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7/24/2019 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% ðer& isa"pha#etica" order as separate $ords% ðer& 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 :&:&
>>>>
:;:; :;:;