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    Organic Chemistry Chemy220 Chapter 7

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    Imran Parvez
    This document summarizes key information about alcohols, phenols, and thiols. It discusses their structures, properties like boiling points and acidity, reactions including substitution, oxidation, and dehydration. Phenols are more acidic than alcohols due to resonance stabilization of the phenoxide ion. Both undergo electrophilic aromatic substitution and oxidation reactions. Thiols are similar to alcohols but are stronger acids and can oxidize to form disulfide bonds.

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    Organic Chemistry Chemy220 Chapter 7

    Uploaded by

    Imran Parvez
    39 views8 pages
    This document summarizes key information about alcohols, phenols, and thiols. It discusses their structures, properties like boiling points and acidity, reactions including substitution, oxidation, and dehydration. Phenols are more acidic than alcohols due to resonance stabilization of the phenoxide ion. Both undergo electrophilic aromatic substitution and oxidation reactions. Thiols are similar to alcohols but are stronger acids and can oxidize to form disulfide bonds.

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    Organic chemistry chemy220 chapter 7

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    This document summarizes key information about alcohols, phenols, and thiols. It discusses their structures, properties like boiling points and acidity, reactions including substitution, oxidation, and dehydration. Phenols are more acidic than alcohols due to resonance stabilization of the phenoxide ion. Both undergo electrophilic aromatic substitution and oxidation reactions. Thiols are similar to alcohols but are stronger acids and can oxidize to form disulfide bonds.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    39 views8 pages

    Organic Chemistry Chemy220 Chapter 7

    Uploaded by

    Imran Parvez
    This document summarizes key information about alcohols, phenols, and thiols. It discusses their structures, properties like boiling points and acidity, reactions including substitution, oxidation, and dehydration. Phenols are more acidic than alcohols due to resonance stabilization of the phenoxide ion. Both undergo electrophilic aromatic substitution and oxidation reactions. Thiols are similar to alcohols but are stronger acids and can oxidize to form disulfide bonds.

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    © All Rights Reserved
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    of 8

    Chapter 7: Alcohols, phenols and thiols.

    Alcohols

     Numbering of OH group has priority over multiple bonds.

    Phenols

     Carboxylic and carbonyl groups have priority over alcohols.

     Boiling Point: H-OH > R-OH > R-OR > R-H


     Alcohols have high BP due to hydrogen bonding just like water.
     In an alcohol, as the carbon length increases, BP increases but solubility in water
    decreases.

    Acidity and basicity

    Bronsted Lowry definition

     Acid: Proton donor


     Base: Proton acceptor

     Ka: Equilibrium acidity constant (ionization constant)


     More Ka (or less pKa) means stronger acid.
     If an acid is strong, its conjugate base is weak and vice versa.

    Lewis definition

     Acid: Can accept electron pair (BF3, AlCl3, FeCl3, positively charged ions)
     Base: Can donate electron pair (NH3, negatively charged ions)
     Amphoteric: Can act as acid or base (ex: water)

    Acidity of alcohols and phenols

     Alcohols are weak acids because the alkoxides ions are unstable
     Phenols are also weak acids but stronger acids compared to alcohols because the
    phenoxide ions are stable due to resonance.

     Increasing carbon length in ROH makes decreases acidity.


     Electron withdrawing groups (such as F) increases acidity by stabilizing conjugate
    base. Electron donating groups decrease acidity by destabilizing conjugate base.

    Inductive effect

     In phenols, electron withdrawing groups increase acidity by induction and


    resonance.
    Producing alkoxides

     Alcohols react with metals to form alkoxides which are white solids.

     Since alkoxides are strong conjugate bases compared to NaOH, the following
    reactions is shifted backwards.

     Phenol reacts with NaOH to form phenoxides.

    Basicity of alcohols and phenols

     They act as lewis base (donate electrons).


     These weak bases can react with strong acids.
    Dehydration of alcohols

     Small amounts of strong acids remove water from alcohols when heated.

     Tertiary alcohols dehydrate by E1 mechanism.

     Primary alcohols dehydrate by E2 mechanism.

     In dehydration, alcohols act as base.


     The ease of alcohol dehydration is tertiary > secondary > primary (similar to stability
    of carbocation)
     If more than one alkene is produced, the alkene with most substituted double bond
    (most R groups) will be the major product.

    Reaction with HX

     Since halide ions are good nucleophiles, substitution occurs.

     Speed of reaction: Tertiary > Secondary > Primary


     Tertiary alcohols undergo SN1 mechanism.
    Mechanism:

     Primary alcohols undergo SN2 mechanism.

    Mechanism:

    Other ways to prepare RX

     Pure RX can be obtained since SO2 and HCl leave as gases. This method is not
    effective for preparing low boiling RX (less C).

     For low boiling RX, the following method can be used since phosphorus acid has a
    high BP. The RX can be recovered by distillation.

    Comparison of alcohols and phenols

     For substitution, the C-OH group in alcohols can be easily broken with the help of an
    acid catalyst.
     C-OH bond is difficult to break in phenols because the positive carbon in the phenyl
    cation is sp-hybridized and must be linear. But this is prevented due to the ring
    structure. Thus phenyl cations are unstable.

     Therefore phenols cannot undergo SN1 and SN2 mechanisms.


    Oxidation of alcohols

     Tertiary alcohols do not undergo the above kind of oxidation.


     Jones reagent: CrO3 dissolved in sulfuric acid. Acetone used as solvent.

     PCC: Pyridinium chlorochromate


    - Prepared as follows:

    - Oxidation of primary alcohols can be stopped at aldehyde stage by using PCC

    Multiple OH groups

     Ethylene glycol: used as antifreeze


     Glycerol: Its nitration produces a shock-sensitive explosive

     Sorbitol: Used in candy making and as a sugar substitute for diabetics.


    Electrophillic aromatic substitution in phenols

     OH groups strongly activates the ring to allow electrophillic substitution

    Oxidation of phenols

    1,4-dihydroxybenzene  quinone

    Phenols as antioxidants

     Phenols react with and destroy peroxy (ROO.) and (.OH) radicals which could
    otherwise oxidize food.
     The resulting phenoxy radical is stable due to resonance.

     BHA (butylated hydroxyanisole) and BHT (butylated hydroxytoluene) are examples


    of commercial antioxidants.

    Thiols

     Thiols are also called mercaptans because they react with mercuric ion to form
    mercaptides.
     They are formed by nucleophillic displacement of RX with SH (sulfhydryl ion)

     R-SH are more acidic than R-OH

     Thiols oxidize to disulfides.

     The odor of fresh garlic is caused by diallyl disulfide:

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