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    Phenols: Ahmet Kaan Dikici 03130021005

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    Ahmet Kaan Dikici
    This document discusses the structure, properties, reactions, and uses of phenol compounds. It describes the basic structure of phenols including common substituents. Phenols have higher boiling points than similar compounds due to intermolecular hydrogen bonding. They undergo electrophilic aromatic substitution reactions and can be oxidized to quinones. Phenols are stronger acids than alcohols due to resonance stabilization of the phenoxide ion. Spectroscopic methods like IR, 1H NMR, and 13C NMR can be used to analyze phenol structures.

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    Phenols: Ahmet Kaan Dikici 03130021005

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    Ahmet Kaan Dikici
    51 views23 pages
    This document discusses the structure, properties, reactions, and uses of phenol compounds. It describes the basic structure of phenols including common substituents. Phenols have higher boiling points than similar compounds due to intermolecular hydrogen bonding. They undergo electrophilic aromatic substitution reactions and can be oxidized to quinones. Phenols are stronger acids than alcohols due to resonance stabilization of the phenoxide ion. Spectroscopic methods like IR, 1H NMR, and 13C NMR can be used to analyze phenol structures.

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    Organic Chemistry

    Original Title

    Phenols

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    This document discusses the structure, properties, reactions, and uses of phenol compounds. It describes the basic structure of phenols including common substituents. Phenols have higher boiling points than similar compounds due to intermolecular hydrogen bonding. They undergo electrophilic aromatic substitution reactions and can be oxidized to quinones. Phenols are stronger acids than alcohols due to resonance stabilization of the phenoxide ion. Spectroscopic methods like IR, 1H NMR, and 13C NMR can be used to analyze phenol structures.

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    © All Rights Reserved
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    Download as pptx, pdf, or txt
    51 views23 pages

    Phenols: Ahmet Kaan Dikici 03130021005

    Uploaded by

    Ahmet Kaan Dikici
    This document discusses the structure, properties, reactions, and uses of phenol compounds. It describes the basic structure of phenols including common substituents. Phenols have higher boiling points than similar compounds due to intermolecular hydrogen bonding. They undergo electrophilic aromatic substitution reactions and can be oxidized to quinones. Phenols are stronger acids than alcohols due to resonance stabilization of the phenoxide ion. Spectroscopic methods like IR, 1H NMR, and 13C NMR can be used to analyze phenol structures.

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    © All Rights Reserved
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    of 23

    PHENOLS

    Ahmet Kaan Dikici


    03130021005
    Structure and Nomenclature
    of Phenols

    OH
    OH OH

    Phenol 1-Naphthol 9-Phenanthrol


    (-naphthol)
    Nomenclature of Phenols
    Cl CH3
    NO2

    OH OH
    OH

    4-Chlorophenol 2-Nitrophenol 3-Methylphenol


    (p-chlorophenol) (o-nitrophenol) (m-cresol)
    The benzenediols also have common names
    OH OH OH
    OH

    OH
    OH
    1,2-Benzenediol 1,3-Benzenediol 1,4-Benzenediol
    (catechol) (resorcinol) (hydroquinone)
    Naturally Occurring Phenols
    O CO2CH3


    OH
    O
    H NH3+
    HO
    L-Tyrosine Methyl salicylate
    (oil of wintergreen)
    OH
    CH3 OH
    OCH3
    H

    H H
    HO
    Eugenol Estradiol
    (oil of cloves)
    Physical Properties of Phenols

    C6H5CH3 C6H5OH C6H5F

    Molecular weight 92 94 96

    Melting point (°C) –95 43 –41

    Boiling 111 132 85


    point (°C,1 atm)

    Solubility in 0.05 8.2 0.2


    H2O (g/100 mL,25°C)
    Properties of Phenols
     The structure around O of the phenol is similar to that in water, sp3
    hybridized.
     Phenols have much higher boiling points than similar alkanes and
    alkyl halides.
     A positively polarized OH hydrogen atom from one molecule is
    attracted to a lone pair of electrons on a negatively polarized
    oxygen atom of another molecule.
     This produces a force that holds the two molecules together.
     These intermolecular attractions are present in solution but not in
    the gas phase, thus elevating the boiling point of the solution.
    Phenols and Their Uses
     Industrial process from readily available cumene
     Forms cumene hydroperoxide with oxygen at high
    temperature
     Converted into phenol and acetone by acid
    Mechanism of Formation of Phenol
    Reactions of Phenols:Electrophilic
    Aromatic Substitution
     The hydroxyl group of phenols is a strong activator and
    o-/p-director.
    a. Halogenation:Phenols are so highly activated that they
    often react with Br2 and Cl2 without a catalyst.

    b. Nitration:

    c. Sulfonation:
    d. Friedel-Crafts Alkylation:

    e. Friedel-Crafts Acylation:

    Acylation of Phenols: In the absence if AlCl3, phenols


    react with acid chlorides to afford phenyl esters.
    Carboxylation of Phenols Aspirin and the Kolbe-Schmitt
    Reaction:Synthesis of salicylic acid(o-hydroxybenzoic acid)
    from phenol.

    Preparation of Aryl Ethers:The phenoxide ion is a good


    nucleophile and reacts with 1° and 2° alkyl halides and
    tosylates afford aryl ethers (Williamson ether synthesis)
    Cleavage of Aryl Ethers by Hydrogen Halides: Aryl alkyl
    ethers can be cleaved by HX to give phenols.

    Claisen Rearrangement: Thermal rearrangement of an


    aryl allyl ether to an o-allyl phenol.
    Oxidation of Phenols: Quinones
     Reaction of a phenol with strong oxidizing agents yields a
    quinone.
     Fremy's salt [(KSO ) NO] works under mild conditions
    3 2
    through a radical mechanism.
    Quinones in Nature
     Ubiquinones mediate electron-transfer processes
    involved in energy production through their redox
    reactions.
    Phenol Acidity
     Phenols (pKa ~10) are much more acidic than alcohols
    (pKa ~ 16) because of resonance stabilization of the
    phenoxide ion.
     Phenols react with NaOH solutions (but alcohols do not),
    forming salts that are soluble in dilute aqueous solution.
     A phenolic component can be separated from an organic
    solution by extraction into basic aqueous solution and is
    isolated after acid is added to the solution.
    Strength of Phenols as Acids
     Phenols are much stronger acids than alcohols.
    Nitro-Phenols
     Phenols with nitro groups at the ortho and para positions
    are much stronger acids.
    Factors that influence acidity
    Inductive effect:
    CH3CH2OH FCH2CH2OH F2CHCH2OH F3CCH2OH (F3C)3COH

    pKa ~ 16.0 14.4 13.3 12.4 5.4

    Electron-withdrawing groups make an


    alcohol a stronger acid by stabilizing
    the conjugate base (alkoxide)

     A benzene ring is generally considered electron


    withdrawing and stabilizes the negative charge through
    inductive effects.
    Resonance effect: The benzene ring stabilizes the
    phenoxide ion by resonance delocalization of the negative
    charge.

    Substituent Effects on the Acidity of Phenols:


    Electron-donating substituents make a phenol less acidic by
    destabilizing the phenoxide ion (resonance effect).

    X= -H-CH3 -OCH3 -NH2


    pKa ~ 10 10.3 10.2 10.5
    Electron-withdrawing substituents make a phenol more acidic by
    stabilizing the phenoxide ion through delocalization of the
    negative charge and through inductive effects.

    X= -H-Cl -Br -NO2


    pKa ~ 10 9.4 9.3 7.2

    The influence of a substituent on phenol acidity is also


    dependent on its position relative to the –OH.

    pKa X= -Cl 9.4 9.1


    -NO2 7.2 8.4
    -OCH3 10.2 9.6
    -CH3 10.3 10.1
    The effect of multiple substituents on phenol acidity
    is additive.
    Spectroscopic Analysis of Phenols
    Infrared Spectra
     Phenols show O-H stretching in the 3400-3600 cm-1 region.
    1H NMR
     The position of the hydroxyl proton of phenols depends on concentration.
     In phenol itself the O-H proton is at  2.55 for pure phenol and

    at  5.63 for 1%a .1% solution.


     Phenol protons disappear from the spectrum when

    2H2O is added.
     The aromatic protons7of- phenols9occur in the  7-9
    region.
    13C NMR
     The carbon atoms of phenols appear in the region  135-170.

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