Dr. Wolf's CHM 201 & 202 4- 1
Chapter 4Chapter 4
Alcohols and Alkyl HalidesAlcohols and Alkyl Halides
Dr. Wolf's CHM 201 & 202 4- 2
(1) alcohol + hydrogen halide(1) alcohol + hydrogen halide
ROH + HX ROH + HX RX + H RX + H22OO
(2) alkane + halogen(2) alkane + halogen
RH + XRH + X22 RX + HX RX + HX
Both are substitution reactionsBoth are substitution reactions
Overview of ChapterOverview of Chapter
This chapter introduces chemical reactions and This chapter introduces chemical reactions and their mechanisms by focusing on two reactionstheir mechanisms by focusing on two reactionsthat yield alkyl halides.that yield alkyl halides.
Dr. Wolf's CHM 201 & 202 4- 3
4.14.1
Functional GroupsFunctional Groups
Dr. Wolf's CHM 201 & 202 4- 4
a structural unit in a molecule responsible for itsa structural unit in a molecule responsible for itscharacteristic behavior under a particular set ofcharacteristic behavior under a particular set ofreaction conditionsreaction conditions
Functional GroupFunctional Group
Dr. Wolf's CHM 201 & 202 4- 5
AlcoholAlcohol ROHROH
Alkyl halideAlkyl halide RRXX ( (XX = F, Cl, Br, I) = F, Cl, Br, I)
AmineAmine primary amine: Rprimary amine: RNHNH22
secondary amine: Rsecondary amine: R22NHNH
tertiary amine: Rtertiary amine: R33NN
Families of organic compoundsFamilies of organic compoundsand their functional groupsand their functional groups
Dr. Wolf's CHM 201 & 202 4- 6
EtherEther RROOR'R'
NitrileNitrile RRCNCN
NitroalkaneNitroalkane RRNONO22
SulfideSulfide RSR'RSR'
ThiolThiol RSHRSH
EpoxideEpoxide CC CC
OO
Families of organic compoundsFamilies of organic compoundsand their functional groupsand their functional groups
Dr. Wolf's CHM 201 & 202 4- 7
OO
CC
Carbonyl groupCarbonyl group
OO
CC
Acyl groupAcyl group
RR
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 8
OO
CC
Carbonyl groupCarbonyl group
OO
CC
AldehydeAldehyde
RR HH
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 9
OO
CC
Carbonyl groupCarbonyl group
OO
CC
KetoneKetone
RR R'R'
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 10
OO
CC
Carbonyl groupCarbonyl group
OO
CC
Carboxylic acidCarboxylic acid
RR OHOH
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 11
OO
CC
Carbonyl groupCarbonyl group
OO
CC
EsterEster
RR OR'OR'
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 12
OO
CC
Carbonyl groupCarbonyl group
OO
CC
AmideAmide
RR NHNH22
Many classes of organic compounds contain Many classes of organic compounds contain a carbonyl groupa carbonyl group
Dr. Wolf's CHM 201 & 202 4- 13
4.24.2
IUPAC NomenclatureIUPAC Nomenclature
of Alkyl Halidesof Alkyl Halides
Dr. Wolf's CHM 201 & 202 4- 14
The two that are most widely used are:The two that are most widely used are:functional class nomenclaturefunctional class nomenclaturesubstitutive nomenclaturesubstitutive nomenclature
Both types can be applied to alcohols andBoth types can be applied to alcohols andalkyl halides.alkyl halides.
IUPAC NomenclatureIUPAC Nomenclature
There are several kinds of IUPAC nomenclature.There are several kinds of IUPAC nomenclature.
Dr. Wolf's CHM 201 & 202 4- 15
Name the alkyl group and the halogen asName the alkyl group and the halogen asseparate words (separate words (alkylalkyl + + halidehalide))
Functional Class Nomenclature of Alkyl HalidesFunctional Class Nomenclature of Alkyl Halides
CHCH33FF CHCH33CHCH22CHCH22CHCH22CHCH22ClCl
CHCH33CHCH22CHCHCHCH22CHCH22CHCH33
BrBr
HH
II
Dr. Wolf's CHM 201 & 202 4- 16
Name the alkyl group and the halogen asName the alkyl group and the halogen asseparate words (separate words (alkylalkyl + + halidehalide))
Functional Class Nomenclature of Alkyl HalidesFunctional Class Nomenclature of Alkyl Halides
CHCH33FF CHCH33CHCH22CHCH22CHCH22CHCH22ClCl
CHCH33CHCH22CHCHCHCH22CHCH22CHCH33
BrBr
Methyl fluorideMethyl fluoride Pentyl chloridePentyl chloride
1-Ethylbutyl bromide1-Ethylbutyl bromide Cyclohexyl iodideCyclohexyl iodide
HH
II
Dr. Wolf's CHM 201 & 202 4- 17
Name as halo-substituted alkanes.Name as halo-substituted alkanes.
Number the longest chain containing theNumber the longest chain containing thehalogen in the direction that gives the lowesthalogen in the direction that gives the lowestnumber to the substituted carbon.number to the substituted carbon.
Substitutive Nomenclature of Alkyl HalidesSubstitutive Nomenclature of Alkyl Halides
CHCH33CHCH22CHCH22CHCH22CHCH22FF CHCH33CHCHCHCH22CHCH22CHCH33
BrBr
CHCH33CHCH22CHCHCHCH22CHCH33
II
Dr. Wolf's CHM 201 & 202 4- 18
Name as halo-substituted alkanes.Name as halo-substituted alkanes.
Number the longest chain containing theNumber the longest chain containing thehalogen in the direction that gives the lowesthalogen in the direction that gives the lowestnumber to the substituted carbon.number to the substituted carbon.
Substitutive Nomenclature of Alkyl HalidesSubstitutive Nomenclature of Alkyl Halides
CHCH33CHCH22CHCH22CHCH22CHCH22FF CHCH33CHCHCHCH22CHCH22CHCH33
BrBr1-Fluoropentane1-Fluoropentane
3-Iodopentane3-Iodopentane
2-Bromopentane2-BromopentaneCHCH33CHCH22CHCHCHCH22CHCH33
II
Dr. Wolf's CHM 201 & 202 4- 19
Substitutive Nomenclature of Alkyl HalidesSubstitutive Nomenclature of Alkyl Halides
Halogen and alkyl groupsHalogen and alkyl groupsare of equal rank when are of equal rank when it comes to numberingit comes to numberingthe chain.the chain.
Number the chain in theNumber the chain in thedirection that gives the direction that gives the lowest number to thelowest number to thegroup (halogen or alkyl)group (halogen or alkyl)that appears first.that appears first.
CHCH33
ClCl ClCl
CHCH33
Dr. Wolf's CHM 201 & 202 4- 20
Substitutive Nomenclature of Alkyl HalidesSubstitutive Nomenclature of Alkyl Halides
5-Chloro-2-methylheptane5-Chloro-2-methylheptane
2-Chloro-5-methylheptane2-Chloro-5-methylheptane
CHCH33
ClCl ClCl
CHCH33
Dr. Wolf's CHM 201 & 202 4- 21
4.34.3
IUPAC NomenclatureIUPAC Nomenclature
of Alcoholsof Alcohols
Dr. Wolf's CHM 201 & 202 4- 22
Name the alkyl group and add "alcohol" as aName the alkyl group and add "alcohol" as aseparate word.separate word.
Functional Class Nomenclature of AlcoholsFunctional Class Nomenclature of Alcohols
CHCH33CHCH22OHOH
CHCH33CHCHCHCH22CHCH22CHCH22CHCH33
OHOH
CHCH33CCHCCH22CHCH22CHCH33
OHOH
CHCH33
Dr. Wolf's CHM 201 & 202 4- 23
Name the alkyl group and add "alcohol" as aName the alkyl group and add "alcohol" as aseparate word.separate word.
Functional Class Nomenclature of AlcoholsFunctional Class Nomenclature of Alcohols
CHCH33CHCH22OHOH
CHCH33CHCHCHCH22CHCH22CHCH22CHCH33
OHOH
CHCH33CCHCCH22CHCH22CHCH33
OHOH
CHCH33
Ethyl alcoholEthyl alcohol
1-Methylpentyl alcohol1-Methylpentyl alcohol
1,1-Dimethylbutyl1,1-Dimethylbutylalcoholalcohol
Dr. Wolf's CHM 201 & 202 4- 24
Name as "alkanols." Replace -e ending of alkaneName as "alkanols." Replace -e ending of alkanename by -ol.name by -ol.
Number chain in direction that gives lowest numberNumber chain in direction that gives lowest numberto the carbon that bears the —OH group.to the carbon that bears the —OH group.
Substitutive Nomenclature of AlcoholsSubstitutive Nomenclature of Alcohols
CHCH33CHCH22OHOH
CHCH33CHCHCHCH22CHCH22CHCH22CHCH33
OHOH
CHCH33CCHCCH22CHCH22CHCH33
OHOH
CHCH33
Dr. Wolf's CHM 201 & 202 4- 25
Name as "alkanols." Replace -e ending of alkaneName as "alkanols." Replace -e ending of alkanename by -ol.name by -ol.
Number chain in direction that gives lowest numberNumber chain in direction that gives lowest numberto the carbon that bears the —OH group.to the carbon that bears the —OH group.
Substitutive Nomenclature of AlcoholsSubstitutive Nomenclature of Alcohols
CHCH33CHCH22OHOH
CHCH33CHCHCHCH22CHCH22CHCH22CHCH33
OHOH
CHCH33CCHCCH22CHCH22CHCH33
OHOH
CHCH33
EthanolEthanol
2-Hexanol2-Hexanol2-Methyl-2-pentanol2-Methyl-2-pentanol
Dr. Wolf's CHM 201 & 202 4- 26
OHOH
CHCH33
Substitutive Nomenclature of AlcoholsSubstitutive Nomenclature of Alcohols
Hydroxyl groups outrank Hydroxyl groups outrank alkyl groups when alkyl groups when it comes to numberingit comes to numberingthe chain.the chain.
Number the chain in theNumber the chain in thedirection that gives the direction that gives the lowest number to thelowest number to thecarbon that bears thecarbon that bears theOH groupOH group
CHCH33
OHOH
Dr. Wolf's CHM 201 & 202 4- 27
Substitutive Nomenclature of AlcoholsSubstitutive Nomenclature of Alcohols
6-Methyl-3-heptanol6-Methyl-3-heptanol
5-Methyl-2-heptanol5-Methyl-2-heptanol
OHOH
CHCH33
CHCH33
OHOH
Dr. Wolf's CHM 201 & 202 4- 28
4.44.4
Classes of AlcoholsClasses of Alcohols
and Alkyl Halidesand Alkyl Halides
Dr. Wolf's CHM 201 & 202 4- 29
Alcohols and alkyl halides are classified asAlcohols and alkyl halides are classified asprimaryprimarysecondarysecondarytertiarytertiary
according to their "degree of substitution."according to their "degree of substitution."
Degree of substitution is determined by countingDegree of substitution is determined by countingthe number of carbon atoms directly attached tothe number of carbon atoms directly attached tothe carbon that bears the halogen or hydroxyl group.the carbon that bears the halogen or hydroxyl group.
ClassificationClassification
Dr. Wolf's CHM 201 & 202 4- 30
CHCH33CHCH22CHCH22CHCH22CHCH22FF
CHCH33CHCHCHCH22CHCH22CHCH33
BrBr
primary alkyl halideprimary alkyl halide
secondary alkyl halidesecondary alkyl halide
ClassificatioClassificationn
CHCH33CCHCCH22CHCH22CHCH33
OHOH
CHCH33
tertiary alcoholtertiary alcohol
HH
OHOH
secondary alcoholsecondary alcohol
Dr. Wolf's CHM 201 & 202 4- 31
4.54.5
Bonding in AlcoholsBonding in Alcohols
and Alkyl Halidesand Alkyl Halides
Dr. Wolf's CHM 201 & 202 4- 32
HH
HH
HH
alcohols and alkyl halides are polaralcohols and alkyl halides are polar
= 1.7 D= 1.7 D = 1.9 D= 1.9 D
HH
HH
CC OO
HH
HH
CC ClCl++
––––++
++
Dipole MomentsDipole Moments
Dr. Wolf's CHM 201 & 202 4- 33
alcohols and alkyl halides are polaralcohols and alkyl halides are polar
= 1.7 D= 1.7 D = 1.9 D= 1.9 D
Dipole MomentsDipole Moments
Dr. Wolf's CHM 201 & 202 4- 34
+ + – –
– – + +
+ + – – + + – – + + – –
Dipole-Dipole Attractive ForcesDipole-Dipole Attractive Forces
Dr. Wolf's CHM 201 & 202 4- 35
+ + – –
– – + +
+ + – – + + – – + + – –
Dipole-Dipole Attractive ForcesDipole-Dipole Attractive Forces
Dr. Wolf's CHM 201 & 202 4- 36
Boiling pointBoiling point
Solubility in waterSolubility in water
DensityDensity
4.64.6
Physical Properties of Physical Properties of
Alcohols and Alkyl Halides:Alcohols and Alkyl Halides:
Intermolecular ForcesIntermolecular Forces
Dr. Wolf's CHM 201 & 202 4- 37
4444 4848 4646
-42-42 -32-32 +78+78
00 1.91.9 1.71.7
CHCH33CHCH22CHCH33 CHCH33CHCH22FF CHCH33CHCH22OHOH
MolecularMolecularweightweight
BoilingBoilingpoint, °Cpoint, °C
DipoleDipolemoment, Dmoment, D
Effect of Structure on Boiling PointEffect of Structure on Boiling Point
Dr. Wolf's CHM 201 & 202 4- 38
4444
--4242
00
CHCH33CHCH22CHCH33
MolecularMolecularweightweight
BoilingBoilingpoint, °Cpoint, °C
DipoleDipolemoment, Dmoment, D
Intermolecular forcesIntermolecular forcesare weak.are weak.
Only intermolecularOnly intermolecularforces are inducedforces are induceddipole-induced dipoledipole-induced dipoleattractions.attractions.
Effect of Structure on Boiling PointEffect of Structure on Boiling Point
Dr. Wolf's CHM 201 & 202 4- 39
4848
-32-32
1.91.9
CHCH33CHCH22FF
MolecularMolecularweightweight
BoilingBoilingpoint, °Cpoint, °C
DipoleDipolemoment, Dmoment, D
A polar molecule;A polar molecule;therefore dipole-dipoletherefore dipole-dipoleand dipole-inducedand dipole-induceddipole forces contributedipole forces contributeto intermolecular to intermolecular attractions.attractions.
Effect of Structure on Boiling PointEffect of Structure on Boiling Point
Dr. Wolf's CHM 201 & 202 4- 40
4646
+78+78
1.71.7
CHCH33CHCH22OHOH
MolecularMolecularweightweight
BoilingBoilingpoint, °Cpoint, °C
DipoleDipolemoment, Dmoment, D
Highest boiling point;Highest boiling point;strongest intermolecularstrongest intermolecularattractive forces.attractive forces.
Hydrogen bonding isHydrogen bonding isstronger than otherstronger than otherdipole-dipole attractions.dipole-dipole attractions.
Effect of Structure on Boiling PointEffect of Structure on Boiling Point
Dr. Wolf's CHM 201 & 202 4- 41
++––
––++
Figure 4.4 Hydrogen bonding in ethanolFigure 4.4 Hydrogen bonding in ethanol
Dr. Wolf's CHM 201 & 202 4- 42
Figure 4.4 Hydrogen bonding in ethanolFigure 4.4 Hydrogen bonding in ethanol
Dr. Wolf's CHM 201 & 202 4- 43
Boiling point increases with increasingBoiling point increases with increasingnumber of halogensnumber of halogens
CHCH33ClCl -24°C-24°C
CHCH22ClCl22 40°C40°C
CHCHClCl33 61°C61°C
CCClCl44 77°C77°C
CompoundCompound Boiling PointBoiling Point
Even though CClEven though CCl4 4 is the only compound in this list without a is the only compound in this list without a
dipole moment, it has the highest boiling point.dipole moment, it has the highest boiling point.
Induced dipole-induced dipole forces are greatest in Induced dipole-induced dipole forces are greatest in CClCCl44 because it has the greatest number of Cl atoms. because it has the greatest number of Cl atoms.
Cl is more polarizable than H. Cl is more polarizable than H.
Dr. Wolf's CHM 201 & 202 4- 44
But trend is not followed when halogenBut trend is not followed when halogenis fluorineis fluorine
CHCH33CHCH22FF -32°C-32°C
CHCH33CHCHFF22 -25°C-25°C
CHCH33CCFF33 -47°C-47°C
CCFF33CCFF33 -78°C-78°C
CompoundCompound Boiling PointBoiling Point
Dr. Wolf's CHM 201 & 202 4- 45
But trend is not followed when halogenBut trend is not followed when halogenis fluorineis fluorine
CHCH33CHCH22FF -32°C-32°C
CHCH33CHCHFF22 -25°C-25°C
CHCH33CCFF33 -47°C-47°C
CCFF33CCFF33 -78°C-78°C
CompoundCompound Boiling PointBoiling Point
Fluorine is not very polarizable and induced dipole-Fluorine is not very polarizable and induced dipole-induced dipole forces decrease with increasing induced dipole forces decrease with increasing fluorine substitution.fluorine substitution.
Dr. Wolf's CHM 201 & 202 4- 46
Solubility in waterSolubility in water
Alkyl halides are insoluble in water.Alkyl halides are insoluble in water.
Methanol, ethanol, isopropyl alcohol areMethanol, ethanol, isopropyl alcohol arecompletely miscible with water.completely miscible with water.
The solubility of an alcohol in waterThe solubility of an alcohol in waterdecreases with increasing number of decreases with increasing number of carbons (compound becomescarbons (compound becomesmore hydrocarbon-like).more hydrocarbon-like).
Dr. Wolf's CHM 201 & 202 4- 47
++––
––
++
––++
Figure 4.5 Hydrogen Bonding Figure 4.5 Hydrogen Bonding Between Ethanol and WaterBetween Ethanol and Water
Dr. Wolf's CHM 201 & 202 4- 48
DensityDensity
Alkyl fluorides and alkyl chlorides Alkyl fluorides and alkyl chlorides areareless dense than water.less dense than water.
Alkyl bromides and alkyl iodides are Alkyl bromides and alkyl iodides are more dense than water.more dense than water.
All liquid alcohols have densities of All liquid alcohols have densities of about 0.8 g/mL.about 0.8 g/mL.
Dr. Wolf's CHM 201 & 202 4- 49
4.74.7
Preparation of Alkyl Halides fromPreparation of Alkyl Halides from
Alcohols and Hydrogen HalidesAlcohols and Hydrogen Halides
ROH + HX ROH + HX RX + H RX + H22OO
Dr. Wolf's CHM 201 & 202 4- 50
RROOHH + + HHXX R RXX + + HHOOHH
Hydrogen halide reactivityHydrogen halide reactivity
HHFF HHClCl HHBrBr HHII
Reaction of Alcohols with Hydrogen HalidesReaction of Alcohols with Hydrogen Halides
least reactiveleast reactive most reactivemost reactive
Dr. Wolf's CHM 201 & 202 4- 51
Alcohol reactivityAlcohol reactivity
CHCH33OOHH RCH RCH22OOH H RR22CHCHOOH H RR33CCOOHH
MethanolMethanol PrimaryPrimary SecondarySecondary TertiaryTertiary
RROOH H + + HHXX R RXX + + HHOOHH
Reaction of Alcohols with Hydrogen HalidesReaction of Alcohols with Hydrogen Halides
least reactiveleast reactive most reactivemost reactive
Dr. Wolf's CHM 201 & 202 4- 52
(CH(CH33))33CCOHOH + H + HClCl (CH(CH33))33CCClCl + H + H22OO
78-88%78-88%
25°C25°C
CHCH33(CH(CH22))55CHCH22OHOH + H + HBrBr
CHCH33(CH(CH22))55CHCH22BrBr + H + H22OO
87-90%87-90%
120°C120°C
Preparation of Alkyl HalidesPreparation of Alkyl Halides
73%73%
80-100°C80-100°C
OHOH ++ HHBrBr
BrBr ++ HH22OO
Dr. Wolf's CHM 201 & 202 4- 53
CHCH33CHCH22CHCH22CHCH22OHOH CHCH33CHCH22CHCH22CHCH22BrBr
NaNaBrBrHH22SOSO44
70-83%70-83%heatheat
A mixture of sodium bromide and sulfuric A mixture of sodium bromide and sulfuric acid may be used in place of HBr.acid may be used in place of HBr.
Preparation of Alkyl HalidesPreparation of Alkyl Halides