CH 08

8
Introduction to
Organic
Chemistry
2 ed
William H. Brown
8-1
Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved.
8
Alcohols,
Ethers, and
Thiols
Chapter 8
8-2
8 Structure - Alcohols
• The functional group of an alcohol
is an -OH group bonded to an sp3
hybridized carbon
• bond angles about the hydroxyl
oxygen atom are approximately 109.5°
• Oxygen is also sp3 hybridized
• two sp3 hybrid orbitals form sigma
bonds to carbon and hydrogen
• the remaining two sp3 hybrid orbitals
each contain an unshared pair of
electrons
8-3
8 Structure - Ethers
• The functional group of an ether is an oxygen
atom bonded to two carbon atoms
• Oxygen is sp3 hybridized with bond angles of
approximately 109.5°. In dimethyl ether, the C-O-
C bond angle is 110.3°
H H
••
H C O C H
••
H H
8-4
8 Structure - Thiols
• The functional group of a thiol is an
-SH (sulfhydryl) group bonded to an
sp3 hybridized carbon
• The bond angle about sulfur in
methanethiol is 100.3°, which
indicates that there is considerably
more p character to the bonding
orbitals of divalent sulfur than there
is to oxygen
8-5
8 Nomenclature-Alcohols
• IUPAC names
• the longest chain that contains the -OH group is taken
as the parent.
• the parent chain is numbered to give the -OH group the
lowest possible number
• the suffix -e is changed to -ol
• Common names
• the alkyl group bonded to oxygen is named followed
by the word alcohol
8-6
8 Nomenclature - Alcohols
OH
CH3 CH 2 CH 2 OH CH 3 CHCH 3 CH3 CH2 CH2 CH 2 OH
1-Propanol 2-Propanol 1-Butanol
(Propyl alcohol) (Isopropyl alcohol) (Butyl alcohol)
CH3
OH CH 3 CH 3 COH
CH3 CH 2 CHCH3 CH3 CH 3 CHCH 2 OH
2-Butanol 2-Methyl-1-propanol 2-Methyl-2-propanol
(sec-Butyl alcohol) (Isobutyl alcohol) (tert-Butyl alcohol)
8-7
• Problem: write IUPAC names for these alcohols
CH 3 OH OH
(a) CH 3 CHCH 2 CHCH 3 (b)
CH3
CH 2 OH
(c) CH 3 ( CH 2 ) 6 CH 2 OH (d) C
H3 C CH 2 CH 3
H
8-8
• Compounds containing more than one -OH group
are named diols, triols, etc.
CH 2 CH 2
HO OH
1,2-Ethanediol
(Ethylene glycol)
CH 3 CHCH 2 CH 2 CHCH 2
HO OH HO HO OH
1,2-Propanediol 1,2,3-Propanetriol
(Propylene glycol) (Glycerol, Glycerin)
8-9
• Unsaturated alcohols
• the double bond is shown by the infix -en-
• the hydroxyl group is shown by the suffix -ol
• number the chain to give OH the lower number
1 2 5 6
HOCH2 CH 2 CH2 CH 3
3 4
C C
H H
trans-3-Hexen-1-ol
8-10
8 Nomenclature - Ethers
• IUPAC: the longest carbon chain is the parent. Name the
OR group as an alkoxy substituent
• Common names: name the groups attached to oxygen
followed by the word ether
CH 3 CH 2 OCH 2 CH 3
Ethoxyethane
(Diethyl ether)
CH 3 OH
CH3 OCCH 3
CH 3 OCH 2 CH 3
2-Methoxy-2-methylpropane trans-2-Ethoxycyclohexanol
(methyl tert-butyl ether, MTBE)
8-11
8 Nomenclature - Ethers
• Although cyclic ethers have IUPAC names, their
common names are more widely used
O
O
O O O
Ethylene Tetrahydro- Tetrahydro- 1,4-Dioxane
oxide furan, THF pyran
8-12
8 Nomenclature - Thiols
• IUPAC names:
• the parent is the longest chain that contains the -SH
group
• change the suffix -e to -thiol
• Common names:
• name the alkyl group bonded to sulfur followed by the
word mercaptan
SH
CH3 CH 2 CH2 CH 2 SH CH3 CH2 CHCH3
1-Butanethiol 2-Butanethiol
(Butyl mercaptan) (sec-Butyl mercaptan)
8-13
8 Physical Prop - Alcohols
• Alcohols are polar compounds
H
+ -
C O
H +
H H
• Alcohols are associated in the liquid state by

hydrogen bonding
8-14
• Hydrogen bonding: the attractive force between a
partial positive charge on hydrogen and a partial
negative charge on a nearby oxygen, nitrogen, or
fluorine atom
• the strength of hydrogen bonding in water is
approximately 5 kcal/mol
• hydrogen bonds are considerably weaker than
covalent bonds
• nonetheless, they can have a significant effect on
physical properties
8-15
• Ethanol and dimethyl ether are constitutional
isomers.
• Their boiling points are dramatically different
• ethanol forms intermolecular hydrogen bonds which
increases attractive forces between its molecules,
which results in a higher boiling point
CH 3 CH2 OH CH 3 OCH 3
Ethanol Dimethyl ether
bp 78°C bp -24°C
8-16
8 Physical Prop. - Alcohols
• In relation to alkanes of comparable size and
molecular weight, alcohols
• have higher boiling points
• are more soluble in water
• The presence of additional -OH groups in a
molecule further increases boiling points and
solubility in water
8-17
8 Physical Prop. - Alcohols
bp Solubility
Formula Name MW (°C) in Water
CH 3 OH methanol 32 65 infinite
CH 3 CH 3 ethane 30 -89 insoluble
CH 3 CH 2 OH ethanol 46 78 infinite
CH 3 CH 2 CH 3 propane 44 -42 insoluble
CH 3 CH 2 CH 2 OH 1-propanol 60 97 infinite
CH 3 CH 2 CH 2 CH 3 butane 58 0 insoluble
HO ( CH 2 ) 4 OH 1,4-butanediol 90 230 infinite

CH 3 ( CH 2 ) 4 OH 1-pentanol 88 138 2.3 g/100 g
CH 3 ( CH 2 ) 4 CH 3 hexane 86 69 insoluble
8-18
8 Physical Prop. - Ethers
• Ethers are polar molecules;
• the difference in electronegativity
between oxygen (3.5) and carbon
(2.5) is 1.0
• each C-O bond is polar covalent
• oxygen bears a partial negative
charge and each carbon a partial
positive charge
8-19
8 Physical Prop. - Ethers
• Ethers are polar molecules, but because of steric
hindrance, only weak attractive forces exist
between their molecules in the pure liquid state
• Boiling points of ethers are
• lower than alcohols of comparable MW and
• close to those of hydrocarbons of comparable MW
• Ethers hydrogen bond with H2O and are more
soluble in H2O than are hydrocarbons
8-20
8 Physical Prop. - Thiols
• Low-molecular-weight thiols have a STENCH
• the scent of skunks is due primarily to these two thiols
CH3
CH 3 CHCH 2 CH 2 SH CH3 CH= CH CH 2 SH
3-Methyl-1-butanethiol 2-Butene-1-thiol
8-21
8 Physical Prop. - Thiols
• The difference in electronegativity between S
(2.5) and H (2.1) is 0.4. Because of the low
polarity of the S-H bond, thiols
• show little association by hydrogen bonding
• have lower boiling points and are less soluble in water
than alcohols of comparable MW
Thiol bp (°C) Alcohol bp (°C)

methanethiol 6 methanol 65
ethanethiol 35 ethanol 78
1-butanethiol 98 1-butanol 117
8-22
8 Acidity of Alcohols
• In dilute aqueous solution, alcohols are weakly
acidic
+
-
CH 3 O-H + O H CH 3 O + H O H
H H
[CH 3 O - ] [H 3 O + ]
Ka = = 15.5
[CH 3 OH]
8-23
8 Acidity of Alcohols
Compound Formula pKa
hydrogen chloride HCl -7 Stronger
acid
acetic acid CH 3 CO2 H 4.8
methanol CH 3 OH 15.5
water H2 O 15.7
ethanol CH 3 CH2 OH 15.9
2-propanol (CH 3 ) 2 CHOH 17
Weaker
2-methyl-2-propanol (CH 3 ) 3 COH 18 acid
8-24
8 Basicity of Alcohols
• In the presence of strong acids, the oxygen atom
of an alcohol behaves as a weak base
• proton transfer from the strong acid forms an oxonium
ion
••
+
••
H2 SO 4
CH 3 O H + H O H
••
H
A base An acid +
•• ••
O H +
••
CH 3 O H
H H
An oxonium ion
8-25
8 Reaction with Metals
• Alcohols react with Li, Na, K, and other active
metals to liberate hydrogen gas and form metal
alkoxides
2 CH 3 OH + 2 Na 2 CH 3 O - Na + + H2
Methanol Sodium
methoxide
8-26
8 Conversion of ROH to RX
• Conversion of an alcohol to an alkyl halide
involves substitution of halogen for -OH at a
saturated carbon
• the most common reagents for this purpose are the
halogen acids, HX, and thionyl chloride, SOCl2
8-27
8 Reaction with HX
• Water-soluble 3° alcohols react very rapidly with
HCl, HBr, and HI. Low-molecular-weight 1° and 2°
alcohols are unreactive under these conditions
CH 3 CH 3
CH 3 COH + HCl 25°C CH 3 CCl + H2 O
CH 3 CH 3
2-Methyl-2- 2-Chloro-2-
propanol methylpropane
8-28
8 Reaction with HX
• Water-insoluble 3° alcohols react by bubbling
gaseous HX through a solution of the alcohol
dissolved in diethyl ether or THF
OH Cl
0 oC
+ HCl + H2 O
ether CH 3
CH 3
1-Methylcyclo- 1-Chloro-1-methyl-
hexanol cyclohexane
8-29
8 Reaction with HX
• 1° and 2° alcohols require concentrated HBr and
HI to form alkyl bromides and iodides
H2 O
CH3 CH 2 CH 2 CH 2 OH + HBr
reflux
1-Butanol
CH3 CH 2 CH 2 CH 2 Br + H 2 O
1-Bromobutane
8-30
8 Mechanism: 3° ROH + HCl
• An SN1 reaction
• Step 1: rapid, reversible acid-base reaction that
transfers a proton to the OH group
CH 3 rapid and
••
+
•• reversible
CH 3 - C O- H + H O H
••
CH 3 H
CH 3 H
2-Methyl-2-propanol + ••
(tert-Butyl alcohol)
••
••
CH 3 - C O + O H
CH 3 H H
An oxonium ion
8-31
• Step 2: loss of H2O to give a carbocation intermediate
CH 3 H rate-limiting CH3
+ step ••
+
••
O H
••
CH 3 -C O CH 3 -C +
CH 3 H CH3 H
An oxonium ion A 3° carbocation
intermediate
8-32
• Step 3: reaction of the carbocation intermediate (a
Lewis acid) with halide ion (a Lewis base)
CH 3 CH 3
•• ••
rapid
••
••
••
CH 3 - C + + Cl
••
CH 3 - C- Cl
••
CH 3 CH 3
2-Chloro-2-methylpropane
(tert-Butyl chloride)
8-33
8 Mechanism: 1°ROH + HBr
• An SN2 reaction
• Step 1: rapid and reversible proton transfer
rapid and
+ •• •• reversible
CH 3 CH 2 CH2 CH 2 - O-H + H O H
••
H
H
+ ••
+
••
••
CH 3 CH 2 CH2 CH 2 -O O H
H H
An oxonium ion
8-34
8 Mechanism: 1° ROH + HX
• Step 2: displacement of HOH by halide ion
H rate-limiting
•• + step
••
••
+ CH3 CH2 CH2 CH2 -O
••
Br
••
S N2
H
H
••
••
••
••
CH3 CH2 CH2 CH2 -Br + O
••
H
8-35
8 Mechanisms: SN1 vs SN2
• Reactivities of alcohols for SN1 and SN2 are in
opposite directions
SN 1 Increasing stability of cation intermediate
3° alcohol 2° alcohol 1° alcohol
Increasing ease of access to the reaction site SN 2
8-36
8 Reaction with SOCl2
• Thionyl chloride is the most widely used reagent
for the conversion of 1° and 2° alcohols to alkyl
chlorides
• a base, most commonly pyridine or triethylamine, is
added to neutralize the HCl
pyridine
CH 3 (CH 2 ) 5 CH 2 OH + SOCl 2
1-Heptanol Thionyl
chloride
CH 3 (CH 2 ) 5 CH 2 Cl + SO 2 + HCl
1-Chloroheptane
8-37
8 Dehydration of ROH
• An alcohol can be converted to an alkene by
elimination of H and OH from adjacent carbons (a
b-elimination)
• 1° alcohols must be heated at high temperature in the
presence of an acid catalyst, such as H2SO4 or H3PO4
• 2° alcohols undergo dehydration at somewhat lower
temperatures
• 3° alcohols often require temperatures only at or
slightly above room temperature
8-38
H2 SO 4
CH 3 CH 2 OH CH 2 =CH 2 + H 2 O
o
180 C
OH
H2 SO 4
+ H 2O
140oC
Cyclohexanol Cyclohexene
CH3 CH 3
H2 SO 4
CH 3 COH CH 3 C= CH 2 + H2 O
o
50 C
CH3 2-Methylpropene
(Isobutylene)
8-39
• Where isomeric alkenes are possible, the alkene
having the greater number of substituents on the
double bond generally predominates (Zaitsev
rule)
OH
85% H 3PO4
CH 3 CH 2 CHCH3
heat
2-Butanol
CH 3 CH= CH CH 3 + CH 3 CH 2 CH= CH2
2-Butene 1-Butene
(80%) (20%)
8-40
• A three-step mechanism
• Step 1: proton transfer from H3O+ to the -OH group to
form an oxonium ion
••
rapid and
••
HO
+
•• reversible
CH 3 CHCH 2 CH 3 + H O H
H
H •• + H
O
••
••
CH 3 CHCH 2 CH3 + O H
An oxonium ion H
8-41
• Step 2: the C-O bond is broken and water is lost,
giving a carbocation intermediate
H ••
+ H
O slow and
rate limiting
CH 3 CHCH 2 CH 3
+ ••
••
CH3 CHCH 2 CH3 + H2 O
A 2o carbocation
8-42
• Step 3: proton transfer of H+ from a carbon adjacent to
the positively charged carbon to water. The sigma
electrons of the C-H bond become the pi electrons of
the carbon-carbon double bond
H
+ •• rapid
••
CH 3 - CH - CH - CH 3 + O H
••
+
CH 3 - CH = CH - CH 3 + H O H
8-43
• Acid-catalyzed alcohol dehydration and alkene
hydration are competing processes
acid
catalyst
C C + H2 O C C
H OH
An alkene An alcohol
• large amounts of water favor alcohol formation

• scarcity of water or experimental conditions where
water is removed favor alkene formation
8-44
8 Oxidation: 1° ROH
• A primary alcohol can be oxidized to an aldehyde
or a carboxylic acid, depending on the oxidizing
agent and experimental conditions
OH O O
[O] [O]
CH 3 -CH 2 CH 3 -C- H CH 3 -C- OH
A primary An aldehyde A carboxylic
alcohol acid
8-45
8 Oxidation: chromic acid
• Chromic acid is prepared by dissolving
chromium(VI) oxide or potassium dichromate in
aqueous sulfuric acid
H2 SO 4
CrO 3 + H2 O H2 CrO 4
Chromium(VI) Chromic acid
oxide
H2 SO 4 H2 O
K2 Cr 2 O7 H2 Cr 2 O7 2 H2 CrO 4
Potassium Chromic acid
dichromate
8-46
• Oxidation of 1-octanol by chromic acid gives
octanoic acid
• the aldehyde intermediate is not isolated
CrO3
CH 3 ( CH 2 ) 6 CH 2 OH
H2 SO4 , H 2 O
1-Octanol
O O
CH 3 ( CH 2 ) 6 CH CH3 ( CH2 ) 6 COH
Octanal Octanoic acid
(not isolated)
8-47
8 PCC
• Pyridinium chlorochromate (PCC): a form of
Cr(VI) prepared by dissolving CrO3 in aqueous
HCl and adding pyridine to precipitate PCC
CrO 3 Cl -
N+
H
• PCC is selective for the oxidation of 1° alcohols to
aldehydes; it does not oxidize aldehydes further to
carboxylic acids
8-48
• PCC oxidation of a 1° alcohol to an aldehyde
O
CH 2 OH PCC CH
Geraniol Geranial
8-49
• 2° alcohols are oxidized to ketones by both
chromic acid and and PCC
CH(CH 3 ) 2 CH(CH 3 ) 2
OH H2 CrO 4 O
acetone
CH 3 CH 3
2-Isopropyl-5-methyl- 2-Isopropyl-5-methyl-
cyclohexanol cyclohexanone
(Menthol) (Menthone)
8-50
8 Reactions of ethers
• Ethers, R-O-R, resemble hydrocarbons in their
resistance to chemical reaction
• they do not react with strong oxidizing agents such as
chromic acid, H2CrO4
• they are not affected by most acids and bases at
moderate temperatures
• Because of their good solvent properties and
general inertness to chemical reaction, ethers are
excellent solvents in which to carry out organic
reactions
8-51
8 Epoxides
• Epoxide: a cyclic ether in which oxygen is one
atom of a three-membered ring
• Common names are derived from the name of the
alkene from which the epoxide is formally
derived
CH 2 CH 2 CH 2 CHCH 3
O O
Ethylene oxide Propylene oxide
8-52
8 Synthesis of Epoxides-1
• Ethylene oxide, one of the few epoxides
manufactured on an industrial scale, is prepared
by air oxidation of ethylene
Ag
2 CH 2 =CH 2 + O 2 2 CH 2 CH 2
O
Oxirane
(Ethylene oxide)
8-53
• The most common laboratory method for the
synthesis of epoxides is oxidation of an alkene
using a peroxycarboxylic acid (a peracid) such
as peroxyacetic acid
O
CH3 COOH
Peroxyacetic acid
(Peracetic acid)
8-54
• Epoxidation of cyclohexene
O
+ RCOOH CH 2 Cl 2
A peroxy-
Cyclohexene carboxylic
acid H O
O + RCOH
H
1,2-Epoxycyclohexane A carboxylic
(Cyclohexene oxide) acid
8-55
8 Hydrolysis of Epoxides
• In the presence of an acid catalyst, an epoxide is
hydrolyzed to a glycol
+
CH2 CH2 + H2 O H HOCH2 CH2 OH
O 1,2-Ethanediol
Ethylene oxide (Ethylene glycol)
8-56
• Step 1: proton transfer to the epoxide to form a
bridged oxonium ion intermediate
H2 C CH2 H2 C CH 2
O + O+
H O H
H
H
8-57
• Step 2: attack of H2O from the side opposite the
oxonium ion bridge
H H
O H H
+O
H2 C CH 2 H2 C CH 2
O+ O
H H
8-58
• Step 3: proton transfer to solvent to complete the
hydrolysis
H H
O
H H H
+O O
+
H2 C CH 2 H2 C CH 2 + H O H
O O H
H H
8-59
• Attack of the nucleophile on the protonated
epoxide shows anti stereoselectivity
• hydrolysis of an epoxycycloalkane gives a trans-diol
H OH
H+
O + H2 O
H OH
1,2-Epoxycyclopentane trans -1,2-Cyclopentanediol
(Cyclopentene oxide)
8-60
• Compare the stereochemistry of the glycols
formed by these two methods
H OH
+
RCO3 H H
O
H2 O
H OH
trans-1,2-Cyclopentanediol
OH
Os O4
ROOH
OH
cis-1,2-Cyclopentanediol
8-61
8 Thiols
• Thiols are stronger acids than alcohols
pKa = 8.5 -
CH 3 CH 2 SH + H2 O CH 3 CH 2 S + H3 O+
pKa = 15.9
- +
CH 3 CH 2 OH + H 2 O CH 3 CH 2 O + H 3 O
8-62
8 Thiols
• When dissolved an aqueous NaOH, they are
converted completely to alkylsulfide salts
CH 3 CH 2 SH + Na + OH -
pKa = 8.5
Stronger Stronger
acid base - +
CH 3 CH 2 S Na + H2 O
pKa = 15.7
Weaker base Weaker
acid
8-63
8 Thiols
• Thiols are oxidized to disulfides by a variety of
oxidizing agents, including O2.
• they are so susceptible to this oxidation that they must
be protected from air during storage
1
2 RSH + 2
O2 RSSR + H2 O
A thiol A disulfide
• The most common reaction of thiols in biological

systems in interconversion between thiols and
disulfides, -S-S-
8-64
8
Alcohols,
Ethers, and
Thiols
End of Chapter 8
8-65

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8

• Alcohols are associated in the liquid state by

HO ( CH 2 ) 4 OH 1,4-butanediol 90 230 infinite

Thiol bp (°C) Alcohol bp (°C)

+ CH3 CH2 CH2 CH2 -O

SN 1 Increasing stability of cation intermediate

3° alcohol 2° alcohol 1° alcohol

Increasing ease of access to the reaction site SN 2

• large amounts of water favor alcohol formation

• The most common reaction of thiols in biological

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