StructuresofAlcohols,Phenols,ThiolsandEthers

Alcohols,phenols,thiolsandethersconsistofa
hydrocarbonsinglybondedtoanoxygenorasulfur
AlcoholshaveanOHgroupattachedtoanalkane,phenols
haveanOHgroupattachedtoabenzene,thiolshavean
SHgroupattachedtoanalkaneandethershaveanO
bondedtotwoCs
OH

OH

Alchol

Phenol
O

SH

Thiol

Ether

NamingAlcohols
Parentnameendsinol
FindlongestchaincontainingtheCtowhichtheOH
groupisattached
NumberCsstartingatendnearestOHgroup
Locateandnumbersubstituentsandgivefullname
useanumbertoindicatepositionofOHgroup
cyclicalcoholshavecyclobeforetheparentname;
numberingbeginsattheOHgroup,goingin
directionthatgivessubstituentslowestpossible
numbers
useaprefix(di,tri)toindicatemultipleOH
groupsinacompound

Nomenclature
OH
Ethanol
(Ethyl alcohol)

OH

OH
1-Propanol
(Propyl alcohol)

2-Propanol
(Isopropyl alcohol)

OH
OH
1-Butanol
(Butyl alcohol)

OH
2-Butanol
(sec-Butyl alcohol)

2-Methyl-1-propanol
(Isobutyl alcohol)
OH

OH
2-Methyl-2-propanol
(tert-Butyl alcohol)

Cyclohexanol
(Cyclohexyl alcohol)

ClassificationofAlcohols
Alcoholscanbeclassifiedasmethyl,primary,
secondaryortertiary
Classificationisbasedonthenumberofalkyl
groupsattachedtothecarbontowhichtheOH
groupisattached
IfOHisattachedtoa1C,itsa1alcohol,etc.
H
H

H
OH

H 3C

CH3

CH3
OH

H 3C

OH

C
CH3

Methyl

Primary

Secondary

H 3C

Tertiary

OH

NamingPhenols
PhenolisthecommonnameforanOHgroup
attachedtoabenzene,andisacceptedbyIUPAC
Compoundswithadditionalsubstituentsare
namedassubstitutedphenols
Ortho,metaandparaareusedwhenthereisonly
oneothersubstituent
Iftherearetwoormoreadditionalsubstituents,
eachmustbenumbered,beginningattheOHand
goingindirectionthatgivessubstituentslowest
numbers(oralphabeticalifsameinboth
directions)

Manyphenolshavepleasantodors,andsomearebioactive
Euganol(fromcloves)isatopicalanesthetic
Thymol(fromthyme)isanantiseptic

NamingThiols
Parentnameendsinthiol
FindlongestchaincontainingtheCtowhichtheSH
groupisattached
NumberCsstartingatendnearestSHgroup
Parentnameisalkanenameofcarbonportionoflongest
chain,followedbythiol
Locateandnumbersubstituentsandgivefullname
useanumbertoindicatepositionofSHgroup
cyclicthiolshavecyclobeforetheparentname;
numberingbeginsattheSHgroup,goingindirection
thatgivessubstituentslowestpossiblenumbers
useaprefix(di,tri)toindicatemultipleSHgroupsin
acompound

ThiolsNomenclature
Commonnamesforsimplethiolsare
derivedbynamingthealkylgroupbonded
toSHandaddingtheword"mercaptan"
mercaptan
CH3
CH3CH2SH
Ethanethiol
(Ethyl mercaptan)

CH3CHCH2SH
2-Methyl-1-propanethiol
(Isobutyl mercaptan)

NamingEthers
Simpleethersarenamedbytheircommonnames
Forcommonnames:nameeachalkylgroup
attachedtotheoxygenfollowedbyether
ForcomplexethersIUPACnamesareused
ForIUPACnames:
1.Nameasanalkane,withlargeralkylgroup
beingtheparentchain
2.ThesmalleralkylgroupandtheOarenamed
togetherasanalkoxygroup(replaceylwithoxy)
3.Numberchainstartingatendnearestalkoxy
group
4.Useanumbertogivelocationofalkoxygroup

CH3 CH2 OCH2 CH3

Diethyl ether

OCH3
Cyclohexyl methyl ether
(Methoxycyclohexane)

NamingCyclicEthers
Cyclicethersaregenerallynamedbytheircommonnames
(wewillnotstudytheIUPACnames)
Acyclicethercontainingtwocarbonsiscalledethylene
oxide(generallyknownasepoxides)
Acyclicethercontaining4carbons(with2doublebonds)
iscalledafuran
Acyclicethercontaining5carbons(with2doublebonds)
iscalledapyran
Acyclicethercontaining4carbonsand2oxygensis
calledadioxane
O

ethylene oxide

furan

tetrahydrofuran

pyran

tetrahydropyran

1,4-dioxane

NamingExamples
OH

OH

OH
SH

2-propanol

2-ethyl-4-methylcyclopentanol
OH

Br

propanethiol

O
O

Br

2,4-dibromophenol

diethyl ether

CH3

ortho-methylphenol
O

furan

1,4-dioxane

PhysicalPropertiesofAlcohols,Phenols,ThiolsandEthers
Allofthesetypesofcompoundshaveabentgeometryaroundthe
OortheS,andarepolarcompounds
AlcoholsandphenolscontainaverypolarizedOHbond,andthey
canHbondwiththemselvesandwithotheralcoholsorwater
Smallalcohols(4orlessCs)aresolubleinwater
Phenolissolubleinwater(evenwith6Cs)becauseitpartially
ionizesinwater(itsaweakacid)
Alcoholsandphenolshaverelativelyhighboilingpoints
Thiolsaremuchlesspolarthanalcoholsbecausethe
electronegativityofSisthesameasthatofC(2.5),muchlessthan
thatofO(3.5),soCSandSHbondsarenotpolar
thiolsdonotHbondandhaverelativelylowboilingpoints
EthersdonotHbondwiththemselves,sohaveboilingpoints
similartohydrocarbons
ethersareonlyslightlysolubleinwaterandarehighlyflammable

PhysicalProperties
bpincreasesasMWincreases
solubilityinwaterdecreasesasMWincreases
Molecular
Weight

bp
(C)

Solubility
in Water

Structural Formula

Name

CH3OH
CH3CH3

methanol
ethane

32
30

65
-89

infinite
insoluble

CH3CH2 OH

46
44

78
-42

infinite

CH3CH2 CH3

ethanol
propane

CH3CH2 CH2OH
CH3CH2 CH2CH3

1-propanol
butane

60
58

97
0

CH3CH2 CH2CH2OH
CH3CH2 CH2CH2CH3

1-butanol
pentane

74

117

72

36

insoluble
infinite
insoluble
8 g/100 g
insoluble

AcidityandBasicityofAlcoholsandPhenols

Alcoholsandphenols,likewater,canactaseitherweakacidsorweak
bases(althoughphenolismoreacidic)
Phenolsaremoreacidicbecausetheanionthatformsuponlossofthe
protonisstabilizedbyresonance
H

+HCl

Cl

H
H

NH3

H2O

NH4

+ H3O

CombustionReactionsofAlcoholsandEthers
Bothalcoholsandetherscanburnwithoxygento
producewater,carbondioxideandheat(justlike
hydrocarbons)
However,ethersaremuchmoreflammablethan
alcoholsandcareshouldbetakenwhenworkingwith
ethersinthelaboratory(justasparkfromstatic
electricitycansetoffetherfumes)

Examples:
CH3CH2OH+3O22CO2+3H2O+Heat
CH3OCH3+3O22CO2+3H2O+Heat

DehydrationofAlcoholstoFormAlkenes
Analcoholcanloseawatermoleculetoformanalkeneusinganacid
catalystsuchasH2SO4andheat(aneliminationreaction)
ThisisthereverseoftheadditionofH2Otoanalkene
Dehydrationisfavoredbyusingheat(endothermicreaction)anda
solventotherthanwater(lowerconcentrationofH2O)
Whenmorethanonealkenecanbeformed,Zaitsevsrulestatesthat
themoresubstitutedalkenewillbethemajorproduct
Orderofreactivity=3>2>(1>methyl)
Infactthisreactiononlyworkswith3and2alcohols
OH

H3O+

Heat

H
OH

H
CH3

H3O+
Heat

CH3

H2O

H2O

MechanismofAcidCatalyzedDehydrationofanAlcohol
First,theacidcatalystprotonatesthealcohol
Next,H2Oiseliminatedtoformacarbocation
Finally,aprotonisremovedtoformanalkene+H 3O+

O
H

OH

H
O

+
H

O
H