Functional Groups

Functional Groups
• Functional groups: special groups of
atoms attached to a hydrocarbon
skeleton; the most common sites of
chemical reactivity.
• Functional Groups are the reactive
portions of the molecule that undergo
predictable reactions depending upon
the functional group.
• Organic compounds often contain
elements other than C, H that increase
their reactivity.
• Functional groups are parts of molecules
that result in characteristic features
• About 100 functional groups exist, we will
focus on THE MOST COMMON
• Useful to group the infinite number of
possible organic compounds
• E.g. the simplest group is hydrocarbons
• Made up of only C and H
• Not really a functional “group”
• Further divided into:
• Alkanes, Alkenes, Alkynes, Aromatics
 Hydrocarbons
Alkanes C C Alkenes C C
H H H H H H H H
H C C C C C H H C C C C C H
H H H H H H H H H H

Alkynes C C Aromatics H
H C H
H H H C C
H C C C C C H C C
H C H
H H H
H
List of Organic Functional Groups

8–5
Summary of Important Families of Organic
Compounds

condense molecular formula

• There are other names that describe patterns
of atoms that are parts of functional groups.
• “Hydroxyl” refers to –OH
• “Carbonyl” refers to C=O Must note

• “Carboxyl” refers to COOH

Q: which functional groups contain a hydroxyl
group? A carbonyl group? A carboxyl group?
Hydroxyl: alcohols, carboxylic acids.
Carbonyl:aldehydes, ketones, carboxylic acids,
amides, esters.
Carboxyl: carboxylic acids
Note that properties such as boiling and melting
point change due to functional groups For more lessons, visit
www.chalkbored.com
alkanes
H H
Only carbon and
hydrogen
H C C H
All single bonds

H H
Q: What should you call cyclic hydrocarbons made up
o of just single bonds?
A: Cycloalkanes
alkenes

Only carbon and H H

hydrogen
A carbon to carbon C C
double bond
H H

Q: What should you call a molecule with two C=Cs?

A: A diene
alcohols

Only one oxygen H H

Has an O-H group
Can classify as 1º/2º/3º H C C O H
according to position
of O-H group on H H
carbon skeleton

Q: Why are short-chain alcohols so soluble in water?

A: They can form hydrogen bonds with H2O molecules
phenols

Only one oxygen

O H
Has an O-H group
The O-H group is
directly attached to a
benzene ring

Q: The C6H5- group has a special name. What is it?

A: Phenyl
aldehydes

Only one oxygen

H
O
Has a C=O group
C=O group is at the H C C
end of carbon chain,
so is next door to a
H
hydrogen atom
H

Q: Aldehydes can be easily oxidised to form …?

A: Carboxylic acids
ketones

Only one oxygen H O H

Has a C=O group
C=O group is not H C C C H
at the end of carbon
chain, so is next
door to 2 carbons H H

Q: Ketones cannot easily be oxidised. Why not?

A: No hydrogen atom attached to the C=O group.
carboxylic acids
Has 2 oxygens
H
Has O-H and C=O O
groups on the same
carbon atom H C C
This -COOH group has
to be at the end of a O H
carbon chain H
Q: Write an equation showing how ethanoic acid can
a act as a (weak) acid.
A: CH3COOH(aq) CH3COO–(aq) + H+(aq)
esters

Has 2 oxygens H
O
One oxygen is part H
of a C=O bond, the H C C
other is next door, O C H
sandwiched between H
two carbons H

Q: This ester can be made by reacting ethanoic acid with

a an alcohol. Name the alcohol, and name the ester.
A: Alcohol = methanol; ester = methyl ethanoate
ethers
Has 1 oxygen H H H
No O-H or C=O
group H C C O C H
The oxygen is
sandwiched between H H H
two carbon atoms

Q: Why do ethers have much lower boiling points

t than their isomeric alcohols?
A: No hydrogen bonds between ether molecules
 “What family…?” quiz
Family names:
cycloalkane aldehyde
alkene ketone
primary (1º) alcohol carboxylic acid
secondary (2º) alcohol ester
tertiary (3º) alcohol ether
phenol … are you ready?

5 … 4 … 3 … 2 … 1 … GO!
What family does it belong to? (1)

H H
C C
H H
What family does it belong to? (2)

H
O
H C C
H
H
What family does it belong to? (3)

H
H O H

H C C C H

H H H
What family does it belong to? (4)

C O H

H
What family does it belong to? (5)

H H

H C O C H

H H
What family does it belong to? (6)

H
O
H
H C C
O C H
H
H
What family does it belong to? (7)

H O H

H C C C H

H H
What family does it belong to? (8)

O H
What family does it belong to? (9)

H H
O
H C C C
O H
H H
What family does it belong to? (10)
H

H C H
H

H C C O H

H H H
C
H
What family does it belong to? (11)

H H

C C H

H H
Answers: “What family?” quiz (1)

H H
C C
H H

alkene
Answers: “What family?” quiz (2)

H
O
H C C
H
H
aldehyde
Answers: “What family?” quiz (3)

H
H O H

H C C C H

H H H

secondary alcohol
Answers: “What family?” quiz (4)

C O H

primary alcohol
Answers: “What family?” quiz (5)

H H

H C O C H

H H

ether
Answers: “What family?” quiz (6)

H
O
H
H C C
O C H
H
H

ester
Answers: “What family?” quiz (7)

H O H

H C C C H

H H
ketone
Answers: “What family?” quiz (8)

O H

phenol
Answers: “What family?” quiz (9)

H H
O
H C C C
O H
H H

carboxylic acid
Answers: “What family?” quiz (10)
H

H C H
H

H C C O H

H H H
C
H
tertiary alcohol
Answers: “What family?” quiz (11)

H H

C C H

H H

cycloalkane
“Spot the functional groups” quiz
Functional groups:
alkene aldehyde
primary (1º) alcohol ketone
secondary (2º) alcohol carboxylic acid
tertiary (3º) alcohol ester
phenol ether
arene (NEW!) … are you ready?

5 … 4 … 3 … 2 … 1 … GO!
Spot both the functional groups (1)

OH phenol

OH

O
carboxylic acid
Spot all three functional groups (2)
O

ester
O
O
carboxylic acid
OH
arene
Spot both the functional groups (3)

O
OH
phenol
O
ester
Spot both the functional groups (4)

primary alcohols
OH
OH

OH
secondary alcohol
Spot all three functional groups (5)

O
ketone

tertiary
OH alcohol
alkene
Spot all three functional groups (6)

aldehyde
H
alkene

arene
Spot all three functional groups (7)

ketone

arene
OCH3

ether
Functional groups quiz: results

Maximum score = 18
How did you do?
ALKYL HALIDES
What Is an Alkyl Halide
◼ An organic compound containing at least one carbon-
halogen bond (C-X)
◼ X (F, Cl, Br, I) replaces H
◼ Can contain many C-X bonds
 Alkyl Halides
• Alkyl halides are organic molecules containing a halogen atom bonded to
an sp3 hybridized carbon atom.
• Alkyl halides are classified as primary (1°), secondary (2°), or tertiary (3°),
depending on the number of carbons bonded to the carbon with the
halogen atom.
• The halogen atom in halides is often denoted by the symbol “X”.
 no. of alkyl groups: 2

H
Classification of alkyl halides R' C X
R
o
a) Primary (1 ) c) Tertiary (3o)
no. of alkyl groups: none or one no. of alkyl groups: 3

H H R''
H C X H C X R' C X
H R R
b) Secondary (2o)
no. of alkyl groups: 2

H
R' C X
R
c) tertiary (3o)
no. of alkyl groups: 3
 Classify These:

CH3 CH CH3 CH3CH2F

Cl

(CH3)3CBr CH3I =>

 STRUCTURE OF HALOGENOALKANES

Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)

Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group

Haloarenes - halogen is attached directly to a benzene (aromatic) ring

Structural
difference Halogenoalkanes are classified according to the environment of the halogen

PRIMARY 1° SECONDARY 2° TERTIARY 3°

Names Based on original alkane with a prefix indicating halogens and position.
CH3CH2CH2Cl 1-chloropropane CH3CHClCH3 2-chloropropane
CH2ClCHClCH3 1,2-dichloropropane CH3CBr(CH3)CH3 2-bromo-2-methylpropane
 STRUCTURE OF HALOGENOALKANES

Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)

Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group

Haloarenes - halogen is attached directly to a benzene (aromatic) ring

Structural
difference Halogenoalkanes are classified according to the environment of the halogen

PRIMARY 1° SECONDARY 2° TERTIARY 3°

 IUPAC names: use rules for alkanes
halogen = halo (fluoro, chloro, bromo, iodo)
Cl
CH3CH2CH2CH2-Br CH3CHCH3
1-bromobutane 2-chloropropane
1o 2o
 CH3 CH3
CH3CHCH2CHCH3 CH3CCH3
Br I
2-bromo-4-methylpentane 2-iodo-2-methylpropane
2o 3o

CH3
Cl-CHCH2CH3

2-chlorobutane
2o
 Classes of Halides
• Alkyl: Halogen, X, is directly bonded to
carbon.
• Vinyl: X is bonded to carbon of alkene.
• Aryl: X is bonded to carbon on benzene
ring. Examples:
H H I
H H
H C C Br C C
H H H Cl
alkyl halide vinyl halide aryl halide
Chapter 6
 Types of Alkyl Halides
Other types of organic alkyl halides
include:
• Allylic halides have X bonded to the
carbon atom adjacent to a C-C double
bond.

• Benzylic halides have X bonded to the

carbon atom adjacent to a benzene
ring.

NOT ALKYL HALIDES

• Vinyl halides have a halogen atom (X)
bonded to a C-C double bond.

• Aryl halides have a halogen atom

bonded to a aromatic ring.
 Dihalides
• Geminal dihalide: two halogen atoms
are bonded to the same carbon
• Vicinal dihalide: two halogen atoms are
bonded to adjacent carbons.

H H H H
H C C Br H C C Br
H Br Br H
geminal dihalide vicinal dihalide
 IUPAC Nomenclature
• Name as haloalkane.
• Choose the longest carbon chain, even if the
halogen is not bonded to any of those C’s.
• Use lowest possible numbers for position.

CH3 CH CH2CH3 CH2CH2Br

Cl CH3(CH2)2CH(CH2)2CH3
2-chlorobutane 4-(2-bromoethyl)heptane
 CH3 CH3 CH3
5 4 3 1 6 5 4 3 2 1
2 CH3 CH2 C CH2 CH CH3
CH3 CH2 CH CH CH3
CH3 I
CI Br
iodomethane 3-chloro-2-methylpentane 4-bromo-2,4-dimethylhexane
 Substitutive Nomenclature of Alkyl Halides

5 chloro- 2
methylheptane
Cl Halogen and alkyl groups
are of equal rank when
it comes to numbering
the chain.
CH3
2-choro-5-methy
lheptane
Number the chain in the
CH3 direction that gives the
lowest number to the
group (halogen or alkyl)
that appears first.
Cl
 CH2CH2Br
CH3 CH CH2CH3 CH3(CH2)2CH(CH2)2CH3
Cl

2-chlorobutane 4-(2-bromoethyl)heptane
 • Follow the rules… Name the following…
Br

4-Bromoheptane

Br

Cl

3,4-Dibromoheptane
3-Bromo-1-chloro-4-methylhexane

1,1-Dibromo-3-methyloctane
Name these compounds.

2- chloro-5-methlyheptane

McMurry Organic Chemistry 6th

edition, Chapter 10 (c) 2003
1-bromo-1methycyclohexane bromocylohexane

2-bromoheptane
2-bromo-2-methlyheptane
 3-iodopentane

CH3CH2CH2CH2CH2F CH3CH2CHCH2CH3
1-floropentane I

CH3F CH3CH2CH2CH2CH2Cl
Flouromethane
1-chloropentane

3-bromohexane
CH3CH2CHCH2CH2CH3 H
Br I
iodocyclohexane
CH3CHCH2CH2CH3
2-bromopentane
Br
 CH3CHCH2CH2CH3
CH3CH2CH2CH2CH2F
Br

CH3F CH3CH2CH2CH2CH2Cl

CH3CH2CHCH2CH2CH3 H
Br I

CH3CH2CHCH2CH3

I
Substitutive Nomenclature of Alkyl Halides

Cl
5-Chloro-2-methylheptane

CH3

CH3

2-Chloro-5-methylheptane
Cl
Naming if Two Halides or Alkyl Are Equally
Distant from Ends of Chain
◼ Begin at the end nearer the substituent whose name
comes first in the alphabet
Many Alkyl Halides That Are Widely Used
Have Common Names

◼ Chloroform
◼ Carbon tetrachloride
 Chloromethane: is produced by
giant kelp and algae and also found
in emissions of volcanoes such as
Hawaii’s Kilauea.

Dichloromethane (or methylene

chloride) is an important solvent,
once used to decaffeinate coffee.

Halothane is a safe general

anesthetic
27
 STRUCTURAL ISOMERISM IN HALOGENOALKANES
Different structures are possible due to...
Different positions for the halogen and branching of the carbon chain

1-chlorobutane 2-chlorobutane

2-chloro-2-methylpropane 1-chloro-2-methylpropane
 PHYSICAL PROPERTIES
• BOILING POINTS
- molecules with higher molecular weight have higher
boiling points.
- reasons: the molecule is heavier, slower moving, have
greater surface area, have larger London attractions,
resulting higher boiling points.
- example:

CH3F CH3Cl CH3Br CH3I

RMM 34 50.5 95 142
bp (°C) -78 -24 4 42
- compounds with branched have more spherical
shapes, have smaller surface area, resulting lower
boiling points.
2-chloro-2-methlypropane
2-chlorobutane CH3
1-chlorobutane
CH3 CH3 C Cl
CH3CH2CH2CH2Cl CH3CH2CHCl CH3
bp 78 oC bp 67 oC bp 52 oC

- alkyl halides with more carbon atoms have higher

boiling points.

CH3Cl CH3CH2Cl CH3CH2CH2Cl

bp -24oC bp 12 Co bp 47oC
chloromethane chloroethane 1-chloropropane
Preparing Alkyl Halides
◼ Alkyl halide is from addition of HCl, HBr, HI to
alkenes to give Markovnikov product
REACTIONS OF ALKYL
HALIDES
NUCLEOPHILIC SUBSTITUTION REACTIONS
3) Amine synthesis

R-X NH3 R-NH2 HX

nucleophile

example
CH3CH2 Br H-NH2 CH3CH2 NH2 HBr
ethyl bromide ethylamine (primary amine)

HBr(g) + NH3 (g) NH4Br (s)

amine are also act as nucleophile (more reactive than ammonia)
C2H5Br H N C2H5 (C2H5)2NH + HBr
H diethylamine
(secondary amine)

C2H5Br (C2H5)2NH (C2H5)3N + HBr

triethylamine
(tertiary amine)

C2H5Br (C2H5)3N (C2H5)4N+ Br-

tetraethylammonium bromide
(quaternary salt)
 Relative reactivities of primary,
secondary, and tertiary alkyl halides
• The reactivity of alkyl halides towards nucleophilic
substitution depend on the halogen.

• The rate of reaction decrease in the order

R-I > R-Br > R-Cl > R-F
(most reactive) (least reactive)

• Reason: C-X bond become stronger from I to F

 Elimination reactions-
dehydrohalogenation of alkyl halides
• Elimination: loss of two atoms or groups from the
substrate to form a pi bonds.
• Dehydrohalogenation (removal of hydrogen and a
halogen atom) of alkyl halide to form alkene.

C C C C HX
H X
alkyl halide alkene
HX = HCl or HBr or Hl
Reaction of Alkanes with Halogens
◼ Alkane + Cl2 or Br2, heat or light replaces C-H with C-
X but gives mixtures
◼ Often not a good idea to plan a synthesis that uses
this method
Preparing Alkyl Halides from
Alcohols
◼ Reaction of tertiary C-OH with HX is fast and
effective
◼ Add HCl or HBr gas into ether solution of tertiary
alcohol
◼ Primary and secondary alcohols react very slowly
and often rearrange, so alternative methods are used
Reduction Reactions
◼ Organic reduction is the opposite of oxidation
◼ Results in gain of electron density at carbon
(replacement of electronegative atoms by
hydrogen or carbon)
Reduction: form C-H (or C-C) and break C-O, C-N, C-X
 Halogenation of certain hydrocarbons.
R-H + X2, Δ or hν → R-X + HX
(requires Δ or hν; Cl2 > Br2 (I2 NR); 3o>2o>1o)
yields mixtures!  In syntheses, limited to those
hydrocarbons that yield only one monohalogenated
product.

CH3 CH3
CH3CCH3 + Cl2, heat → CH3CCH2-Cl
CH3 CH3

neopentane neopentyl chloride

2,2-dimethylpropane 1-chloro-2,2-dimethylpropane
From alcohols. #1 synthesis!

With HX
R-OH + HX → R-X + H2O

i) HX = HCl, HBr, HI
ii) may be acid catalyzed (H+)
iii) ROH: 3o > 2o > CH3 > 1o
iv) rearrangements are possible except with most 1o ROH
CH3CH2CH2CH2-OH + NaBr, H2SO4, heat → CH3CH2CH2CH2-Br
n-butyl alcohol (HBr) n-butyl bromide
1-butanol 1-bromobutane

CH3 CH3
CH3CCH3 + HCl → CH3CCH3
OH Cl
tert-butyl alcohol tert-butyl chloride
2-methyl-2-propanol 2-chloro-2-methylpropane

CH3-OH + HI, H+,heat → CH3-I

methyl alcohol methyl iodide
methanol iodomethane
Substitution Reactions With Halides

bromomethane methanol

Rate law:
If concentration of (1) is
doubled, the rate of the rate = k [1-bromo-1,1-dimethylethane]
reaction is doubled.
this reaction is an example of a SN1
reaction.
If concentration of (2) is S stands for substitution
doubled, the rate of the N stands for nucleophilic
reaction is not doubled. 1 stands for unimolecular
CH3CH2CH2-Br + KOH → CH3CH2CH2-OH + KBr

CH3CH2CH2-Br + HOH → CH3CH2CH2-OH + HBr

CH3CH2CH2-Br + NaCN → CH3CH2CH2-CN + NaBr

CH3CH2CH2-Br + NaOCH3 → CH3CH2CH2-OCH3 + NaBr

CH3CH2CH2-Br + NH3 → CH3CH2CH2-NH2 + HBr

CH3CH2CH2-Br + NaI, acetone → CH3CH2CH2-I + NaBr

R-X + :OH- → ROH + :X- alcohol
R-X + H2O → ROH + HX alcohol
R-X + :OR´- → R-O-R´ + :X- ether
R-X + -:CCR´ → R-CCR´ + :X- alkyne
R-X + :I- → R-I + :X- iodide
R-X + :CN- → R-CN + :X- nitrile
R-X + :NH3 → R-NH2 + HX primary
amine
R-X + :NH2R´ → R-NHR´ + HX secondary
amine
R-X + :SH- → R-SH + :X- thiol
 SOME USES OF ALKYL HALIDES
• Solvents
- industrial and household solvents.
- carbon tetrachloride (CCl4) used for dry cleaning, spot
removing.
- methylene chloride (CH2Cl2) is used to dissolve the
caffeine from coffee beans to produce decaffeinated
coffee.
• Anesthetics
- examples: chloroform (CHCl3) and ethyl
chloride.

• Freons: Refrigerants and foaming agents

- Freons (called chlorofluorocarbons, or CFCs)
is used as a refrigerant gas.

• Pesticides
- example: DDT (Dichloro Diphenyl-
Trichloroethane) is used as insecticides.
 USES OF HALOGENOALKANES

Chlorofluorocarbons - CFC’s
dichlorofluoromethane CHFCl2 refrigerant
trichlorofluoromethane CF3Cl aerosol propellant, blowing agent
bromochlorodifluoromethane CBrClF2 fire extinguishers

CCl2FCClF2 dry cleaning solvent, degreasing agent

All are/were chosen because of their LOW REACTIVITY, VOLATILITY, NON-TOXICITY

Nomenclature, Structure
and Synthesis of Alcohols
Nomenclature
Preparation
Reactions
 Classification of Alcohols
• Alcohols can be classified as primary (1°),
secondary (2°), or tertiary (3°) depending on the
number of alkyl groups attached to the carbon
bearing
H
the –OH
H
group.
CH3 CH3

H C H H3C C OH H3C C H H3C C CH3

OH H OH OH

Methanol 1° alcohol 2° alcohol 3° alcohol

ethanol 2-propanol 2-methyl-2-propanol
 Examples of Classifications
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
* *
Primary alcohol Secondary alcohol

CH3
OH
CH3 C* OH
CH3
Tertiary alcohol Phenol
Classify each of the following alcohols
as primary, secondary, tertiary, or
aromatic.

1. 1-butanol
2. 3-pentanol
3. 1-methylcyclopentanol
4. 2-methyl-2-pentanol
 CH3 CH3
CH3CHCH2CHCH3 CH3CCH3
OH OH
4-methyl-2-pentanol tert-butyl alcohol
2-methyl-2-propanol
2o 3o

CH3
HO-CHCH2CH3 CH3CH2CH2-OH

sec-butyl alcohol n-propyl alcohol

2-butanol 1-propanol
2o 1o
Nomenclature:
Common names: “alkyl alcohol”
IUPAC: parent = longest continuous carbon
chain containing the –OH group.
alkane drop -e, add –ol
prefix locant for –OH (lower number for OH)
 Nomenclature for alcohols
Common names for alcohols

• Name the C-atoms of a single alkyl group as for alkanes.

• Add the word “alcohol” following a space after the alkyl
name.

butyl alcohol sec-butyl alcohol isobutyl alcohol tert-butyl alcohol

sec-butanol (isobutanol) tert-butanol
 Nomenclature for alcohols
IUPAC Naming
• 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.
• Name and number other substituents present.
• 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 attached
to C-1.

2-Methyl-2-butanol 2-Methylcyclopentanol
 Alcohol Nomenclature
OH
2
5
3 6
3-heptanol 5-methyl-6-hepten-2-ol OH

2 OH
OH
1 1

3 5
CH3 CH3 CH3 CH3
3,3-dimethylcyclohexanol 5,5-dimethylcyclohex-2-enol
 OH

OH
(S) 2-hexanol (E) 3-methyl-3-penten-2-ol

OH
OH
H
OH
trans 3-isopropylcyclopentanol (R) 2-butyl-1,4-butanediol
(R) 2-butylbutane-1,4-diol
© 2013 Pearson Education, Inc.
 C4H9OH alcohols
H2 H2 OH CH3 CH3
C C C CH3 C OH H3C C OH
H3C C OH H3C H C H3C H C
H2 H2 H2 CH3
1-butanol 2-butanol 2-methyl-1-propanol 2-methyl-2-propanol
n-butyl alcohol sec-butyl alcohol isobutyl alcohol tert-butyl alcohol
OH
H2 H2 H2
C OH C H C
HO C HO C OH
H2
OH
OH H3C OH
HO trans-3-methylcyclohexanol
HO OH
ethanediol
OH
ethylene glycol
1,2,3-propanetriol
glycerin 1-methylcyclopentanol

Chemistry 21A Dr. Dragan Marinkovic

 H2 H2 OH CH3 CH3
C C C CH3 C OH H3C C OH
H3C C OH H3C H C H3C H C
H2 H2 H2 CH3
1-butanol 2-butanol 2-methyl-1-propanol 2-methyl-2-propanol
n-butyl alcohol sec-butyl alcohol isobutyl alcohol tert-butyl alcohol
primary alcohol secondary alcohol primary alcohol tertiary alcohol
H2
C OH OH
HO C H3C OH
H2
OH
HO
ethanediol
ethylene glycol trans-3-methylcyclohexanol 1-methylcyclopentanol

Chemistry 21A Dr. Dragan Marinkovic

 Isomerism for alcohols
Constitutional isomers

Positional isomers
Positional isomers
3-Methyl-1-butanol

1-Pentanol

3-Methyl-2-butanol

2-Pentanol

2-Methyl-1-butanol

3-Pentanol

2-Methyl-2-butanol

2,2-Dimethyl-1-propanol
 • Dialcohols, or diols,
contain two hydroxy
groups in the same
molecule. The IUPAC
names of these alcohols
are formed by attaching
the ending diol to the
alkane name.
• The names will contain two
numbers indicating the
carbons bonded to the two
—OH groups, with the
numbering starting at the
end closest to one of the
—OH groups.
© 2013 Pearson Education, Inc.
 Naming Diols
• Two numbers are needed to locate the two
—OH groups.
• Use -diol as suffix instead of -ol.

1 2 3 4 5 6

hexane-1,6-diol

© 2013 Pearson Education, Inc. Chapter 10 18

Alcohols with more than one OH group
• 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”

1,2-Ethanediol 1,2-Propanediol 1,2,3-Propanetriol

Alkane name + diol, “triol”, etc.

 Some Alcohols
OH OH
CH3CH2OH HO CHCH2NH2 CHCHNHCH3
CH3
ethanol HO
adrenaline (epinephrine) pseudephedrine

OH
HOCH2CHCH2OH H

glycerol H H
HO
cholesterol
 Commonly encountered alcohols
• Methanol (CH3OH) finds use as a solvent in chemical reactions
and in fuel for high-performance combustion engines.
• Drinking methanol is a no-no. It is metabolized to
formaldehyde and formic acid by the liver (alcohol
dehydrogenase):

Formaldehyde Formic acid

alcohol
dehydrogenase
(oxidation) (oxidation)
 Methanol: Not a Beverage

O
ADH +
CH3OH HCH + NADH + H
+
methanol NAD formaldehyde
LD50 = 0.07 g/Kg
 Commonly encountered alcohols
• Ethanol (CH3CH2OH) is also metabolized by the body, and this
reaction produces acetaldehyde and acetic acid:
Acetaldehyde Acetic acid
alcohol
dehydrogenase
(oxidation) (oxidation)

• Excessive drinking leads to liver cirrhosis, physiological

addiction, loss of memory. Drinking during pregnancy poses
risks for birth defects.
• Ethanol is sometimes rendered undrinkable by the addition of
small quantities of toxic substances (e.g. benzene).
• Industrially, ethanol is synthesized by hydration of ethene.
 Ethanol: the Beverage
Ethanol is a central nervous system depressant
- depresses brain areas responsible for judgement
(thus the illusion of stimulation)
O
alcohol dehydrogenase +
CH3CH2OH +
CH3CH + NADH + H
ethanol NAD acetaldehyde
LD50 = 1.9 g/Kg
+
NAD
enz.
+
CH3CO2H + NADH + H
acetic acid
Oldest known organic synthesis:
“fermentation”
Sugar + yeast → ethyl alcohol + CO2

~5-11% ethanol
 Commonly encountered alcohols
• Isopropyl alcohol is used in rubbing alcohol
(70% isopropyl alcohol in H2O) and in
cosmetics.
• Ingested, isopropyl alcohol is metabolized to
acetone:
Acetone

alcohol
dehydrogenase
(oxidation)
Phenols Ar-OH

Phenols are compounds with an –OH group

attached to an aromatic carbon. Although they
share the same functional group with alcohols,
where the –OH group is attached to an aliphatic
carbon, the chemistry of phenols is very different
from that of alcohols.

Chapter 21 27
 Naming Phenols
• Use “phene” (the French name for benzene) as
the parent hydrocarbon name, not benzene.
• Name substituents on aromatic ring by their
position from OH.
H2N
-
O
HO N+ OH
OH O
3-butylphenol 2-aminophenol 4-nitrophenol

28
⧫ Structure and Nomenclature of Phenols
Phenols have hydroxyl groups bonded directly to a benzene ring
Naphthols and phenanthrols have a hydroxyl group bonded to a polycyclic
benzenoid ring

Chapter 21 29
Chapter 21 30
Phenols are usually named as substituted phenols. The
methylphenols are given the special name, cresols. Some other
phenols are named as hydroxy compounds.

OH OH CH3 OH
OH COOH

Br

phenol m-bromophenol o-cresol salicylic acid

OH OH COOH
OH
OH

OH
OH OH

catechol resorcinol hydroquinone p-hydroxybenzoic acid

Chapter 21 31
 OH OH
HO

3-methylphenol 4-ethylphenol
phenol

OH OH
Cl Cl
alcohol

Cl
2,4,6-trichlorophenol benzyl alcohol

Chemistry 21A Dr. Dragan Marinkovic

 Chemical reactions of alcohols
Combustion reactions

• Any organic molecule can undergo a combustion reaction. In

combustion reactions involving alcohols, CO2 and H2O are
produced:
– CH3OH + O2 → CO2 + 2H2O
– CH3CH2OH + O2 → 2CO2 + 3H2O

Or, for 2-Propanol:

2 9 O2 6CO2 8H2O
Combustion of Alcohols
Combustion is the reaction of an alcohol with O2 to
produce CO2 and H2O.

General, Organic, and Biological Chemistry Copyright © 2010 Pearson Education, Inc. 34
A. combustion:

General, Organic, and Biological Chemistry Copyright © 2010 Pearson Education, Inc. 35
Reactions of Alcohols
 Chemical reactions of alcohols
Elimination reactions

• In an intramolecular alcohol dehydration, a water molecule is

lost (eliminated) from a single alcohol molecule.
• The elimination involved loss of the OH group and a H-atom
from an adjacent C-atom (sometimes, there’s more than one
of these)

H2SO4
H-OH
180oC

H2SO4
H-OH
180oC
 Chemical reactions of alcohols
Elimination reactions

• 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 product:

1-butene

loss of CH3 H-atom

H2SO4
+ H2O
180oC
loss of CH2 H-atom

2-butene
 Chemical reactions of alcohols
Elimination reactions

• Zaitsev’s Rule (for alcohol dehydrations): for cases where

more than one alkene product might be formed from an
elimination reaction, the hydrogen atom tends to be removed
from the carbon that already possesses the fewest hydrogens.

this carbon has this carbon has 1-butene

two H-atoms three H-atoms

H2SO4
+ H2O
180oC

2-butene
major product
 Chemical reactions of alcohols
Elimination reactions

• The alcohol dehydration reaction (like all chemical reactions)

is an equilibrium. Since it occurs through elimination of an
H2O molecule, conditions that favor H2O loss (dry conditions
(concentrated H2SO4), high temperatures) favor alkene
formation.
• On the other hand, if this reaction were run in dilute H2SO4,
alcohol formation would be favored.

Hydration
H2O
Dehydration
Reactions of Alcohols
Reactions of Alcohols
Reactions of Alcohols
Reactions of Alcohols
 Chemical reactions of alcohols
Oxidation reactions

• Oxidation/reduction reactions involving organic compounds

result in a change in the number of H-atoms and/or the
number of O-atoms bound to carbons in the molecule:
– Oxidations increase the number of C-O bonds and/or
decrease the number of C-H bonds in a molecule.
– Reductions decrease the number of C-O bonds and/or
increase the number of C-H bonds in a molecule.

Methanol Formaldehyde Formic acid

oxidation oxidation

reduction reduction
 Chemical reactions of alcohols
Oxidation reactions
• Primary and secondary alcohols can be oxidized by mild oxidizing agents to
produce compounds with C-O double bonds (aldehydes, ketones,
carboxylic acids).

[O] [O]

an aldehyde a carboxylic acid

a primary alcohol

[O]
mild oxidizing
agent = [O]
a ketone

a secondary alcohol
No H on OH-bearing
carbon to remove here.
[O]
no reaction

a tertiary alcohol
Reaction of alcohols with HX:

R-OH + HX → R-X + H2O

a) HX: HI > HBr > HCl

CH3CH2CH2CH2-OH + NaBr, H2SO4, heat → CH3CH2CH2CH2-Br
n-butyl alcohol n-butyl bromide
1-butanol 1-bromobutane

CH3 CH3
CH3C-OH + HCl → CH3C-Cl (room temperature)
CH3 CH3
tert-butyl alcohol tert-butyl chloride
2-methyl-2-propanol 2-chloro-2-methylpropane

CH3CH2-OH + HI, H+, heat → CH3CH2-I

ethyl alcohol ethyl iodide
ethanol iodoethane