds and alcohols. It defines hydroxyl groups and classifies alcohols as primary, secondary or tertiary. The document also describes production of alcohols, naming conventions, characteristic reactions including oxidation, dehydration, and esterification. Common tests for identifying alcohols like reaction with iodine to form triiodomethane are also covered.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    16 views38 pages

    16 Hydroxyl compound-24-STD

    Uploaded by

    Manh Doan Duc
    The document discusses hydroxyl compounds and alcohols. It defines hydroxyl groups and classifies alcohols as primary, secondary or tertiary. The document also describes production of alcohols, naming conventions, characteristic reactions including oxidation, dehydration, and esterification. Common tests for identifying alcohols like reaction with iodine to form triiodomethane are also covered.

    Copyright:

    © All Rights Reserved
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    of 38

    17.

    Hydroxyl Compounds
    A hydroxy or hydroxyl group is a
    functional group composed of
    one oxygen atom covalently
    bonded to one hydrogen atom
    and having the chemical
    formula OH
    Content

    Production Reactions Classifying Alcohol


    of Alcohols of Alcohols and Dissociation
    Testing for
    Alcohols
    CLASSIFICATION OF ALCOHOLS
    Aliphatic • general formula CnH2n+1OH - provided there are no rings
    • the OH replaces an H in a basic hydrocarbon skeleton

    Aromatic • in aromatic alcohols (or phenols) the OH is attached directly to the ring
    • an OH on a side chain of a ring behaves as a typical aliphatic alcohol

    Structural
    differences • alcohols are classified according to the environment of the OH group
    • chemical behaviour, eg oxidation, often depends on the structural type

    PRIMARY 1° SECONDARY 2° TERTIARY 3°


    NAMING ALCOHOLS
    Alcohols are named according to standard IUPAC rules

    1. select the longest chain of C atoms containing the O-H group

    2. remove the e and add ol after the basic name


    3. number the chain starting from the end nearer the O-H group
    4. the number is placed after the an and before the ol ... e.g butan-2-ol
    5. as in alkanes, prefix with alkyl substituents
    6. side chain positions are based on the number allocated to the O-H group

    CH3 - CH(CH3) - CH2 - CH(OH) - CH3


    5-methylpentan-2-ol
    a. Electrophilic addition of alkenes
    Alkene + hot steam + concentrated (Al2O3 or H3PO4: Phosphoric acid) as a
    catalyst  alcohol
    b. Oxidation of alkenes

    Alkenes + Cold, dilute KMnO4 A diol (hydroxyl, -OH, groups)


    c. Nucleophilic substitution of halogenoalkanes

    Halogenoalkanes + NaOH(aq) + heat alcohol


    d. Reduction of aldehyde & ketones using NaBH4 or LiAlH4

     Aldehydes are reduced to primary alcohols

     Ketones are reduced to secondary alcohols

    1. NaBH4 (Sodium boranuide


    or Sodium
    tetrahydridoborate)
    2. LiAlH4 (Lithium aluminium
    hydride or Lithium
    tetrahydridoaluminate(III))
    e. Reduction of carboxylic acids
    Carboxylic acids are reduced by NaBH4 or LiAlH4 or (H2 using a nickel catalyst and
    heat) to primary alcohols

    NaBH4
    f. Hydrolysis of ester

    When an ester is heated with dilute acid or alkali  the carboxylic acid and alcohol
    will be reformed
    1. Combustion
    2. substitution to halogenoalkanes

    2. 3. The reaction with Na(s)


    4. Oxidation with acidifed K2Cr2O7 or acidifed KMnO4
    Reactions to:

    of Alcohols 1. Primary alcohols give aldehydes which can be


    further oxidised to carboxylic acids
    2. Secondary alcohols give ketones
    3. Tertiary alcohols cannot be oxidised
    5. Dehydration to an alkene
    6. Esterification
    1. Complete combustion of alcohols

    Alcohol + oxygen  carbon dioxide + water

    •Reagent : Oxygen supply


    Condition : Heat
    Product : Carbon dioxide(and carbon monoxide) and water
    2. Substitution to halogenoalkanes

    ROH+ HX  RX + H2O
    In the substitution of alcohols, a hydroxy group (-OH) is replaced by a halogen to
    form an halogenoalkane

    The halogen can be obtained from three sources:


    1.Hydrogen halide, HX ; where X = Cl/Br/I with H2SO4 or H3PO4
    2.Phosphorus halide, PCl5 or PCl3
    3.Thionyl chloride(or sulfur dichloride oxide), SOCl2
    3. The reaction with Na(s)

    Alcohol + sodium  sodium alkoxide + hydrogen

    Alcohol reacts with a reactive metal such as sodium (Na), the oxygen-hydrogen
    bond in the hydroxy group breaks and a basic compound (alkoxide) is formed. If
    the excess ethanol is evaporated off after the reaction a white crystalline solid of
    sodium alkoxide is left
    4. OXIDATION OF ALCOHOLS

    Class of Reaction conditions Product


    alcohol
    Primary Gentle heating Aldehyde

    Stronger heating under reflux with excess Carboxylic acid


    potassium dichromate (Vl)

    Secondary Heat under reflux Ketone

    Tertiary No reaction
     The oxidising agents used to prepare aldehydes and ketones from alcohols
    include acidified potassium dichromate (K2Cr2O7) and acidified potassium
    manganate (KMnO4)

     When the alcohols are oxidised the orange dichromate ions (Cr2O7-) are
    reduced to green Cr3+ ions

     When the alcohols are oxidised the purple manganate ions (MnO4–) are reduced

    to colourless Mn2+ ions


    o Primary alcohols get mildly oxidized with acidified K2Cr2O7  aldehydes
    o Secondary alcohols get mildly oxidizedwith acidified K2Cr2O7 ketones
    o Tertiary alcohols do not undergo oxidation

    • Therefore, only the oxidation of primary and secondary alcohols will change the colour of K2Cr2O7
    solution as the orange Cr2O72- ions are reduced to green Cr3+ ions
    OXIDATION OF PRIMARY ALCOHOLS

    1. Primary alcohols are easily oxidised to aldehydes if the alcohol used is in excess

    2. If the alcohol used is limited and heated under reflux, the primary alcohol will be
    oxidised to aldehyde then to carboxylic acid
    OXIDATION OF SECONDARY ALCOHOLS

    Secondary alcohols are easily oxidised to ketones

    The alcohol is refluxed with acidified K2Cr2O7


    Oxidation of ethanol by
    acidified K2Cr2O7 to form
    an aldehyde by
    distillation and
    carboxylic acid by
    refluxing
    Oxidation of ethanol by
    acidified K2Cr2O7 to form
    an aldehyde by
    distillation and
    carboxylic acid by
    refluxing
    5. ELIMINATION OF WATER (DEHYDRATION)

    Reagent/catalyst conc. sulphuric acid (H2SO4) or H3PO4 or Al2O3


    Conditions reflux at 180°C
    Product alkene
    Equation C2H5OH(l) ——> CH2 = CH2(g) + H2O(l)

    Link: How to Make Ethene


    MECHANISM OF DEHYDRATION

    Step 1 protonation of the alcohol using a lone pair on oxygen


    Step 2 loss of a water molecule to generate a carbocation
    Step 3 loss of a proton (H+) to give the alkene
    Note 1There must be an H on a carbon atom adjacent the carbon with the OH

    Note 2 Alcohols with the OH in the middle of a chain


    can have two ways of losing water.

    In Step 3 of the mechanism, a proton can be lost


    from either side of the carbocation. This gives a
    mixture of alkenes from unsymmetrical alcohols...
    6. ESTERIFICATION OF ALCOHOLS

    Reagent(s) carboxylic acid


    Conditions Heat under reflux with concentrated sulfuric acid (H2SO4) or H3PO4
    Product ester
    Equation Carboxylic acid + alcohol  ester + water

    CH3OH + CH3COOH  CH3COOCH3 + H2O


    from ethanoic acid METHYL ETHANOATE

    Notes Concentrated H2SO4 is a dehydrating agent - it removes water causing the equilibrium to move
    to the right and increases the yield

    Uses of esters Esters are fairly unreactive but that doesn’t make them useless
    Used as flavourings

    Naming esters Named from the alcohol and carboxylic acid which made them...
    Reactions of hydroxyl compounds
    1. Complete combustion of ethanol with heat

    2. Substitution ethanol to halogenoalkanes by reaction with HX or KBr with


    H2SO4 or H3PO4; or with PCl3 and heat; or with PCl5; or with SOCl2

    3.Acid-base reaction: ethanol with Na(s)


    Reactions of hydroxyl compounds
    4. Oxidation with acidifed K2Cr2O7 or acidifed KMnO4 to:
    1. Ethanol give aldehydes with gentle heat which can be further oxidised to carboxylic acids
    with stronger heat under reflux with excess potassium dichromate (Vl)

    2. Propan-2-ol give ketones with heat under reflux

    Both reactions change the colour of K2Cr2O7 solution as the orange Cr2O72- ions are reduced to green
    Cr3+ ions)
    Reactions of hydroxyl compounds

    5. Elimination of water (Dehydration) of ethanol to an alkene with conc.


    sulphuric acid (H2SO4) or H3PO4 or Al2O3 and reflux at 180°C

    6. Esterification of methanol to ester with heat under reflux with


    concentrated sulfuric acid (H2SO4) or H3PO4
    1. State characteristic distinguishing
    reactions, e.g. mild oxidation with acidifed
    3. Testing for K2Cr2O7, colour change from orange to

    Alcohols green

    2. Deduce the presence of a CH3CH(OH)–


    group in an alcohol, CH3CH(OH)–R, from its
    reaction with alkaline I2(aq) to form a yellow
    precipitate of tri-iodomethane and an ion,
    RCO2 –
    Test for Alcohols

     Triiodomethane (iodoform): CHI3 react to identify the presence of a


    CH3CH(OH) group in alcohols.
     Iodine solution is added to a small amount of an alcohol, followed by
    just enough sodium hydroxide solution to remove the colour of the
    iodine. If nothing happens in the cold, it may be necessary to warm
    the mixture very gently.
     A positive result is the appearance of a very pale yellow precipitate
    of triiodomethane (previously known as iodoform) - CHI3.
    Test for Alcohols
    Triiodomethane (iodoform): CHI3 react to identify the presence of a
    CH3CH(OH) group in alcohols.

     If "R" is hydrogen, then you have the primary alcohol


    ethanol, CH3CH2OH.
     If "R" is a hydrocarbon group, then you have a
    secondary alcohol. Note that, only secondary
    alcohols have a methyl group attached to the carbon
    with the -OH group can react.
     No tertiary alcohols give the triiodomethane
    (iodoform) reaction because no tertiary alcohols can
    have a hydrogen atom attached to the carbon with
    the -OH group
    Test for Alcohols
    • Tri-iodomethane (iodoform): CHI3

    This reaction involves a halogenation and


    hydrolysis step
    o In the halogenation step, all three H-atoms
    in the -CH3 (methyl) group are replaced for
    iodine atoms, forming –CI3
    o The intermediate compound is hydrolysed by
    alkaline solution to form a sodium salt
    (RCO2– Na+) and a yellow precipitate of
    CHI3
    Iodoform & alcohols 1

     If the -OH group is on the


    carbon atom next to a methyl
    group of secondary alcohol , it
    will firstly get oxidised to
    CH3CH(OH)- by the alkaline 2
    solution  to form RCOCH3
     The methyl ketone will then first Butanone

    get halogenated and then


    hydrolysed to form the sodium
    salt and the yellow precipitate
    NOTE:
    • We can use alkaline aqueous iodine to indicate the primary alcohol
    ethanol CH3CH2OH and all secondary alcohols with the 2–ol
    structure R–CH(OH)–CH3 and the aldehyde ethanal CH3CHO and
    all ketones with the 2–one structure R–CO–CH3 ('methyl ketones')
     yellow precipitate

    • Iodoform is heated with an alkaline solution of iodine  a sodium


    salt (RCO2– Na+) and a yellow precipitate of CHI3
    4. Alcohol Explain the acidity of alcohols
    Dissociation compared with water
    Acidity of Alcohols
    • Alcohols have a low degree of dissociation (do not dissociate (split up) to a great extent )
    ROH (aq)  RO– (aq) + H+ (aq)
    Alcohol alkoxide ion

    o The position of the equilibrium lies to the left, means that more alcohol
    molecules than RO– and H+ ions

    • When water dissociates, the position of the equilibrium still lies to the left, but
    there are more H+ ions compared to the dissociation of alcohols
    H2O (l)  OH– (aq) + H+(aq)

    • As alcohols have a lower [H+ (aq)] in solution compared to water, alcohols are
    weaker acids than water

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