Alkyl

Halides
Chem 2/L – Organic Chemistry Learning
Outcomes:
■ Draw structure of alkyl halides and its derivatives given
IUPAC/ common name & vice-versa.
■ Write chemical equations for the reactions of alkyl halides
■ Describe sources and properties of alkyl
[Link]
Alkyl halides (Organohalides)
§ Also known as haloalkanes
§ Compounds in which one or more hydrogen atoms in an
alkane have been replaced by halogen atoms
§ Fluorine
§ Chlorine
§ Bromine
§ IodineHaloalkanes ( Organohalides )
Organohalides are compounds that contain one or more
halogen atoms.
Halogen-substituted organic compounds are widespread in
nature, and more than 5000 organohalides have been found
in algae and various other marine organisms.
Chloromethane
C
Seaweeds produce an
array of both simple and
complex organohalogens,
presumably for chemical
defense

Ocean Kelp Organohalides

Halogen-containing compounds also have a vast array of
industrial applications, including their use as solvents,
inhaled
anesthetics, refrigerants, and pesticides.
Fire Extinguisher Inhaled Anesthetics RefrigerantsTetrachloromethane
2-bromo-2-chloro-1,1,1-trifluoroethane
(halothane)
dichlorodifluoromethane
Chlorofluorocarbon
Dichlorodiphenyltrichloroethane

(DDT) Haloalkanes (Organohalides)

Primary (1º) haloalkane
§ The carbon bonded to the halogen atom is only attached to one
other alkyl group.
Secondary (2º) haloalkane
§ The carbon bonded with the halogen atom is joined directly to
two other alkyl groups that can be the same or

different Haloalkanes (Organohalides)

Tertiary (3º) haloalkane
§ The carbon atom holding the halogen is attached directly to
three alkyl groups, which may be any combination of same or

different. Naming Alkyl Halides

Step 1: Find the longest chain, and name it as the parent.
Step 2: Number the carbons of the parent chain beginning at
the end
nearer the first substituent, whether alkyl or halo.
§ If there are substituents the same distance from both
ends, begin numbering at the end nearer the
substituent with alphabetical priority.
Step 3: Write the name.
§ List all substituents in alphabetical order, and use one of
the prefixes di-
, tri-, and so forth if more than one of the

same substituent is present. Naming Alkyl

Halides
Step 3: Write the name.
§ List all substituents in alphabetical order, and use one of
the prefixes di-
, tri-, and so forth if more than one of the
same substituent is present.
2 di- 6 hexa-
3 tri- 7 hepta-
4 tetra- 8 octa-

5 penta- Naming Alkyl Halides

4-bromo-2-chloro-5-cyclopropyl-6-methylhexane
1-bromo-3-chloro-2-flouro-4-iodocyclobutane
2-bromo-6-chloro-4-flourohepta-2,5-diene

2-bromo-1-t-butyl-3,5-chloro-4-ethylcyclohexane Naming Alkyl

Halides
3,3-dibromo-4-iodohexane
2-bromo-7-chloro-4,4,6,6-tetramethyloctane
bromocyclopentane 4-cyclopropyl-5-flouro-2-iodoheptane Naming
Alkyl Halides
2-chloropropane
4-bromo-3,6-dichloro-5-methyloctane
1-chloropropane

1-chloroethane Naming Alkyl Halides

3,5-dibromo-4-chloroheptane
2,3-diiodo-4,5-dimethylhexane
1-bromo-3,4-dichloro-2-propylcyclopentene

4-bromo-2-chloro-6-iodohept-2-ene Naming Alkyl

Halides
2-bromobutane 3-chloro-2-methylpentane 1-chloro-4-methylbutane
1,3-dichloro-3-methylbutane 1-bromo-4-chlorobutane 1-chloro-4-

bromopentane Naming Alkyl Halides

2-Chloro-3,3-dimethylhexane 3,3-Dichloro-2-methylhexane
3-Bromo-3-ethylpentane 2-Bromo-5-chloro-3-
methylhexane Naming Alkyl Halides
3,5-dibromo-4-isopropylheptane
3,5-dibromo-3-ethyl-4,4-dimethylheptane
1-bromo-2-chloroethane

1-chlorobutane Naming Alkyl Halides

1,3-difluoro-2,4-dimethylcyclobutane
2-t-butyl-6-chloro-3,5-diflouroheptane

1,1-dichloro-1,1-diflouromethane tetrachloromethane Naming

Alkyl Halides
2,3-dichloro-2,3-difluoro-4-methylpentane
1,4-dibromo-2-chloro-5-isopropylcyclohexane
4-bromo-1,3-dichloro-5-iodohex-1-yne
4-chloro-3-methylhex-2-ene Naming Alkyl Halides
2,4,6-tribromo-5-sec-butyl-8-chloro-3-fluorononane
2-bromo-3-t-butyl-4-chloro-6-fluoro-7,8-dimethylnonane
1-bromo-2-fluoroethane

Physical Properties of
1,2-dibromo-3-chloropropane

Alkyl Halides
§ All alkyl halides are insoluble in water and soluble in
common
organic solvents
§ The boiling point increases in the order F < Cl < Br < I.
§ Boiling point also increases for straight-chain isomers.
Ex.
<<
§ More branching lowers the boiling point of alkyl
Physical Properties of Alkyl
halides

HalidesBoiling point of Alkyl

Halides
>Boiling point of Alkyl Halides
<Boiling point of Alkyl Halides
<Preparation of Alkyl Halides
1. Free-radical substitution of alkanes
Δ (Light)

2. Electrophilic addition of HX or X2 to

alkanes Reactions of Alkyl Halides

Formation of Grignard Reagents
.

§ Discovered by Victor Grignard

§ Grignard reagent is an organometallic compound which can be
described by the chemical formula 'R-Mg-X’
§ where R refers to an alkyl or aryl group and X refers to a
halogen.
§ They are generally produced by reacting an aryl halide or an
alkyl halide with magnesium and ether as the solvent.
§ The halogen can be Cl, Br, or I, but not F.SN2
Reaction
Substitution, Nucleophilic, bimolecular
Bimolecular means that the two molecules,
nucleophile
and alkyl halide take part in the step
§ Methyl Halides, Primary and secondary Haloalkane
are
reactive substrates in this reaction.
§ Tertiary Haloalkane, Vinylic Halides and aryl halides are
S 2 Reaction
unreactive toward SN2 reaction. N
§ An SN2 reaction takes place in a single step without
intermediates when the entering nucleophile approaches the
substrate from a direction 180° away from the leaving group.
§ As the nucleophile comes in on one side of the molecule, an
electron pair on the nucleophile Nu:- forces out the
leaving
group X:- , which departs from the other side of the molecule
and takes with it the electron pair from the C-X bond.
§ In the transition state for the reaction, the new Nu-C bond is
partially forming at the same time the old C-X bond is partially
breaking, and the negative charge is shared by both the
incoming nucleophile and the outgoing leaving group. S N2
Reaction
Mechanism:
1
§ The nucleophile –OH uses
its lone-pair electrons to
attack the alkyl halide
carbon 180° away from the
departing halogen.
§ This leads to a transition
state with a partially formed
C–OH bond and a partially
broken C–Br bond. NS 2 Reaction
Mechanism:
2
§ The stereochemistry at
carbon is inverted as the
C–OH bond forms fully
§ The bromide ion departs
with the electron pair from
the former C–Br bond. SN2 ReactionSN1
Reaction
Substitution, Nucleophilic, Unimolecular
§ Most nucleophilic substitutions take place by the SN2 pathway,
but an alternative called the SN1 reaction can also occur.
§ In general, SN1 reactions take place only on tertiary
substrates and only under neutral or acidic
conditions in a
hydroxylic solvent such as water or alcohol.
Tertiary (3º) Haloalkane SN1 Reaction
§ Unlike what occurs in an SN2 reaction, where the leaving group
is displaced at the same time that the incoming nucleophile
approaches, an SN1 reaction occurs by spontaneous loss
of
the leaving group before the incoming nucleophile
approaches.
§ Loss of the leaving group gives a carbocation
intermediate,
which then reacts with the nucleophile in a second step to yield
the substitution product. N S 1 Reaction
Mechanism:
1
§ The –OH group is first
protonated by HBr.
2
§ Spontaneous dissociation of
the protonated alcohol
occurs in a slow, rate-
limiting step to yield a
carbocation intermediate
plus water. NS 1 Reaction
Mechanism:
3
§ The carbocation intermediate
reacts with bromide ion in a
fast step to yield the neutral
substitution product. E2 Reaction (Elimination,
bimolecular)
§ C–H and C–X bonds break simultaneously, giving the
alkene
in a single step without intermediates.
Mechanism
1
§ Base (B:) attacks a neighboring
hydrogen and begins to remove
the H at the same time as the
alkene double bond starts to form
and the X group starts to leave. E2 Reaction
Mechanism
2
§ Neutral alkene is produced when
the C–H bond is fully broken, and
the X group has departed with the
C–X bond electron pair. E1 Reaction (Elimination,
unimolecular)
§ C–X bond breaks first to give a carbocation
intermediate,
followed by base removal of a proton to yield the alkene.
Mechanism
1
§ Spontaneous dissociation of the
tertiary alkyl chloride yields an
intermediate carbocation in a slow,
E1 Reaction
rate-limiting step.
Mechanism
2
§ Loss of a neighboring H+ in a fast
step yields the neutral alkene
product.
§ The electron pair from the C–H
bond goes to form the alkene =
bond. Zaitsev’s Rule
§ Formulated by Russian Chemist, Alexander Zaitsev
§ Elimination reactions generally give the more stable alkene
product.
§ More stable alkenes are those with more alkyl
substituents on the
double-bond carbon.
CH3– CH2– CH – CH3
CH3CH2O– Na+
CH3CH2OH
CH3– CH = CH – CH3
CH3– CH2– CH = CH2

ClSummary of Reaction
SN2 SN1 E1 E2
1o 2o 3o 3o 1o 2o
Strong
Nucleophilic
Weak
Nucleophile &
Base
(I, Br, SCN, N3)
Weak
Nucleophile &
Base
(I, Br, SCN, N3)
Strong Bases
(HO, RO)

Heat (Δ) References

Textbooks:
• McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-
3098 USA. pp 222-245
• Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-
3098 USA. References
Online:
• [Link]
• [Link]
• [Link]
•
c_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Alkyl_Halide
s

Alcohol, Phenol,
& Ethers
Chem 2/L – Organic Chemistry Learning
Outcomes:
■ Draw structures of alcohols, phenols, ethers and their
derivatives given IUPAC/ Common name & vice-versa.
■ Write chemical equations for the reactions of alcohols,
phenols and ethers.
■ Describe sources and properties of alcohols, phenol and
ethers. Overview
Alcohol and Phenols can be thought of as organic
derivatives of water in which one of the water hydrogens is
replaced by an organic group.
R

Water Alcohol Phenol Overview

Alcohol is not only found in sugarcane, barley, corn,
wheat, and potatoes but the same is also found in natural
substances like petroleum and oils.
Ethanol was one of the first organic chemical to be
prepared and purified.
■ Used to make automobile fuel, a blend of 85% ethanol
and 15% gasoline. Overview
Phenol is a common component of oil refinery wastes.
■ It may enter the environment from oil refinery discharges,
coal conversion plants, municipal waste treatment plant
discharges, or spills. Alcohol
Structure
■ Alcohols have the general formula: R-OH, where “R” involves a
saturated C-atom.
Primary alcohol (1°)
■ Has only (1) R bonded to the hydroxyl-bearing C.

Propanol Butanol Alcohol

The secondary alcohol (2°) has two (R),
Pentan-2-ol Butan-2-ol
The tertiary alcohol (3°) has three (R).

2-methylbutan-2-ol 3-Ethylpentan-3-ol Naming

■ Simple alcohols are named in the IUPAC system as
derivatives of the parent alkane, using the suffix -ol.
■ The locant indicating the position of the hydroxyl group in
the parent chain is placed immediately before the -ol suffix.
■ The -e is deleted to prevent the occurrence of two
adjacent
vowels: propanol rather than propaneol, for example.
Methane → Methanol
Butane → Butanol
Heptane → Heptanol
Ethane → Ethanol
Pentane → Pentanol
Octane → Octanol
Propane → Propanol
Hexane → Hexanol

Nonane → Nonanol Naming

Step 1
group.
■ Select the longest carbon chain containing the hydroxyl
Step 2
■ Number the carbons of the parent chain beginning at the
end nearer the hydroxyl group.
■ Number all substituents adding to their position on the
chain. Naming
Step 3:
■ Write the name listing the substituents in alphabetical order
and identifying the position to which the OH is bonded.
■ The name for the corresponding alkane chain loses the “e” and
picks up “ol”.
■ For cyclic alcohols, the OH group is understood to be attached
to C-1.
■ Note that in naming cyclohexane-1,4-diol, the final -e of
cyclohexane is not deleted because the next letter (d) is not a
vowel; that is, cyclohexanediol rather than

cyclohexandiol. Naming
Step 3:
■ Polyhydroxyl alcohols possess more than one OH group.
Multipliers when naming with multiple OH group attached:
2→ diol
3→ triol
4→ tetrol
5→ pentol
6→ hexol
7 → heptol

Ethane-1,2-diol Propane-1,2,3-triol Hexane-2,3,4,5-tetrol Naming

Most simple alcohols are named by their common name.
■ Name the C-atoms of a single alkyl group as for alkanes.
■ Add the word “alcohol” following a space after the alkyl
name. Naming
Most simple alcohols are named by their common name.
■ Name the C-atoms of a single alkyl group as for alkanes.
■ Add the word “alcohol” following a space after the alkyl
name. Naming
4
OH
1 2 3 4 5.
CH3CCH2CH2CH3
1
2
1
2
3
3
CH3
4
2-methylpentan-2-ol
Cyclohexane-1,4-diol

3-phenylbutan-2-ol Naming
Pentan-1-ol 3-ethyl-4,4-dimethylhexan-2-
ol
Hexane-2,4-diol

Butan-2-ol 5-bromohexan-2-ol 3-methylcyclopentan-1-ol Naming

Ethan-1-ol 3,5-dimethylheptane-2,4-diol Methanol

Pentan-3-ol Propan-1-ol 4-ethylhexane-2,3,5-triol Properties

■ Alcohols consist of a non-polar (alkane-like) chain and a
polar hydroxyl group.
■ Alcohols might be water-soluble, or not (depending on the
length of the carbon chain).
■ As the length of the chain increases, however, the
solubility of alcohols in water decreases; the molecules
become more like hydrocarbons and less like
water. Properties
■ The same with alkanes, alcohol also increase its boiling
points with increasing chain length
■ It is due to stronger intermolecular forces holding
molecules together.
■ Alcohols with more than one hydroxyl group (polyhydroxy
alcohols) have higher boiling points than monohydroxy
alcohols because of more Hydrogen bonds that are
stronger than London Forces. Properties
Compound Ethane Methanol Ethanol Ethane-1,2-diol Boiling Point -
89oC 65oC 78oC 197oC IMF
London
London, H-bonding
London, H-bonding

London, more H-bonding Phenol

■ The word phenol is used both as the name of a specific
substance (hydroxybenzene) and as the family name for
all hydroxy-substituted aromatic compounds.
■ Substituted phenols are named for aromatic compounds
with the suffix -phenol used as the parent name rather
than –benzene.
■ Benzenes that are substituted with both OH and CH3
groups are called cresols.
m-Methylphenol
(m-cresol) Naming
ortho-cresol meta-cresol para-cresol
For dihydroxy-benzene structures:
Catechol Resorcinol

Hydroquinone Naming
4-methylcatechol 2-t-butyl-5-chlorophenol 5-ethyl-2-methylphenol

2,3,6-trimethylphenol 4,5-dimethylgallol 3-ethylcatechol Naming

3,5-dibromocatechol 4-ethyl-5,6-dimethylresorcinol 4-isopropylcatechol

4-ethyl-5-methylcatechol m-cresol m-sec-butylphenol Ether

R-O-R
■ Like alcohol, ether are also derivatives of water but have
two organic groups bonded to the same oxygen atom
rather one.
■ Diethyl ether is a component of starting fluids and is used
as a solvent in the manufacture of synthetic dyes and
plastics. Naming
■ Simple ethers that contain no other functional groups are
named by identifying the two organic groups ( alkyl groups)
arranged in alphabetical order and adding the word
ether. Naming
■ If other functional groups are present, the ether part is
named as an alkoxy substituent.
■ One of the alkoxy (alkyl with oxygen) groups is handled as
a
substituent attached to a parent chain, with the longest
carbon chain selected as the parent chain.
■ Alkyl substituents have a -oxy ending in place of the -yl.
Methyl → Methoxy Ethane → Ethoxy Propyl → Propoxy
Butyl → Butoxy
Pentyl → Pentoxy
Hexyl → Hexoxy NamingNaming
2-methoxypentane 1-ethoxy-3-methylpent-1-ene 1-t-butoxycyclohexane

2-t-butoxypentane 1-ethoxyethane 1-ethoxypropane Ether

R-O-R
■ The electronegative oxygen atom gives ethers a slight
dipole moment.
■ Boiling point of ethers are often slightly higher the boiling
points of alkanes. Ether
Ether Boiling Point oC CH3OCH3– 25 CH3CH2OCH2CH3 34.6 65 158
Hydrocarbon Boiling Point oC
CH3CH2CH3– 45
CH3CH2CH2CH2CH3 36
49

136Reactions of Alcohols
Combustion
§ In combustion reactions involving alcohols, CO2 and H2O
are produced.
Examples:
2CH3OH + 3O2 → 2CO2 + 4 H2O
CH3CH2OH + 3 O2 → 2 CO2 + 3 H2O Reactions of
Alcohols
Dehydration
§ Alcohols undergo dehydration—the elimination of H2O—
to give alkenes.
§ A method that works particularly well for secondary and
tertiary alcohols is treatment with a strong acid.
Examples: Reactions of Alcohols
Dehydration
§ In general, these kinds of reactions (eliminations) proceed as
follows:
§ If there is more than one adjacent carbon atom from which
loss of a H-atom can occur, there will be more than one

possible alkene dehydration products. Reactions of

Alcohols
Oxidation
§ The most valuable reaction of alcohols is their oxidation
to yield carbonyl compounds.
§ Primary alcohols yield aldehydes or carboxylic acids.
Note: [O] = K2Cr2O7 Carboxylic Acid

= I2/NaOH Aldehyde Reactions of Alcohols

Oxidation
§ Secondary alcohols yield ketones.
Note: [O] = K2Cr2O7
§ Tertiary alcohols don’t normally react with oxidizing
agents. Reactions of Phenols
Electrophilic Aromatic Substitution Reactions
§ The hydroxyl group is a strongly activating, ortho- and
para- directing substituents in electrophilic aromatic
substitution reactions.
§ As a result, phenols are highly reactive substrates for
electrophilic halogenation, nitration, sulfonation, and
Friedel-crafts [Link] Aromatic Substitution
Reactions
X
Halogenation
Acylation
NO2
R
SO3H
Nitration
Alkylation
Sulfonation
O
C
RElectrophilic Aromatic Substitution Reactions
Halogenation
FeBr3+ Br2 +Electrophilic Aromatic Substitution Reactions
Nitration
NO2
HNO3
.

H2O
+
Electrophilic Aromatic Substitution Reactions
NO2

Sulfonation
SO3H
H2SO4
+ SO3 +
SO HElectrophilic Aromatic Substitution Reactions
3

Friedel-Crafts Alkylation
AlCl3+ +Electrophilic Aromatic Substitution Reactions
Friedel-Crafts Acylation
AlCl3+ +Oxidation of Phenols: Quinones
§ Phenols don’t undergo oxidation in the same way that
alcohols do because they don’t have a hydrogen atom
on the hydroxyl-bearing carbon.
§ Instead, reaction of a phenol with a strong oxidizing
agent yields a quinone.
§ Fremy’s Salt [potassium nitrosodisulfonate, (KSO3)2NO]
is used as oxidant in this [Link] of
Phenols: Quinones
(KSO3)2NO
.

H2OOxidation of Phenols: Quinones

§ Quinones are valuable class of compounds because of
their oxidation – reduction, redox, properties.
They can be easily reduced to hydroquinone by
reagents such as NaBH4 and SnCl2.
(KSO3)2NO
Hydroquinone can be easily re-oxidized back to
quinone by Fremy’s [Link] of Phenols:
Quinones
§ The redox properties of quinones are crucial to the
functioning of living cells, where compounds called
ubiquinone act as biochemical oxidizing agents to
mediate the electron-transfer process involved in
energy production.
§ Ubiquinone, also called coenzymes Q are components
of the cells of all aerobic organisms, from the simplest
bacterium to [Link] of Ethers: Acidic
Cleavage
§ Ethers are unreactive to many reagents used in organic
chemistry, a property that accounts for their wide use as
reaction solvents.
§ Halogens, dilute acids, bases, and nucleophiles have no
effect on most ethers.
§ In fact, ethers undergo only one truly general reaction—
they are cleaved by strong acids.
§ Aqueous HBr and HI both work well, but HCl does not
cleave [Link] of Ethers: Acidic
Cleavage
HBr2
.

H2O + CH3CH2BrReference
Textbooks:
1. McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic Chemistry.
Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA. pp 256-285
2. Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological Chemistry.
Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA.
Online:
1. [Link]
2. [Link]
3. [Link]
4. [Link]
5. [Link]

Chapter
7
Chem 2/L – Organic Chemistry

Prepared by: Jaizel R. Pa-oner Overview

Carbonyl compounds are characterized by an
oxygen double
bonded with alkyl group.
Can be found everywhere. Despite their relatively
low
abundance, they may also cause harmful effects
on the marine
environment.
C

Carbonyl group Aldehydes

&
Ketones
Chem 2/L – Organic Chemistry

Prepared by: Jaizel R. Pa-oner Learning

Outcomes:
■ Draw structures of aldehydes and ketones given
IUPAC/
Common name & vice-versa.
■ Write chemical equations for the reactions of
aldehydes and
ketones
■ Describe sources and properties of aldehydes

and ketones. Overview

Aldehydes and ketones are organic compounds
which
incorporate a carbonyl functional group, C=O.
■ The carbon atom of this group has two
remaining bonds that
may be occupied by hydrogen, alkyl or aryl
substituents.
CCC

Carbonyl group Aldehyde Ketone Structure

Aldehydes and ketones are among the first
examples of
compounds that possess a C=O double

bond. Aldehyde
The general formula:
Examples
*
CNaming
■ Aldehydes are named by replacing the terminal -
e of the
corresponding alkane name with -al.
■ The parent chain must contain the -CHO group.
■ Numbering begins at the -CHO carbon, which is

always C1. Naming

■ For more complex aldehydes in which the -CHO
group is
attached to a ring, the suffix -carbaldehyde is
used.
Cyclohexanecarbaldehyde Benzenecarbaldehyde

(Benzaldehyde) Naming
A few simple and well-known aldehydes have
common names

that are recognized by IUPAC. Naming

3-ethylhexan-1-al Ethan-1-al Cyclopentanecarbaldehyde
Hexan-1-al 4-t-butyl-3-methylhexan-1-al 3,4-dimethylpentan-1-

al Naming
5-methylhex-2-en-1-al Pent-3-yn-1-al 3,5-
dimethylcyclohexanecarbaldehyde

5,6-dimethylhept-5-en-1-al Naming
2-ethylbutan-1-al
2-ethyl-3-methylbutan-1-al 5-t-butyl-2,6-dimethylnon-1-al

2-bromo-3-methylcyclobutanecarbaldehyde Naming
Propan-1-al
5-cyclopropane-4-fluoro-3-methylhexan-1-al

5-methyl-2-isopropanehex-4-en-1-al Butan-1-al Ketone

The general formula:
Examples

C Naming
■ Ketones are named by replacing the terminal –e
of the
corresponding alkane name with –one.
However, if the following letter is consonant the
terminal –e
will not be removed.
■ The parent chain is the longest one that contains
the ketone
group, and numbering begins at the end nearer
the carbonyl

carbon. Naming
■ For cyclic ketones, the carbonyl carbon is C-1
and the name
begins with “cyclo”.
Cyclohexanone 3-methylcyclopentan-1-one Naming
Pentan-2-one
Hepta-2,5-dien-4-one
Heptan-3-one

2,6-dibromo-5-t-butyl-7-methyloctan-4-one Naming
5-bromo-2-methylhex-1-en-3-one 6-methylnon-2-al

Pentan-3-al Naming
2-bromocyclobutan-1-one
acetophenone
Cyclehexan-1-one 2-bromo-4-methylcyclobutan-1-

one Learning Check

I. Name the following structures:
1. 2. 4. 5. 7. 6.
8.
[Link] Check
I. Draw the structure of the following IUPAC name:
1. 3- methylbutan-1-al
2. 3-methylbut-3-en-1-al
3. 4-chloropentan-2-one
4. 2-methylhexan-1-al
5. 2,2-dimethylcyclohexanecarbaldehyde
6. Cyclohexane-1,3-dione
7. 2-bromopropan-1-alReference
Textbooks:
1. McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic
Chemistry. Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA. pp 294-316
2. Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological
Chemistry. Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA.
Online:
1. [Link]
2. [Link]
3. [Link]
[Link]://[Link]/Bookshelves/Organic_Chemistry/
Supplemental_Modules_(Org
anic_Chemistry)/Aldehydes_and_Ketones/
Nomenclature_of_Aldehydes_and_Ketone
Online:
[Link]://[Link]/doi/pdf/10.4319/
lo.1995.40.3.0521

Chapter
8
Chem 2/L – Organic

Chemistry Amines
Chem 2/L – Organic Chemistry Learning
Outcomes:
■ Draw structures of amines given IUPAC/ Common name
&
vice-versa.
■ Write chemical equations for the reactions of amines.
■ Describe sources and properties of
amines. Overview
Amines occur widely in all living organisms.
Trimethylamine, for instance, occurs in animal tissues and is
partially responsible for the distinctive odor of
fish; Overview
Amines are any member of a family of nitrogen-
containing organic compounds that are derivatives of
ammonia
in the same way that alcohols and ethers are organic
derivatives of water.
Usually, diamines arise from the decomposition of decaying
tissue.
R.. ..

Ammonia Amine Amine

Amines can be either alkyl-substituted (alkylamines) or
aryl-substituted (arylamines) and can be classed depending
on
the number of organic substituents attached to
Amine
nitrogen.

Primary AmineAmine

Secondary AmineAmine
Tertiary Amine Amine
Quaternary Amine
Compounds containing a nitrogen atom with four attached
groups also exist, but the nitrogen atom must carry a formal
positive charge.
Such compounds are called quaternary ammonium
Naming
salts.
The suffix -amine is added to the name of the alkyl
substituent. NamingNaming
N-methylethylamine
Isopropylamine
N-dimethylethylamine

3-methylpentan-1-amine Naming
pentan-3-amine
Cyclopentylamine
3-methylbutan-1-amine

Trimethylamine Naming
m-aminobenzoic acid 2,4-dimethylaniline
5-amino-4-methylhexan-2-one

1,3-diaminobutan-1-ol Properties
■ Like alcohols, amines with fewer than five carbon atoms
are
generally water-soluble.
■ Primary and Secondary amines form hydrogen bonds, as
a
result amines have higher boiling points than alkanes of
similar molecular weight.
■ One other characteristic of amines is their odor.
– Low-molecular-weight amines such as trimethylamine
have a distinctive fishlike aroma, Synthesis of
Amines
SN2 reaction of alkyl halides
■ Ammonia and other amines are good nucleophiles in SN2
reactions.
■ As a result, the simplest method of alkylamine synthesis
is by SN2 alkylation of ammonia or an alkylamine with an
Synthesis of Amines
alkyl halide.

SN2 reaction of alkyl halidesSynthesis of

Amines
Reduction of azides
■ A better method for preparing primary amines from alkyl
halides is to use azide ion, N3_ , as the nucleophile rather
than ammonia.
■ The product is an alkyl azide, which is not nucleophilic, so
overalkylation can’t occur.
■ Subsequent reduction of the alkyl azide with LiAlH4 then
leads to the desired primary amine. Synthesis of
Amines
Reduction of azidesReductive amination of
aldehydes and ketones
■ Amines can be synthesized from an aldehyde or ketone in
a single step by reaction with ammonia or an amine in the
presence of a reducing agent, a process called reductive
amination.
■ In the laboratory, NaBH4 is often used as the reducing
agent rather than H2 and [Link] of
nitrobenzenes
■ Arylamines are prepared by nitration of an aromatic
starting
material, followed by reduction of the nitro group.
■ Iron, tin, and stannous chloride (SnCl2) in aqueous acid
are
effective in reducing nitrobenzenes. Reaction of
Amines
Alkylation and AcylationReference
Textbooks:
1. McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic Chemistry.
Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA. pp 404-424
2. Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological Chemistry.
Cengage
Learning. 20 Davis Drive Belmont, CA 94002-3098 USA.
Online:
1. [Link]
2. [Link]
PALAWAN STATE UNIVERSITY
College of Sciences
Chem 2/L - ORGANIC
CHEMISTRY
MODULE 9
CARBOXYLIC ACIDSLearning
Outcomes
After going through in this module, you should be
able to:
✔ Draw structures of carboxylic acids and
derivatives given IUPAC/ Common name & vice-
versa.
✔ Write chemical equations for the reactions of
carboxylic acids and derivatives.
✔ Describe sources and properties of carboxylic
acids and derivatives.
2

Page 217 Overview

Because carboxylic acids and their derivatives are
involved in so many industrial processes and most biological
pathways, an understanding of their properties and behavior
is fundamental to understanding organic and biological
chemistry. In this module, we’ll first discuss carboxylic acids
themselves and will then explore in detail the most common
reaction of carboxylic acid derivatives—the nucleophilic acyl
substitution reaction.
3

Page 218 Initial Activity

Analyze the two structures below. Write their similarities and
differences in the table below.
Aspirin (Acetylsalicylic Acid) Citric Acid
Similarities Differences
_______________________ _______________________
4
_______________________ _______________________
_______________________ _______________________
_______________________ _______________________
_______________________ _______________________

Page 219 Discussion

8.1 Structure of Carboxylic Acids
Carboxylic acids and their derivatives are the most
abundant of all organic compounds, both in the laboratory
and in living organisms. Although there are many different
kinds of carboxylic acid derivatives, we’ll be concerned only
with some of the most common ones: acid halides, acid
anhydrides, esters, amides, and related compounds called
nitriles. In addition, acyl phosphates and thioesters are acid
derivatives of particular importance in numerous biological
processes. The common structural feature of all these
compounds is that they contain an acyl group bonded to an
electronegative atom or substituent that can act as a leaving
group in substitution reactions.
5

Page 220 Discussion

8.2 Naming Carboxylic Acids and Derivatives
8.2.1 Carboxylic Acids: RCO2H
Simple open-chain carboxylic acids are named by replacing
the terminal -e of the corresponding alkane name with -oic
acid. The CO2H carbon is numbered C1.
Compounds that have a CO2H group (a carboxyl group)
bonded to a ring are named using the suffix -carboxylic acid.
The carboxyl carbon is attached to C1 on the ring and is not
itself numbered.
6

Page 221 Discussion

Table 8.1 Some Common Names of Carboxylic Acids and
Acyl Groups
7
8.2.2 Acid Halides: RCOX
Acid halides are named by identifying first the acyl group, as
in Table 8.1, and then the halide. Those cyclic carboxylic
acids that take a -carboxylic acid ending use -carbonyl for the
name ending of the corresponding acyl group. For example:
Page 222 Discussion
8.2.3 Acid Anhydrides: RCO2COR′
Symmetrical anhydrides from simple carboxylic acids and
cyclic anhydrides from dicarboxylic acids are named by
replacing the word acid with anhydride.
Unsymmetrical anhydrides—those prepared from two
different carboxylic acids—are named by citing the two acids
alphabetically and then adding anhydride.
8
8.2.4 Amides: RCONH2
Amides with an unsubstituted -NH2 group are named by
replacing the -oic acid or -ic acid ending with -amide, or by
replacing the -carboxylic acid ending with -carboxamide.
Page 223 Discussion
If the nitrogen atom is substituted, the amide is named by first
identifying the substituent groups and then the parent amide.
The substituents are preceded by the letter N to identify them
as being directly attached to nitrogen.
8.2.5 Esters: RCO2R′
Esters are named by first giving the name of the alkyl group
attached to oxygen and then identifying the carboxylic acid,
with -ic acid replaced by -ate.
9

Page 224 Discussion

8.2.6 Nitriles: R-CΞN
Compounds containing the -CΞN functional group are called
nitriles. Simple acyclic nitriles are named by adding -nitrile as
a suffix to the alkane name, with the nitrile carbon numbered
C1.
More complex nitriles are named as derivatives of carboxylic
acids by replacing the -ic acid or -oic acid ending with -
onitrile, or by replacing the -carboxylic acid ending with -
carbonitrile. In this system, the nitrile carbon atom is attached
to C1 but is not itself numbered.
10

Page 225 Learning Check

Exercise 1:
A. Give IUPAC names for the following carboxylic acids:
B. Draw structures corresponding to the following names:
(a) 2,3-Dimethylhexanoic acid
(b) 4-Methylpentanoic acid
(c) o-Hydroxybenzoic acid
(d) trans-Cyclobutane-1,2-dicarboxylic acid
C. Give IUPAC names for the following acyl derivatives:
11

Page 226 Learning Check

D. Draw structures corresponding to the following names:
(a) 2,2-Dimethylpropanoyl chloride
(b) N-Methylbenzamide
(c) 5,5-Dimethylhexanenitrile
(d) tert-Butyl butanoate
(e) trans-2-Methylcyclohexanecarboxamide
(f) p-Methylbenzoic anhydride
(g) cis-3-Methylcyclohexanecarbonyl bromide
(h) p-Bromobenzonitrile
12

Page 227 Discussion

8.3 Reactions of Carboxylic Acids
8.3.1 Conversion into acid chlorides
Carboxylic acids are converted into acid chlorides by
treatment with thionyl chloride, SOCl2. The reaction occurs by
a nucleophilic acyl substitution pathway in which the
carboxylic acid is first converted into an acyl chlorosulfite
intermediate, thereby replacing the -OH of the acid with a
much better leaving group. The chlorosulfite then reacts with
a nucleophilic chloride ion.
13
8.3.2 Conversion into esters (Fischer esterification)
Perhaps the most useful reaction of carboxylic acids
is their conversion into esters by reaction with an alcohol—
the substitution of -OH by -OR. Called the Fischer
esterification reaction, the simplest method involves heating
the carboxylic acid with an acid catalyst in an alcohol solvent.
Page 228 Discussion
8.3.3 Conversion into amides
Amides are carboxylic acid derivatives in which the acid -OH
group has been replaced by a nitrogen substituent, -NH2,
-
NHR, or -NR2. Amides are difficult to prepare directly from
acids by substitution with an amine because amines are
bases, which convert acidic carboxyl groups into their
unreactive carboxylate anions. Thus, the -OH must be
activated by making it a better, nonacidic leaving group.
14

Page 229 Discussion

8.4 Reactions of Acid Halides
8.4.1 Conversion into carboxylic acids
Acid chlorides react with water to yield carboxylic acids—the
substitution of -Cl by -OH. This hydrolysis reaction is a typical
nucleophilic acyl substitution process and is initiated by attack
of the nucleophile water on the acid chloride carbonyl group.
The initially formed tetrahedral intermediate undergoes loss
of HCl to yield the product.
8.4.2 Conversion into esters
Acid chlorides react with alcohols to yield esters in a reaction
analogous to their reaction with water to yield acids.
15

Page 230 Discussion

8.4.3 Conversion into amides
Acid chlorides react rapidly with ammonia and with amines to
give amides— the substitution of -Cl by -NR2. Both
monosubstituted and disubstituted amines can be used. Note
that one extra equivalent of ammonia is added to react with
the HCl generated.
16

Page 231 Discussion

8.5 Reactions of Acid Anhydrides
8.5.1 Conversion into esters
Aspirin (an ester) is prepared by reaction of acetic anhydride
with o-hydroxybenzoic acid.
8.5.2 Conversion into amides
Acetaminophen (an amide; the active ingredient in Tylenol) is
prepared by reaction of acetic anhydride with p-
hydroxyaniline.
17

Page 232 Discussion

8.6 Reactions of Esters
8.6.1 Conversion into acids
Esters are hydrolyzed either by aqueous base or by aqueous
acid to yield a carboxylic acid plus an alcohol.
8.6.2 Conversion into primary alcohols by reduction
Esters are reduced to primary alcohols by treatment with
LiAlH4. The reaction occurs by an initial nucleophilic acyl
substitution reaction in which hydride ion adds to the carbonyl
group followed by elimination of an alkoxide ion to give an
aldehyde intermediate. Further reduction of the aldehyde by a
typical nucleophilic addition process gives the primary
alcohol.
18

Page 233 Discussion

8.6.3 Conversion into tertiary alcohols by Grignard
reaction
Grignard reagents react with esters to yield tertiary alcohols
in which two of the substituents on the hydroxyl-bearing
carbon are identical. For example, methyl benzoate reacts
with 2 equivalents of CH3MgBr to yield 2-phenylpropan-2-ol.
The reaction occurs by nucleophilic addition of a Grignard
reagent to the ester, elimination of alkoxide ion to give an
intermediate ketone, and further nucleophilic addition to the
ketone to yield the tertiary alcohol.
19

Page 234 Discussion

8.6 Reactions of Amides
8.7.1 Conversion into carboxylic acids
Amides undergo hydrolysis in either aqueous acid or base to
yield carboxylic acids plus amine. Although the reaction is
slow and requires prolonged heating, the overall
transformation is a typical nucleophilic acyl substitution of -
OH for -NH2. In biochemistry, the reaction is particularly
useful for hydrolyzing proteins to their constituent amino
acids.
8.7.2 Conversion into amines by reduction
Like other carboxylic acid derivatives, amides are reduced by
LiAlH4. The product of this reduction, however, is an amine
rather than an alcohol.
20

Page 235 Discussion

8.6 Reactions of Nitriles
8.8.1 Conversion into carboxylic acids
Nitriles are hydrolyzed in either acidic or basic solution to
yield carboxylic acids and ammonia (or an amine).
8.8.2 Conversion into amines by reduction
Reduction of a nitrile with LiAlH4 gives a primary amine,
RNH2, just as reduction of an ester gives a primary alcohol,
ROH.
21

Page 236 Discussion

8.8.3 Conversion into ketones by Grignard reaction
Grignard reagents, RMgX, add to nitriles to give intermediate
imine anions that can be hydrolyzed to yield ketones. For
example, benzonitrile reacts with ethylmagnesium bromide to
give propiophenone.
22

Page 237 Evaluation

Refer to the Modelling Activity Sheet that accompanies this
module and do the Modelling Activity 8.
23

Page 238 Evaluation

1. Give the IUPAC name of the following compounds
.
24

Page 239 Evaluation

II. Answer the following
A. How might you prepare the following ester using a Fischer
esterification reaction?
B. Show how you could prepare ethyl benzoate by reaction of an acid
chloride with an alcohol.
25
C. What is the product of the following reaction?
Page 240 Evaluation
D. How could you prepare N-ethylaniline by reduction of an amide
with LiAlH4?
E. How would you prepare the following ketone by reaction of a
Grignard reagent and a nitrile?
26

Page 241 References

Textbooks:
1. McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-3098
USA. pp 325-363
2. Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-3098
USA.
Online:
1. [Link]
2. [Link]
3. [Link]
27
Page 242
PALAWAN STATE UNIVERSITY
College of Sciences
Chem 2/L - ORGANIC
CHEMISTRY
MODULE 5
ALKYL HALIDESLearning Outcomes
After going through in this module, you should be able
to:
✔ Draw structures of alkyl halides and its derivatives
given IUPAC/ Common name & vice-versa.
✔ Write chemical equations for the reactions of alkyl
halides.
✔ Describe sources and properties of alkyl halides.
2

Page 123 Overview

Alkyl halides (also known as haloalkanes) are
compounds in which one or more hydrogen atoms in an
alkane have been replaced by halogen atoms (fluorine,
chlorine, bromine or iodine). Alkyl halides fall into different
classes depending on how the halogen atom is positioned on
the chain of carbon atoms; there are some chemical
differences between the various types.
Alkyl halides (R-X) are encountered much less
frequently than their oxygen-containing relative alcohols (R-
OH), but some of the kinds of reactions they undergo—
nucleophilic substitutions and eliminations—are encountered
frequently. Thus, alkyl halide chemistry acts as a relatively
simple model for many mechanistically similar but structurally
more complex reactions. We’ll begin with a look at how to
draw structures, name and prepare alkyl halides, and we’ll
then make a detailed study of their substitution and
elimination reactions—two of the most important and well-
studied reaction types in organic chemistry. Finally, we will
look into the sources and properties of this family of organic
compounds.
3

Page 124 Initial Activity

Do you know what CFC’s are? Write something about CFC’s
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
_________________________________________________
4

Page 125 Discussion

5.1 Organohalides
Organohalides are compounds that contain one or
more halogen atoms. Halogen-substituted organic
compounds are widespread in nature, and more than 5000
organohalides have been found in algae and various other
marine organisms. Halogen-containing compounds also have
a vast array of industrial applications, including their use as
solvents, inhaled anesthetics, refrigerants, and pesticides.
The modern electronics industry, for example, relies on
halogenated solvents such as trichloroethylene for cleaning
semiconductor chips and other components.
5

Page 126 Discussion

Haloalkanes maybe primary, secondary or tertiary.
In a primary (1°) haloalkane, the carbon bonded to the
halogen atom is only attached to one other alkyl group. Some
examples of primary alkyl halides include the compounds
below.
In a secondary (2°) haloalkane, the carbon bonded with the
halogen atom is joined directly to two other alkyl groups that
can be the same or different. Some examples of secondary
alkyl halides include the compounds below.
6
In a tertiary (3°) halogenoalkane, the carbon atom holding
the halogen is attached directly to three alkyl groups, which
may be any combination of same or different. Some
examples of tertiary alkyl halides include the compounds
below.
Page 127 Discussion
5.2 Naming Alkyl Halides
Although commonly called alkyl halides, halogen-
substituted alkanes are named systematically as haloalkanes,
treating the halogen as a substituent on a parent alkane
chain.
Step 1: Find the longest chain, and name it as the parent.
If a multiple bond is present, the parent chain must contain it.
Step 2: Number the carbons of the parent chain
beginning at the end nearer the first substituent, whether
alkyl or halo. Assign each substituent a number according to
its position on the chain. If there are substituents the same
distance from both ends, begin numbering at the end nearer
the substituent with alphabetical priority.
7

Page 128 Discussion

Step 3: Write the name. List all substituents in alphabetical
order, and use one of the prefixes di-
, tri-
, and so forth if more
than one of the same substituent is present.
In addition to their systematic names, many simple
alkyl halides are also named by identifying first the alkyl
group and then the halogen. For example, CH3I can be called
either iodomethane or methyl iodide. Such names are well
entrenched in the chemical literature and in daily usage, but
they won’t be used in this book.
8

Page 129 Learning Check

Skills Practice 5.1
A. Give the IUPAC names of the following alkyl halides:
B. Draw structures corresponding to the following names:
(a) 2-Chloro-3,3-dimethylhexane
(b) 3,3-Dichloro-2-methylhexane
(c) 3-Bromo-3-ethylpentane
(d) 2-Bromo-5-chloro-3-methylhexane
9

Page 130 Discussion

5.3 Physical Properties of Alkyl Halides
All alkyl halides are insoluble in water and soluble in
common organic solvents. As with alkanes, the boiling ponit
increases as molecular weight increases. The boiling point
increases in the order F<Cl<Br<I. Boiling point also
increases for straight-chain isomers. Ex. CH3CH2Cl<
CH3CH2CH2Cl < CH3CH2CH2CH2Cl. More branching lowers
the boiling point of alkyl halides as shown in the table below.
10

Page 131 Discussion

5.4 Preparation of Alkyl Halides
How are haloalkanes made? There are several ways
in which haloalkanes can be made. This includes the
following:
1. free- radical substitution of alkanes
2. electrophilic addition of HX or X2 to alkenes.
11

Page 132 Discussion

12

Page 133 Discussion

5.4 Reactions of Alkyl Halides
1. Formation of Grignard Reagents
Alkyl halides, RX, react with magnesium metal in ether
solvent to yield alkylmagnesium halides, RMgX. The
products, called Grignard reagents after their discoverer,
Victor Grignard, are examples of organometallic compounds
because they contain a carbon–metal bond. In addition to
alkyl halides, alkenyl (vinylic) and aryl (aromatic) halides also
react with magnesium to give Grignard reagents. The
halogen can be Cl, Br, or I, but not F.
13
2. SN2 Reaction: backside attack of nucleophile on alkyl
halide
Page 134 Discussion
An SN2 reaction takes place in a single step without
intermediates when the entering nucleophile approaches the
substrate from a direction 180° away from the leaving group.
As the nucleophile comes in on one side of the molecule, an
electron pair on the nucleophile Nu:- forces out the leaving
group X:-
, which departs from the other side of the molecule
and takes with it the electron pair from the C-X bond. In the
transition state for the reaction, the new Nu-C bond is partially
forming at the same time the old C-X bond is partially
breaking, and the negative charge is shared by both the
incoming nucleophile and the outgoing leaving group.
14

Page 135 Discussion

Mechanism:
1. The nucleophile–OH uses its lone-
pair electrons to attack the alkyl halide
carbon 180° away from the departing
halogen. This leads to a transition
state with a partially formed C–OH
bond and a partially broken C–Br
bond.
2. The stereochemistry at carbon is
inverted as the C–OH bond forms fully
and the bromide ion departs with the
electron pair from the former C–Br
bond.
15

Page 136 Discussion

3. SN1 Reaction: carbocation intermediate is involved
Most nucleophilic substitutions take place by the
SN2 pathway just discussed, but an alternative called the
SN1 reaction can also occur. In general, SN1 reactions take
place only on tertiary substrates and only under neutral or
acidic conditions in a hydroxylic solvent such as water or
alcohol.
Unlike what occurs in an SN2 reaction, where the
leaving group is displaced at the same time that the incoming
nucleophile approaches, an SN1 reaction occurs by
spontaneous loss of the leaving group before the incoming
nucleophile approaches. Loss of the leaving group gives a
carbocation intermediate, which then reacts with the
nucleophile in a second step to yield the substitution product.
16

Page 137 Discussion

Mechanism:
1. The–OH group is first
protonated by HBr.
2. Spontaneous dissociation of
the protonated alcohol occurs in a
slow, rate-limiting step to yield a
carbocation intermediate plus water.
Carbocation:
17
3. The carbocation
intermediate reacts with bromide ion in
a fast step to yield the neutral
substitution product.
Page 138 Discussion
4. E2 Reaction
C–H and C–X bonds break simultaneously, giving the alkene
in a single step without intermediates.
Mechanism:
1. Base (B:) attacks a neighboring
hydrogen and begins to remove the H
at the same time as the alkene double
bond starts to form and the X group
starts to leave.
18
2. Neutral alkene is produced when
the C–H bond is fully broken and the X
group has departed with the C–X bond
electron pair.
Page 139 Discussion
5. E1 Reaction
C–X bond breaks first to give a carbocation intermediate, followed by
base removal of a proton to yield the alkene.
Mechanism:
1. Spontaneous dissociation of the tertiary
alkyl chloride yields an intermediate
carbocation in a slow, rate-limiting step.
19
Carbocation:
2. Loss of a neighboring H+ in a fast step
yields the neutral alkene product. The
electron pair from the C–H bond goes to
form the alkene bond.
Page 140 Discussion
6. E1cB Reaction
loses X– to form the alkene.
C–H bond breaks first, giving a carbanion intermediate that
1. Spontaneous dissociation of the tertiary alkyl chloride yields an
intermediate carbocation in a slow, rate-limiting step.
2. Loss of a neighboring H+ in a fast step yields the neutral alkene
product. The electron pair from the C–H bond goes to form the
alkene bond complete.
20

Page 141 Evaluation

Refer to the Modelling Activity Sheet that accompanies this
module and do the Modelling Activity 5.
21

Page 142 Evaluation

Laboratory Exercise/Activity
Make an editorial of not less than 300 words regarding the
CFCs.
22

Page 143 Evaluation

A. Give the IUPAC name of the following compounds
23

Page 144 Evaluation

B. Supply each blank with the necessary reactants or products
to complete the given equations below.
1. + HBr 🡪
_______________
2. + _______ 🡪
3. _________ + Br2 (light) 🡪
24
4. + Br2 (light) 🡪
______________
Page 145 Evaluation
B. Tell whether each of the following reactions is likely to be S N1,
SN2, E1, E1cB, or E2:.
25

Page 146 References

Textbooks:
1. McMurray, J.E. 2011. Seventh Edition: Fundamentals of Organic
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-3098
USA. pp 222-245
2. Stoker, H.S. 2013. Sixth Edition: General, Organic and Biological
Chemistry. Cengage Learning. 20 Davis Drive Belmont, CA 94002-3098
USA.
Online:
1. [Link]
2. [Link]
3. [Link]
4. c_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Alkyl_Halides
26
Page 147
PALAWAN STATE UNIVERSITY College of Sciences

Chem 2/L - ORGANIC CHEMISTRY

MODULE 6

ALCOHOLS, PHENOLS, AND ETHERS

Learning Outcomes

After going through in this module, you should be able to:

✔ Draw structures of alcohols, phenols, ethers and

their derivatives given IUPAC/ Common name & vice

-versa.

✔ Write chemical equations for the reactions of

alcohols, phenols and ethers.

✔ Describe sources and properties of alcohols, phenol

and ethers.

Overview

Up to this point, we’ve focused on developing some general ideas of organic reactivity
and on looking at the chemistry of hydrocarbons and alkyl halides. With that background,
it’s now time to begin a study of oxygen- containing functional groups, which lie at the
heart of organic and biological chemistry. In fact, practically every one of the hundreds of
thousands of different compounds in your body contains oxygen. We’ll look at
compounds with C-O single bonds in this module.

Page 150

Initial Activity

In this time of pandemic, we are expected to practice health protocols to help minimize or
even stop the spread of COVID- 19. One of the health practices that we must apply is the
use of disinfectants and sanitizers. List the disinfectants and sanitizers that you know of
and which of this is the most common among people?

_________________________________________________
_________________________________________________
_________________________________________________
_________________________________

Page 151

Discussion

6.1 Structure and Classification of Alcohols

Alcohols have the general formula: R-OH, where “R” involves a saturated C-atom (bound to
hydrogen atoms and/or other carbons). Examples are shown below:

Discussion
Alcohols are classified as primary (1°), secondary (2°), or

tertiary (3°), depending on the number of carbon substituents (R) bonded to the
hydroxyl-bearing carbon. A primary alcohol (1°), has only (1) R bonded to the hydroxyl-
bearing C, The secondary alcohol (2°) has two (R), while the tertiary alcohol (3°) has three (R).

Page 153

Discussion

6.2 . Naming Alcohols 6.2.1 In the IUPAC system, one way of naming alcohols follow these
steps: Step 1. Find longest, continuous C-chain to which the OH group (hydroxyl) is
bound. Number the chain in a way that gives the OH group the lowest numbering. Step 2.
Name and number other substituents present. Step 3. The name for the corresponding
alkane chain (e.g. for a 6-C chain, hexane) loses the “e” and picks up “ol” (hexanol).

• For cyclic alcohols, the OH group is understood to be 7

attached to C-1.

Page 154

Discussion

• Polyhydroxyl alcohols possess more than one OH group. • Alcohols which possess two OH
groups are called “diols” and those with three OH groups are called “triols”

Page 155

Discussion

The newer post-1993 naming system may also be used,

Simple alcohols are named in the IUPAC system as derivatives of the parent alkane, using
the suffix -ol. As always, the locant indicating the position of the hydroxyl group in the
parent chain is placed immediately before the -ol suffix in the

STEP 1: Select the longest carbon chain containing the hydroxyl group, and replace the -e
ending of the corresponding alkane with -ol. The -e is deleted to prevent the occurrence
of two adjacent vowels: propanol rather than propaneol, for example.

STEP 2: Number the carbons of the parent chain beginning at the end nearer the hydroxyl
group.
9

STEP 3: Number all substituents adding to their position on the chain, and write the
name listing the substituents in alphabetical order and identifying the position to which
the OH is bonded. Note that in naming cis-cyclohexane1,4-diol, the final -e of cyclohexane
is not deleted because the next letter (d) is not a vowel; that is, cyclohexanediol rather
than

cyclohexandiol. Page 156

Discussion

6.2.2. Common Name for Alcohols Most simple alcohols are named by their common name.

• Name the C-atoms of a single alkyl group as for alkanes. • Add the word “alcohol” following
a space after the alkyl name.

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Discussion

6.3. Properties of Alcohols

Alcohols consist of a non-polar (alkane-like) chain and a polar hydroxyl [Link],

alcohols might be water-soluble, or not (depending on the length of the carbon
chain).We already saw that the boiling points of alkanes increase with increasing chain
length. The same is true for alcohols due to stronger intermolecular forces holding molecules
together. Alcohols with more than one hydroxyl group (polyhydroxy alcohols) have higher
boiling points than monoydroxy alcohols because of more H-bonds that are stronger than
London Forces.

11

Compound

IMF

Ethane London Methanol London, H-bonding Ethanol London, H-bonding 1,2-ethanediol

London, more H-bonding

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Boiling Point -89oC 65oC 78oC 197oC

Discussion
The water-solubility of alcohols depends on the length of the alkyl chain in the alcohol.
Monohydroxy alcohols having chains longer than three carbons are not very water-soluble.
Polyhydroxy alcohols are more soluble because they have more opportunities for hydrogen-
bonding with water. Alcohols have higher boiling points than alkanes of the same chain
length (because they hydrogen bond to each other; the intermolecular forces for alkanes
are only London forces). Alcohols of a given chain length are far more water-soluble than
alkanes.

12

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Discussion

6.4 Naming Phenols

The word phenol is used both as the name of a specific substance (hydroxybenzene) and
as the family name for all hydroxy-substituted aromatic compounds. Substituted phenols
are named as described previously in Section 5.2 for aromatic compounds, with -phenol used
as the parent name rather than –[Link] that are substituted with both OH and
CH3 groups are called cresols (IUPAC-accepted common names):

13

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Discussion

For dihidroxy-benzene structures, the following IUPAC- accepted common names are used:
(d) 1-Chloro-3,5- dimethylbenzene

14

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Discussion

6.5 Naming Ethers

Simple ethers that contain no other functional groups are named by identifying the two
organic groups( alkyl groups) arranged in alphabetical order and adding the word ether.

If other functional groups are present, the ether part is named as an alkoxy substituent. For
example:

15
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Learning Check

Skills Practice A. Classify the following alcohols as primary, secondary, or tertiary.

1.

2.

3.

4. OH

16

5.

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Learning Check

B. Name the following structures below.

C. Draw structures corresponding to the following IUPAC names:

(a) 2-Methyl -2- hexanol (b) Hexane-1,5-diol (c) 2-Ethy-2-pentanol (d) 3-Methycyclohexanol (e)
o-Bromophenol (f) 2,4,6-Trinitrophenol (g) diethyl ether. (h) methoxypropane

Learning Check

D. Name the following ethers by IUPAC rules:.

Discussion

6.6 Reactions of Alcohols

6.6.1 Combustion

In combustion reactions involving alcohols, CO2 and H2O are produced.

Examples:

CH3OH + O2 → CO2 + 2 H2O

CH3CH2OH + 3 O2 → 2 CO2 + 3 H2O

6.6.2. Dehydration

Alcohols undergo dehydration—the elimination of H2O— to give alkenes. A method that

works particularly well for secondary and tertiary alcohols is treatment with a strong acid.
19

Examples:

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Discussion

In general, these kinds of reactions (eliminations) proceed as follows:

If there is more than one adjacent carbon atom from which loss of a H-atom can occur,
there will be more than one possible alkene dehydration products.

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Discussion

6.6.3 Oxidation

Perhaps the most valuable reaction of alcohols is their oxidation to yield carbonyl
compounds—the opposite of the reduction of carbonyl compounds to give alcohols.
Primary alcohols yield aldehydes or carboxylic acids, and secondary alcohols yield ketones,
but tertiary alcohols don’t normally react with oxidizing agents.

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Discussion

6.7 Reactions of Phenols

6.8.1 Acidic cleavage with HBr or HI

Ethers are unreactive to most common reagents, a property that accounts for their
frequent use as reaction solvents. Halogens, mild acids, bases, and nucleophiles have no
effect on most ethers. In fact, ethers undergo only one general reaction—they are
cleaved by strong acids such as aqueous HI or HBr.

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Learning Check

Skills Practice Predict the major product of the following reactions: 1.

2.

3.

4.

5.

Evaluation

Refer to the Modelling Activity Sheet that accompanies this module and do the Modelling
Activity 6.

24

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Evaluation

Answer the following: A. Classify the following alcohols:

Evaluation

C. Predict and write structure of the products of the following reactions: x2

1. dehydration reaction of 2-butanol 2. oxidation of 1-butanol 3. combustion of ethyl alcohol

4. reaction of diethyl ether with acidic HI.