Ethers and Thioethers

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    Ethers andEthers and ThioethersThioethers

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    112112

    HH

    OO

    HH

    105105 108.5108.5

    (CH(CH33))33CCOO

    C(CHC(CH33))33

    132132

    HH

    OO

    CHCH33

    CHCH33OO

    CHCH33

    Bond angles at oxygen are sensitiveBond angles at oxygen are sensitive

    to steric effectsto steric effects

    Bond angles at oxygen are sensitiveBond angles at oxygen are sensitive

    to steric effectsto steric effects

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    name the groups attached to o!gen inname the groups attached to o!gen ina"pha#etica" order as separate $ords% &ether& isa"pha#etica" order as separate $ords% &ether& is

    "ast $ord"ast $ord

    CHCH33OOCHCH

    22CHCH

    33

    eth!"eth!"meth!"meth!"etherether

    CHCH33CHCH22OOCHCH22 CHCH33

    didieth!"eth!"etherether

    CHCH33CHCH22OOCHCH22CHCH22CHCH22C"C"

    3'ch"oroprop!"3'ch"oroprop!"eth!"eth!"etherether

    Functional Class IUPAC Names of EthersFunctional Class IUPAC Names of Ethers

    Functional Class IUPAC Names of EthersFunctional Class IUPAC Names of Ethers

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    most sta#"e con*ormation o* dieth!" ethermost sta#"e con*ormation o* dieth!" ether

    resem#"es pentaneresem#"es pentane

    An oxygen atom affects geometry in much theAn oxygen atom affects geometry in much thesame ay as a C!same ay as a C!""grou#grou#

    An oxygen atom affects geometry in much theAn oxygen atom affects geometry in much thesame ay as a C!same ay as a C!""grou#grou#

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    most sta#"e con*ormation o* tetrah!drop!ranmost sta#"e con*ormation o* tetrah!drop!ran

    resem#"es c!c"oheaneresem#"es c!c"oheane

    An oxygen atom affects geometry in much theAn oxygen atom affects geometry in much thesame ay as a C!same ay as a C!""grou#grou#

    An oxygen atom affects geometry in much theAn oxygen atom affects geometry in much thesame ay as a C!same ay as a C!""grou#grou#

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    (+1,)(+1,)

    CHCH33CHCH22CHCH22CHCH22OO-a -a CHCH33CHCH22//

    CHCH33CHCH22CHCH22CHCH22OOCHCH22CHCH33 -a/-a/

    PREPARATIONPREPARATIONPREPARATIONPREPARATION

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    #oi"ing point#oi"ing point

    3C3C

    35C35C

    11+C11+C

    Ethers resemble al$anes more than alcoholsEthers resemble al$anes more than alcohols

    ith res#ect to boiling #ointith res#ect to boiling #oint

    Ethers resemble al$anes more than alcoholsEthers resemble al$anes more than alcohols

    ith res#ect to boiling #ointith res#ect to boiling #oint

    OO

    OHOH

    /ntermo"ecu"ar h!drogen/ntermo"ecu"ar h!drogen

    #onding possi#"e in#onding possi#"e in

    a"coho"s% not possi#"ea"coho"s% not possi#"e

    in a"anes or ethers.in a"anes or ethers.

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    so"u#i"it! in $ater (g100 m)so"u#i"it! in $ater (g100 m)

    er! sma""er! sma""

    +.5+.5

    Ethers resemble alcohols more than al$anesEthers resemble alcohols more than al$anes

    ith res#ect to solubility in aterith res#ect to solubility in ater

    Ethers resemble alcohols more than al$anesEthers resemble alcohols more than al$anes

    ith res#ect to solubility in aterith res#ect to solubility in ater

    OO

    OHOH

    H!drogen #onding toH!drogen #onding to

    $ater possi#"e *or ethers$ater possi#"e *or ethers

    and a"coho"s% notand a"coho"s% not

    possi#"e *or a"anes.possi#"e *or a"anes.

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    .. Ethers are re"atie"! unreactie.Ethers are re"atie"! unreactie.

    Their "o$ "ee" o* reactiit! is one reason $h!Their "o$ "ee" o* reactiit! is one reason $h!ethers are o*ten used as so"ents in chemica"ethers are o*ten used as so"ents in chemica"reactions.reactions.

    Ethers oidi4e in air to *orm ep"osieEthers oidi4e in air to *orm ep"osieh!droperoides and peroides.h!droperoides and peroides.

    Summary of reactions of ethersSummary of reactions of ethersSummary of reactions of ethersSummary of reactions of ethers

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    REACTIONSREACTIONSREACTIONSREACTIONS

    CHCH33CHCHCHCH22CHCH33

    OCHOCH33

    CHCH33rrHHrr

    (81,)(81,)

    CHCH33CHCHCHCH22CHCH33

    rrheatheatH

    H

    H

    CH3OCH3CH3OCH3

    H

    H

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    name as a"!"thio deriaties o* a"anesname as a"!"thio deriaties o* a"anes

    CHCH33

    66CHCH22

    CHCH33

    meth!"thiometh!"thioethaneethane

    CHCH33CHCH2266CHCH22 CHCH33

    eth!"thioeth!"thioethaneethane

    (meth!"thio)c!c"opentane(meth!"thio)c!c"opentane

    Substitutive IUPAC Names of SulfidesSubstitutive IUPAC Names of SulfidesSubstitutive IUPAC Names of SulfidesSubstitutive IUPAC Names of Sulfides

    6CH6CH33

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    c!c"opent!"c!c"opent!"

    meth!"meth!"

    su"*idesu"*ide

    ana"ogous to ethers7 #ut rep"ace ether9 as "astana"ogous to ethers7 #ut rep"ace ether9 as "ast$ord in the name #! su"*ide.9$ord in the name #! su"*ide.9

    CHCH33

    66CHCH22

    CHCH33

    eth!"eth!"meth!" su"*idemeth!" su"*ide

    CHCH33CHCH2266CHCH22 CHCH33

    didieth!"eth!"su"*idesu"*ide

    Functional Class IUPAC Names of SulfidesFunctional Class IUPAC Names of SulfidesFunctional Class IUPAC Names of SulfidesFunctional Class IUPAC Names of Sulfides

    66CHCH33

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    prepared #! nuc"eophi"ic su#stitution (6prepared #! nuc"eophi"ic su#stitution (6--2)2)

    Pre#aration of %S%&Pre#aration of %S%&Pre#aration of %S%&Pre#aration of %S%&

    :;:; >>>

    >>

    >>

    >>>>

    >>>>:: 66 :;:;

    >>>>

    CHCH33CHCHCHCH CHCH22

    C"C"

    -a6CH-a6CH33

    methano"methano"CHCH33CHCHCHCH CHCH22

    6CH6CH33

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    either the su"*oide or the su"*one can #e iso"atedeither the su"*oide or the su"*one can #e iso"ateddepending on the oidi4ing agent and reactiondepending on the oidi4ing agent and reactionconditionsconditions

    'xidation of %S%&'xidation of %S%&'xidation of %S%&'xidation of %S%&

    >>>>:: 66 :;:;

    >>>>

    >>>>:: 66 :;:;

    OO >>>>

    >>>>>>>>

    ==

    :: 66 :;:;

    OO >>>>

    >>>>>>>>

    ==

    OO >>>>>

    >>>

    >>>> ==

    su"*idesu"*ide su"*oidesu"*oide su"*onesu"*one

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    product is a su"*onium sa"tproduct is a su"*onium sa"t

    Sulfides can act as nucleo#hilesSulfides can act as nucleo#hilesSulfides can act as nucleo#hilesSulfides can act as nucleo#hiles

    :&:& >

    >>

    >>>>:: 66 :&:&

    >>>>

    :;:; :;:;