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    CHEM1102 Lecture Notes 12

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    Callum Biggs
    This document provides an overview of organic chemistry topics including alcohols, ethers, and thiols. It discusses the structures, nomenclature, physical properties, and reactions of these functional groups. For alcohols, it describes how primary alcohols can be oxidized to aldehydes or carboxylic acids using different oxidizing agents like chromic acid or pyridinium chlorochromate. Ethers are described as polar but with weak intermolecular forces. Their lower boiling points compared to alcohols is attributed to this. Thiols are more acidic than alcohols due to their polarity. They have lower boiling points than alcohols and oxidize to

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    CHEM1102 Lecture Notes 12

    Uploaded by

    Callum Biggs
    197 views18 pages
    This document provides an overview of organic chemistry topics including alcohols, ethers, and thiols. It discusses the structures, nomenclature, physical properties, and reactions of these functional groups. For alcohols, it describes how primary alcohols can be oxidized to aldehydes or carboxylic acids using different oxidizing agents like chromic acid or pyridinium chlorochromate. Ethers are described as polar but with weak intermolecular forces. Their lower boiling points compared to alcohols is attributed to this. Thiols are more acidic than alcohols due to their polarity. They have lower boiling points than alcohols and oxidize to

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    This document provides an overview of organic chemistry topics including alcohols, ethers, and thiols. It discusses the structures, nomenclature, physical properties, and reactions of these functional groups. For alcohols, it describes how primary alcohols can be oxidized to aldehydes or carboxylic acids using different oxidizing agents like chromic acid or pyridinium chlorochromate. Ethers are described as polar but with weak intermolecular forces. Their lower boiling points compared to alcohols is attributed to this. Thiols are more acidic than alcohols due to their polarity. They have lower boiling points than alcohols and oxidize to

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    197 views18 pages

    CHEM1102 Lecture Notes 12

    Uploaded by

    Callum Biggs
    This document provides an overview of organic chemistry topics including alcohols, ethers, and thiols. It discusses the structures, nomenclature, physical properties, and reactions of these functional groups. For alcohols, it describes how primary alcohols can be oxidized to aldehydes or carboxylic acids using different oxidizing agents like chromic acid or pyridinium chlorochromate. Ethers are described as polar but with weak intermolecular forces. Their lower boiling points compared to alcohols is attributed to this. Thiols are more acidic than alcohols due to their polarity. They have lower boiling points than alcohols and oxidize to

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    Chemistry 1102

    Charlie Bond
    MCS Rm 4.16/4.27
    [email protected]
    What is Organic Chemistry?
    Organic Reactions I II
    Alkanes (Ch 21)
    Conformational Analysis (Ch 21)
    Stereochemistry I II III (Ch 22)
    Alkyl Halides I II (Ch 24)
    Alcohols and Ether I II (Ch 24)

    Oxidation of alcohols
    Primary alcohols can be oxidised to aldehydes or carboxylic acids
    [O] = 1 oxidising equivalent, a generic way of describing an oxidant

    [O]

    Secondary alcohols can be oxidised to ketones:

    [O]

    [O]

    Tertiary alcohols cannot be simply oxidised:

    Oxidation of Alcohols
    Oxidation of a 1 alcohol gives an aldehyde or a
    carboxylic acid, depending on the oxidizing agent and
    experimental conditions
    the most common oxidizing agent is chromic acid
    CrO3
    + H2O
    Chromium(VI)
    oxide

    H2SO4

    H2CrO4

    Chromicacid

    Eg chromic acid oxidation of 1-octanol gives octanoic


    acid
    CH3(CH2)6CH2OH
    1Octanol

    CrO3
    H2SO4 , H2O

    O
    CH3(CH2)6CH
    Octanal
    (notisolated)

    O
    CH3(CH2)6COH
    Octanoicacid
    3

    Oxidation of Alcohols
    to oxidize a 1 alcohol to an aldehyde, use PCC
    CrO3 + HCl +

    Pyridine

    CrO3Cl-

    N+
    H
    Pyridiniumchlorochromate
    (PCC)

    PCC oxidation of geraniol gives geranial

    Geraniol

    PCC
    OH CH Cl
    2 2

    Geranial

    Tertiary alcohols are not oxidized by either of these


    reagents; they are resistant to oxidation

    O
    H

    Demonstrations

    Ethers - Structure
    The functional group of an ether is an
    oxygen atom bonded to two carbon atoms
    oxygen is sp3 hybridized with bond angles of
    approximately 109.5
    in dimethyl ether, the C-O-C bond angle is
    110.3
    H
    H

    C
    H

    H
    6

    Ethers - Nomenclature
    IUPAC
    the longest carbon chain is the parent alkane
    name the -OR group as an alkoxy substituent
    Common names:
    name the groups bonded to oxygen followed by the
    word ether
    O
    Et2O
    Ethoxyethane
    (Diethylether)
    CH3
    CH3OCCH3
    CH3

    2Methoxy2methylpropane
    (methyltertbutylether,MTBE)

    OH
    OEt

    trans2Ethoxycyclohexanol
    7

    Ethers - Physical Properties


    Ethers are polar molecules
    each C-O bond is polar covalent
    however, only weak attractive forces exist
    between ether molecules

    Ethers - Physical Properties


    boiling points are lower than those of alcohols
    Boiling
    Molecular Point
    Weight
    (C)
    46
    78
    24
    46

    StructuralFormula
    CH3CH2 OH
    CH3OCH3

    Name
    ethanol
    dimethylether

    CH3CH2 CH2CH2OH

    1butanol

    74

    117

    CH3CH2 OCH2CH3

    diethylether

    74

    35

    88
    90
    88
    90

    138
    230
    71
    84

    CH3CH2 CH2CH2CH2OH 1pentanol


    HOCH2CH2CH2CH2 OH 1,4butanediol
    CH3CH2 CH2CH2OCH3 butylmethylether
    CH3OCH2CH2OCH3
    ethyleneglycol
    dimethylether

    Solubility
    inWater
    infinite
    7.8g/100g
    7.4g/100g
    8g/100g
    2.3g/100g
    infinite
    slight
    infinite
    9

    Ethers - Physical Properties


    ethers are hydrogen bond acceptors
    How many H-bonds can they accept?

    10

    Reactions of Ethers
    Ethers resemble hydrocarbons in their resistance to
    chemical reaction
    they do not react with strong oxidizing agents such as
    chromic acid, H2CrO4
    they are not affected by most acids and bases at
    moderate temperatures
    Because of their good solvent properties and general
    inertness to chemical reaction, ethers are excellent
    solvents in which to carry out organic reactions

    11

    Williamson Synthesis of Ethers


    This method of synthesising ethers brings together two parts of alkyl
    halide and alcohol chemistry:
    the first step is the formation of an alkoxide from an alcohol:

    the second step involves nucleophilic substitution on an alky


    halide where the alkoxide acts as the nucleophile:

    12

    Thiols - Structure

    The functional group of a thiol is an -SH


    (sulfhydryl) group bonded to a tetrahedral
    carbon

    13

    Thiols - Nomenclature
    IUPAC names:
    the parent chain is the longest chain containing the
    -SH group
    add -thiol to the name of the parent chain
    Common names:
    name the alkyl group bonded to sulfur followed by the
    word mercaptan
    alternatively, indicate the -SH by the prefix mercapto
    SH

    SH

    Ethanethiol
    2Methyl1propanethiol
    (Ethylmercaptan)
    (Isobutylmercaptan)

    OH
    HS
    2Mercaptoethanol
    14

    Thiols - Physical Properties


    Low-molecular-weight thiols have a
    STENCH
    Presentinthe
    scentofskunks:

    CH3CH=CHCH2 SH
    2Butene1thiol

    CH3
    CH3CHCH2CH2SH
    3Methyl1butanethiol
    (Isobutylmercaptan)

    CH3
    SH
    Naturalgas
    CH3 -C-SH
    CH3 -CH-CH3
    odorants:
    CH3
    2Methyl2propanethiol
    2Propanethiol
    (tertButylmercaptan) (Isopropylmercaptan)
    15

    Thiols - Physical Properties


    The difference in electronegativity
    between S and H is 2.5 - 2.1 = 0.4
    Because of their low polarity, thiols
    show little association by hydrogen bonding
    have lower boiling points and are less soluble
    in water than alcohols of comparable MW
    Thiol

    BoilingPoint
    (C)

    BoilingPoint
    Alcohol
    (C)

    methanethiol

    methanol

    65

    ethanethiol
    1butanethiol

    35
    98

    ethanol
    1butanol

    78
    117

    16

    Acidity of Thiols
    Thiols are stronger acids than alcohols
    -

    CH3CH2OH + H2 O

    CH3CH2O + H3 O

    pKa =15.9

    CH3CH2SH + H2 O

    +
    CH3CH2S + H3 O

    pKa =8.5

    Thiols react with strong bases to form


    salts
    +

    CH3CH2SH + Na OH
    pKa8.5
    Stronger
    Stronger
    acid
    base

    CH3CH2S Na
    Weaker
    base

    + H2O
    pKa 15.7
    Weaker
    acid

    17

    Oxidation of Thiols
    thiols are oxidized by a variety of oxidizing
    agents, including O2, to disulfides
    disulfides, in turn, are easily reduced to
    thiols by several reagents
    2HOCH2 CH2 SH
    Athiol

    oxidation
    reduction

    HOCH2 CH2S-SCH2 CH2 OH


    Adisulfide

    this easy interconversion between thiols and


    disulfides is very important in protein
    chemistry

    18

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