MSE245

Organic Materials
Chemistry and Processing
Professor Naomi Matsuura
WB 138
naomi.matsuura@utoronto.ca

February 14, 2022

Recall (Week 1): Functional Groups

• Functional Group: An atom or group of atoms

within a molecule that shows a characteristic set of
physical and chemical properties.
• Functional groups are important for three reasons,
they are:
• The units by which we divide organic compounds into
classes.
• The sites of characteristic chemical reactions.
• The basis for naming organic compounds.

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 MSE 245 Course Outline
1. Review: bonding, Lewis structures, hybridization, acid base chemistry
2. Introduction to IUPAC nomenclature (handouts)
3. Alkanes and Cycloalkanes (Ch 3)
4. Alkenes and Alkynes (Ch 4)
5. Reactions of Alkenes/Alkynes (Ch 5)
6. Chirality and the Handedness of Molecules (handouts)
7. Haloalkanes (Ch 7)
8. Alcohols, Ethers, and Thiols (Ch 8)
9. Benzene and its Derivatives (Ch 9)
10. Amines (Ch 10)
11. Aldehydes and Ketones (handouts)
12. Carboxylic Acids and derivatives (Ch 13 &14)
13. Organic Polymer Chemistry and synthesis (Ch 16 + Brazel & Rosen Ch 1 & 2)
14. Polymer Physical properties (Brazel & Rosen Ch 3, 4, 5 and 6)
15. Polymer processing (Ch17 (Brazel & Rosen Ch-17)
16. Polymer recycling, degradation and environmental impact (handouts)
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Chapter 8

• Introduction to alcohols (8.1)

• Reactions and production of alcohols (8.2)
• Ethers – brief overview (8.3)
• Thiols (8.5)
• Reactions of Thiols – brief overview (8.6)

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 ALCOHOLS, ETHERS &
THIOLS
ALCOHOLS

Alcohols - Structure
• The functional group of an alcohol is
an -OH (hydroxyl) 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.
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 Recall (Week 1): Alcohols - Nomenclature
• IUPAC names
• The parent chain is the longest chain that contains the
-OH group.
• Number the parent chain in the direction that gives
the -OH group the lower number.
• Change the suffix -e to -ol.

• Common names
• Name the alkyl group bonded to oxygen followed by
the word alcohol.

Examples: Naming Alcohols

OH
OH
OH
OH
OH
OH
OH
OH
OH OHOH
OHOH OH
OHOH
OH
OH
OH
OHOH
Ethanol
Ethanol 1-Propanol
1-Propanol 2-Propanol
2-Propanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol 1-Propanol
1-Propanol
1-Propanol
1-Propanol
1-Propanol 2-Propanol
2-Propanol
2-Propanol
2-Propanol
2-Propanol
(Ethyl
(Ethylalcohol)
alcohol) (Propyl
(Propyl alcohol)
alcohol) (Isopropyl
(Isopropyl alcohol)
alcohol)
(Ethyl
(Ethyl
(Ethyl
(Ethyl
(Ethylalcohol)
alcohol)
alcohol)
alcohol)
alcohol) (Propyl
(Propyl
(Propyl
(Propyl
(Propyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol) (Isopropyl
(Isopropyl
(Isopropyl
(Isopropyl
(Isopropyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol)
OH
OH
OH
OH
OH
OH
OH
OH
OH OH
OH
OH
OH
OH
OH
OH OH
OHOH
OH
OH
1-Butanol
1-Butanol 2-Butanol
2-Butanol 2-Methyl-1-propanol
2-Methyl-1-propanol
1-Butanol
1-Butanol
1-Butanol
1-Butanol
1-Butanol 2-Butanol
2-Butanol 2-Methyl-1-propanol
2-Methyl-1-propanol
(Butyl
(Butyl alcohol)
alcohol) (sec-Butyl
2-Butanol
2-Butanol
2-Butanol
(sec-Butyl alcohol) 2-Methyl-1-propanol
alcohol) 2-Methyl-1-propanol
2-Methyl-1-propanol
(Isobutylalcohol)
(Isobutyl alcohol)
(Butyl
(Butyl
(Butyl
(Butyl
(Butyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol) (sec-Butyl
(sec-Butyl alcohol)
alcohol)
(sec-Butyl
(sec-Butyl
(sec-Butyl
alcohol)
alcohol) (Isobutyl
alcohol) (Isobutyl
(Isobutyl
(Isobutyl
(Isobutylalcohol)
alcohol)
alcohol)
alcohol)
alcohol)

OH
OH OH
OH
OH
OH
OH
OH
OH OH
OH
OH
OH
OH
2-Methyl-2-propanol
2-Methyl-2-propanol Cyclohexanol
Cyclohexanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol Cyclohexanol
Cyclohexanol
Cyclohexanol
Cyclohexanol
Cyclohexanol
(tert-Butyl
(tert-Butylalcohol) (Cyclohexyl
(Cyclohexyl
alcohol) (Cyclohexyl alcohol)
alcohol) 8
(tert-Butyl
(tert-Butyl
(tert-Butylalcohol)
(tert-Butyl
(tert-Butyl alcohol)
alcohol) (Cyclohexyl
alcohol)
alcohol) (Cyclohexylalcohol)
(Cyclohexyl
(Cyclohexylalcohol)
alcohol)
alcohol)
alcohol)
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 Alcohols - Nomenclature
• Write the name of each alcohol
(a) CH3 (CH 2 )6 CH2 OH

OH
(b)

OH
(c)

Recall (Week 1): Alcohols - Nomenclature

• Compounds containing
• two -OH groups are named as diols.
• three -OH groups are named as triols.
• Compounds containing -OH groups on different carbons
are often called glycols.

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 Recall (Week 1): Alcohols - Nomenclature
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

6 4 2
5 3 1 OH
trans-3-hexene-1-ol
(E)-3-hexene-1-ol
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Physical Properties
• Alcohols are polar compounds
• Both the C-O and O-H bonds are polar covalent
• Partial positive charge on C and H and a partial negative
charge on O
• Alcohols associate in liquid state by hydrogen bonding

H
d+ d-
C O
H d+
H H

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 Hydrogen Bonding (review)
• Alcohols associate in the liquid state by hydrogen bonding
• 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
alcohols is approximately 2 to 5
kcal/mol
• hydrogen bonds are considerably
weaker than covalent bonds (for
example, 110 kcal/mol for an O-H
bond)
• nonetheless, hydrogen bonding can
have a significant effect on physical
properties

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Boiling Points
Alcohols have higher boiling points and are more soluble in water
than hydrocarbons

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 Solubility of alcohols in water
• The small alcohols are completely
soluble in water.
• In both pure water and pure ethanol the
main intermolecular attractions are
hydrogen bonds.
• In addition, there is an increase in the
disorder of the system - an increase in
entropy.
• Solubility falls as the hydrocarbon chain
in the alcohol increases.
• The -OH end of the alcohol molecules can
form new hydrogen bonds with water
molecules, but the hydrocarbon "tail"
doesn't form hydrogen bonds.
• The attractions are much weaker. Even
allowing for the increase in disorder, the
process becomes less feasible 15

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ALCOHOLS, ETHERS &

THIOLS
REACTIONS OF ALCOHOLS

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 Acidity of Alcohols
• Most alcohols are about the same or slightly weaker
acids than water

• Aqueous solutions of alcohols have the same pH as that of

pure water
• You can treat small alcohols as water in many cases.
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Acidity of Alcohols
• pKa values for several low-molecular-weight alcohols

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 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

• Thus, alcohols can function as both weak acids and weak

bases, similar to water.

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Reaction with Active Metals

• Alcohols react with Li, Na, K, and other active
metals to liberate hydrogen gas and form metal
alkoxides (alkoxide functional group: RO-)
• Na is oxidized to Na+ and H+ is reduced to H2

• alkoxides are somewhat stronger bases than OH-

• alkoxides can be used as nucleophiles in nucleophilic
substitution reactions
• they can also be used as bases in b-elimination
reactions
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 Example (Review)

• Which are secondary alcohols?

CH3 H OH
CH3 H3C H
H3C C OH C C
OH H CHCH3
CH3
OH
I II III IV

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Recall (last week): Formation of

haloalkanes (alkyl halides)
Most common preparation method is from reacting an
alcohol with a strong acid (hydrogen halide, HX); Chapter 8

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 Recall (Week 1): Acid and Base Strength
• Strong acid: One that reacts completely or almost
completely with water to form H3O+ ions.
• Strong base: One that reacts completely or almost
completely with water to form OH– ions.
• Here are the six most common strong acids and the
four most common strong bases.

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Conversion of ROH to RX
• Water-soluble 3° alcohols react very rapidly with
HCl, HBr, and HI.

• Low-molecular-weight 1° and 2° alcohols are

unreactive under these conditions.
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 Conversion of ROH to RX
• Water-insoluble 3° alcohols react by bubbling gaseous
HCl through a solution of the alcohol dissolved in
diethyl ether or THF.

• 1° and 2° alcohols require concentrated HBr and HI to

form alkyl bromides and iodides.

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Reaction of a 3° ROH with HX

• 3° Alcohols react with HX by an SN1 mechanism

• Step 1: Add a proton. Rapid and reversible proton from the acid to the —
OH group.

• This proton-transfer converts the leaving group from OH–, a poor leaving
group, to H2O, a better leaving group.
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 Reaction of a 3° ROH with HX
• Step 2: Break a bond to form a stable molecule or ion.
Loss of H2O gives a 3° carbocation.

• Step 3: Reaction of an electrophile and a nucleophile to

form a new covalent bond completes the reaction.

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Reaction of a 1° ROH with HX

• 1° alcohols react with HX by an SN2 mechanism.
• Step 1: Add a proton. Proton transfer to OH converts OH–, a
poor leaving group, to H2O a better leaving group.

• Step 2: Reaction of a nucleophile and an electrophile to

form a new covalent bond and break a bond.

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 Reaction of ROH with HX
• Reactions are governed by a combination of
electronic and steric effects

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Acid-catalyzed dehydration of alcohols

• An alcohol can be converted to an alkene by

dehydration, the 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

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 Dehydration of Alcohols

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Dehydration of Alcohols
• When isomeric alkenes are obtained, the more
stable alkene (the one with the greater number of
substituents on the double bond) generally
predominates (Zaitsev’s rule).

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 Dehydration of 3° Alcohols
• Alcohols undergo dehydration - the elimination of H2O, to give alkenes.
• One of the common methods for secondary and tertiary alcohols is
treatment with a strong acid.
• Acid-catalyzed dehydrations usually follow Zaitsev’s rule and yield the
more highly substituted alkene as major products.
• It is an E1 reaction

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Dehydration of a 2° Alcohol

• A three-step mechanism
• Step 1: Add a proton. Proton transfer from H3O+ to the –OH
group converts OH–, a poor leaving group, into H2O, a better
leaving group.

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 Dehydration of a 2° Alcohol
• Step 2: Break a bond to form a stable molecule or ion. Loss
of H2O gives a carbocation intermediate.

• Step 3: Take a proton away. Proton transfer from an

adjacent carbon to H2O gives the alkene and regenerates
the acid catalyst.

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Dehydration of a 1° Alcohol
• A two-step mechanism
• Step 1: Add a proton. Proton transfer from the acid gives
an oxonium ion.

• Step 2: Take a proton away and loss of H2O gives the

alkene and regenerates the acid catalyst.

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 Recall: Addition of H2O to an Alkene
(Hydration)
• Acid-catalyzed hydration of an alkene is regioselective:
hydrogen adds preferentially to the less substituted
carbon of the double bond. Thus H–OH adds to alkenes
in accordance with Markovnikov's rule.

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Hydration-Dehydration
• Acid-catalyzed hydration of an alkene and
dehydration of an alcohol are competing processes.

• Large amounts of water favor alcohol formation.

• Scarcity of water or experimental conditions where
water is removed favor alkene formation.

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 Oxidation of Alcohols
• One of the most valuable reaction of alcohols is their oxidation to
yield carbonyl compounds: CH-OH à C=O
• Primary alcohols yield aldehydes or carboxylic acids (Ch 13/14)
• Secondary alcohols yield ketones
• Tertiary alcohols don’t normally react with oxidizing agents

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Oxidation of Alcohols
• Oxidation of a 1° alcohol gives an aldehyde or a
carboxylic acid, depending on the oxidizing agent
and experimental conditions. Oxidation of a 2°
alcohol gives a ketone.
• The most common oxidizing agent is chromic acid.

• Chromic acid oxidation of 1-octanol gives octanoic acid.

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 Oxidation of Alcohols
• To oxidize a 1° alcohol to an aldehyde, use PCC.

• PCC oxidation of geraniol gives geranial.

• Tertiary alcohols are not oxidized by either of these reagents;

they are resistant to oxidation.
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Example

H2CrO4

OH acetone
H2O

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 Diols
• Diols are named systematically as poly-alcohols
• e.g. HOCH2CH2OH = 1,2-ethanediol, so the same nomenclature rules as for
alcohols apply.
• 1,2-diols are often referred to as vicinal diols.
Functional group suffix = -diol
Functional group prefix = dihydroxy-
Physical Properties:
• The polar nature of the O-H bond, suggest that diols are:
• high melting and boiling points compared to analogous alkanes
• high solubility in aqueous media
Structure:
• Basically the same as for alcohols
• Each alcohol functional group consists of an O atom bonded to a C atom
and a H atom via s bonds.
• Both the C-O and the O-H bonds are polar due to the high electronegativity
of the O atom.
Reactivity:
• In general the chemistry of diols is much the same as that of alcohols. 43

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ALCOHOLS, ETHERS &

THIOLS
PRODUCTION OF ALCOHOLS

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 Production of Alcohols
• Alcohols can be prepared by adding water to an alkene in the presence
of a strong acid such as concentrated sulfuric acid (Ch 5). This reaction
involves adding an H2O molecule across a C=C double bond. Because
these reactions follow Markovnikov’s rule, the product of the reaction is
often a highly substituted 2° or 3° alcohol.

• Less substituted 1° alcohols can be prepared by substitution reactions

(Ch 7) that occur when a primary alkyl halide is allowed to react with
the OH- ion.
CH3CH2CH2Br + OH- à CH3CH2CH2OH + Br -
• Other methods include
• Reduction of aldehydes and ketones
• Reduction of esters
• Reduction of carboxylic acids etc… 45

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Production of ethanol
• Ethanol is manufactured by reacting ethene with steam. The catalyst
used is solid silicon dioxide coated with phosphoric(V) acid. The
reaction is reversible.

• Only 5% of the ethene is converted into ethanol at each pass through

the reactor. By removing the ethanol from the equilibrium mixture
and recycling the ethene, it is possible to achieve an overall 95%
conversion.

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 ALCOHOLS, ETHERS &
THIOLS
ETHERS

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Ethers - Structure
• The functional group of an ether is an oxygen atom
bonded to two carbon atoms (R-O-R’)
• 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

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 Ethers - Nomenclature
• IUPAC
• The longest carbon chain is the parent alkane.
• Name the -OR group as an alkoxy (alkyl + oxygen) substituent.
• Common names:
• Name the groups bonded to oxygen followed by the word
ether.

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Ethers - Nomenclature
• Although cyclic ethers have IUPAC names, their
common names are more widely used.

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 Ethers - Physical Properties
• Ethers are polar molecules.
• Each C-O bond is polar covalent.
• However, only weak attractive forces exist between ether
molecules in the pure liquid.

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Ethers - Physical Properties

• The effect of hydrogen bonding is illustrated by
comparing the boiling points of ethanol and dimethyl
ether

CH 3CH2OH CH3OCH3
Ethanol Dimethyl ether
bp 78°C bp -24°C

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 Ethers - Physical Properties
Boiling points are lower than those of alcohols

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Ethers - Physical Properties

Ethers are hydrogen bond acceptors only. They are not
hydrogen bond donors.

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 Recall: Functional Isomers
• They have the same molecular formula but differ in the nature
of the functional group.
• e.g: Dimethyl Ether: (CH3)2O and Ethanol: C2H5OH.
• Even though the atoms are the same, they are arranged differently. This
yields two different compounds with the same number of atoms. These
compounds have different functional groups. They are functional
isomers (belong to constitutional isomers).
• The first is a gas which will knock you out if inhaled. The other is
common alcohol drunk in spirits. The two molecules are shown below.

Dimethyl Ether Ethanol

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Alcohols versus Ethers

• There are important differences between both the physical and
chemical properties of alcohols and ethers. Consider diethyl ether
and 1-butanol, for example, which are constitutional isomers with
the formula C4H10O.

CH3CH2OCH2CH3 CH3CH2CH2CH2OH
BP = 34.5 C BP = 117.2 C
d = 0.7138 g/mL d = 0.8098 g/mL

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 Reactions of Ethers
• Ethers 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
• But, epoxides (cyclic ether in which O is one atom
of a 3-membered ring) reacts readily because of
angle strain
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Preparation of Ethers
• Ethers are easily prepared from alcohols by
conversion to the alkoxide ion by SN2 reaction.
• The substrate is a primary alkyl halide (Ch 7)

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 ALCOHOLS, ETHERS &
THIOLS
THIOLS

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Thiols - Structure
• The functional group of a thiol is an -SH (sulfhydryl)
group bonded to an sp3 hybridized carbon

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 Thiols - Nomenclature
• The parent chain is the longest chain containing the -SH
group.
• Add -thiol to the name of the parent chain.
• Common names
• Name the alkyl group bonded to sulfur followed by the word
mercaptan.
• Alternatively, indicate the -SH by the prefix mercapto.

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Thiols - Physical Properties

• Low-molecular-weight thiols have a STENCH

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 Thiols - Physical Properties
• The difference in electronegativity between S and
H is 2.5 – 2.1 = 0.4 (nonpolar covalent bond)
• Because of their low polarity, thiols
• show little association by hydrogen bonding.
• have lower boiling points and are less soluble in water
than alcohols of comparable MW.

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Example
• Arrange the compounds in the order of increasing boiling
point (lowest first).

O
H3C CH3 H2O CH3CH2OH CH3CH2SH
I II III IV

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 ALCOHOLS, ETHERS &
THIOLS
REACTIONS OF THIOLS

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Acidity of Thiols
• Thiols are stronger acids than alcohols.

• Thiols react with strong bases to form salts.

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 Oxidation of Thiols
• Thiols are oxidized by a variety of oxidizing agents,
including O2, to disulfides.
• Disulfides, in turn, are easily reduced to thiols by
several reagents.

• This easy interconversion between thiols and disulfides

is very important in protein chemistry.

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Example
• Arrange the compounds in the order of increasing
acidity (least first).

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