Week1-3 OrgChem1 UpdatedStructureNomenclatureLecture 2023

Week 1-3
An Introduction to
Organic Compounds
Structure and
Nomenclature, of the
hydrocarbons: alkanes,
cycloalkanes incl. polycyclic
(fused/bridge/spiro),
alkenes, alkynes, benzene
Dr. C V Raidron
Sources:
© Pearson 2014; www.libtretext.com; www.leah4sci.com
Hydrocarbons
• Hydrocarbons: compounds that contain only
carbon (C) and hydrogen (H) atoms
Hydrocarbons
Alkanes & Alkenes & Alkynes Aromatic

Cycloalkanes Cycloalkenes
Saturated hydrocarbons Unsaturated hydrocarbons

Kekulé Structures and
Condensed Structures
How to Write and Interpret
Structural Formulas
Condensed Structural Formulas
More About Dash Structural
Formulas
 Atoms joined by single bonds can
rotate relatively free with respect to
one another
H
H HH H H H H
H HO H
C C H H C O
C C
H C O C C
H C H
H H H HH H
H H
Equivalent dash formulas for propyl alcohol
Bond-Line Formulas
 Apply the following rules when drawing
bond-line formulas:
● Each line represents a bond
● Each bend in a line or terminus of a
line represents a carbon atom, unless
another group is shown explicitly
● No letter C’s are written for carbon
atoms, except optionally for CH3
groups at the end of a chain or branch
● No letter H’s are shown for hydrogen
atoms, unless they are needed to give a
three-dimensional perspective, in which
case we use dashed or solid wedges
(as explained in the next section)
● The number of hydrogen atoms bonded
to each carbon is inferred by assuming
that as many hydrogen atoms are
present as needed to fill the valence
shell of the carbon, unless a charge is
indicated
● When an atom other than carbon or
hydrogen is present, the symbol for
that element is written at the
appropriate location (i.e., in place of a
bend or at the terminus of the line
leading to the atom)
● Hydrogen atoms bonded to atoms
other than carbon (e.g., oxygen or
nitrogen) are written explicitly
Three-Dimensional Formulas
 A dashed wedge ( ) represents a
bond that projects behind the plane of
the paper
 A solid wedge ( ) represents a bond
that projects out of the plane of the
paper
 An ordinary line ( ) represents a
bond that lies in the plane of the paper
Three-Dimensional Formulas
H
H H H
C H H
OR C C etc.
H C H
H H H
H
Ethane
H H Br
C OR C OR C etc.
H H H
Br Br H
H H H
Bromomethane
Br
H
H OH Cl
H
Examples of bond-line formulas that include
three-dimensional representations
H NH
2 Br H
HO
An example involving An example involving

trigonal planar geometry linear geometry
Alkanes & Cycloalkanes
• contain a carbon-carbon single bond
• Name of alkanes end with -ane
• Alkanes = General formula: CnH2n+2
• Cycloalkanes = alkanes in which all or some of the
carbon atoms are arranged in a ring
– General formula: CnH2n
– Named by placing prefix cyclo before alkane name
cyclopropane cyclobutane cyclopentane cyclohexane cycloheptane

Alkanes: Hydrocarbons That Contain Only Single
Bonds
General Molecular Formula: CnH2n+2
Alkanes
Name # Molecular Cond. Struc. # of Const.
Cs formula Formula Isomers
Methane 1 CH4 CH4 1
Ethane 2 C2H6 CH3CH3 1
Propane 3 C3H8 CH3CH2CH3 1
Butane 4 C4H10 CH3CH2CH2CH3 2
Pentane 5 C5H12 CH3(CH2)3CH3 3
Hexane 6 C6H14 CH3(CH2)4CH3 5
Heptane 7 C7H16 CH3(CH2)5CH3 9
Octane 8 C8H18 CH3(CH2)6CH3 18
Isomers
 Isomers: different compounds that
have the same molecular formula
● Constitutional isomers: isomers
that have the same molecular
formula but different connectivity
–their atoms are connected in a
different order
 Examples
Molecular Constitutional
Formula Isomers
C4H10 and
Butane 2-Methylpropane
Cl
Cl
C3H7Cl and
1-Chloropropane 2-Chloropropane
Isomers
Unbranched/ Branched chain
Straight chain
CH3CH2CH3
Propane ?
CH3CH2CH2CH3 CH3 CH CH3
Butane Constitutional CH3
Isomers
Isobutane
CH3CH2CH2CH2CH3
Pentane CH3 CH CH2 CH3
CH3
Isopentane
Constitutional CH3
Isomers CH3 C CH3
CH3
Neopentane
IUPAC Nomenclature of Alkanes
Nomenclature of unbranched alkyl groups:
• Removing a hydrogen from an alkane results in an
alkyl substituent
Alkane Alkyl group Abbreviation

CH3-H CH3- Me-
Methane Methyl
CH3CH2-H CH3CH2- Et-
Ethane Ethyl
CH3CH2CH2-H CH3CH2CH2- Pr-
Propane Propyl
CH3CH2CH2CH2-H CH3CH2CH2CH2- n-Bu-
Butane Butyl
Homologues
1 CH2 group 2 CH2 groups
Homologues differ by a CH2 group.

Week 1-3:
Video 1
Week 1-3:
Video 2
Naming Straight Chain Alkanes
Week 1-3:
Video 3
Naming Branched Alkanes
Remember: Substituents gets the lowest number !!

Junction
Week 1-3:
Video 4
Naming Alkanes that have branches
on their branches.
They have a substituent on a substituent

Constitutional isomer
Primary, Secondary, and Tertiary
Carbons
A primary carbon is bonded to one carbon.
A secondary carbon is bonded to two carbons.
A tertiary carbon is bonded to three carbons.
Primary hydrogens are attached to primary carbons.

Secondary hydrogens are attached to secondary carbons
Tertiary hydrogens are attached to tertiary carbons.
Chains with the Same Length
When two or more chains have the same length,

the parent hydrocarbon is the chain with the
most substituents.
Common versus Systematic
Nomenclature
• Common names never have numbers.

• Only systematic (IUPAC) names have
numbers.
Week 1-3:
Video 5
Naming Cyclic and Bicyclic Alkanes
Di-Substituted Cycloalkanes
• Substituents are stated in alphabetical order.

• #1 goes to first-listed substituent.
Two Substituents with the
Same Low Number
If more than one name has the same low number,

choose the name with the next lowest number.
Nomenclature of cycloalkanes
• Monocyclic examples
3
4 2
5 1
6
isopropylcyclohexane 1-ethyl-3-methylcyclohexane
OH
CH2CH3
1
6 2
5 3 1
6 2
4
5 3
4
Cl
2-methylcyclohexanol
4-chloro-2-ethyl-1-methylcyclohexane
• Monocyclic cont.
• When a single cyclic ring is attached to a single chain
with a greater number of carbon atoms or when
more than one cyclic rings are attached to a single
chain, then it is named as cycloalkylalkanes
1,3-dicyclohexylpropane 1-cyclobutylpentane
Nomenclature of Bicyclic Ring Systems
3 main ways that the two rings can be connected.
• First: a fused bicyclic ring structure,
• where the two rings share a covalent bond and a have two
bridgehead carbons (marked in red on the structures below).
• a bridgehead is defined as a carbon that is part of two or more
rings.
• Second: a bridged bicyclic molecule,
• the two rings are connected by a bridge containing one or more
carbons.
• Third: a spiro bicyclic molecule,
• the two rings can be joined with a singe bridge head carbon to
form molecules.
Nomenclature of bicycloalkanes
Hydrogens attached to bridge head
• Bicyclic: carbons are often referred to as bridge
head hydrogens
Bridgehead
carbon atom
Two-carbon bridge Two-carbon bridge
Bridgehead One-carbon bridge

carbon atom bicyclo[2.2.1]heptane
• Bridge lengths are indicated by numbers placed in

square brackets and separated by fullstops; order
is longest bridge  shortest bridge.
Nomenclature of bicycloalkanes
• Bicyclic = contain two fused or bridged rings;
• Parent name = name of alkane which corresponds to
the total number of carbon atoms in the rings,
prefaced with bicyclo-
• Terminology:
– Bridgehead carbons = carbon atoms common to
both rings
– Bridge = a bond or chain of atoms connecting
bridgehead atoms
• Bicyclic cont.
• Numbering begins at one of the two "bridgehead" carbons and
proceeds around the longest bridge to the 2nd bridgehead,
then around the next longest bridge and finally around the
shortest bridge. 2
9
1 3
8
4
6
7 5
8-methylbicyclo[4.3.0]nonane
• If the molecule contains one or more substituents, the
bicycloalkane structure is numbered starting with the
bridgehead which results in the first substituent on the larger
bridge having the lowest number.
Naming Spiro Compounds
• Spiro bicyclics are named using the same basic
rules.
• Because there is only one bridgehead carbon only
two numbers will be required in the brackets.
• Also, the word spiro is placed at the beginning.
Examples
Exercise 1
1)
5-(2-methylpropyl)nonane
2)
4-(1,1-dimethylethyl)-5-ethylnonane
3)
6-(1,2-dimethylbutyl)-5-ethylundecane
Exercise 2
• Give IUPAC names for the following
structures:
CH2CH3 CH3 CH2CH2CH3

CH3CH2CH2CHCHCH2CH2CH3 CH3CH2CHCH2CHCH3
C(CH3)3
Exercise 3
Give IUPAC names for the following structures:
a) b) c) d)
e) f) g)
=
h) i) j)
Exercise 3 - Solved
a) Bicyclo[2.1.1]hexane
b) Bicyclo[3.2.1]octane
c) Bicyclo[2.1.0]pentane (more commonly called "housane")
d) Bicyclo[2.2.2]octane
e) cis-Bicyclo[3.3.0]octane
f) cis-Bicyclo[1.1.0]butane
g) Bicyclo[1.1.1]pentane
h) Bicyclo[4.3.3]dodecane
i) Spiro[5.2]octane
j) Spiro[3.3]heptane
Exercise 4
Draw the structures of the following:
a) Bicyclo[2.1.1]hexane
b) Bicyclo[3.2.1]octane
c) Bicyclo[2.1.0]pentane (more commonly called "housane")
d) Bicyclo[2.2.2]octane
e) cis-Bicyclo[3.3.0]octane
f) cis-Bicyclo[1.1.0]butane
g) Bicyclo[1.1.1]pentane
h) Bicyclo[4.3.3]dodecane
i) Spiro[5.2]octane
j) Spiro[3.3]heptane
Tip: See if you get the same structures as in Exercise 3. PS. DON’T CHEAT!
Nomenclature of Alkanes
C6H14 can be arranged in five ways:

Nomenclature of Alkanes
C7H16 can be arranged in nine ways
Nomenclature of Branched-Chain
Alkanes
• Certain common nomenclatures are used in the
IUPAC system, for example, tert-, sec-, iso-, etc:
Common Names
If hydrogen in an alkane is replaced by the following groups:
Alkyl groups are used to build common names:

n = An Unbranched Chain
Common names sometimes use “n” to

indicate an straight-chain alkane.
If a name does not have a prefix “n”, “iso”, “sec”, or

“tert”, we assume that the carbons are in an
unbranched chain.
Alkenes: Structure & Nomenclature
Nomenclature of Alkenes
Replace “ane” of alkane with “ene.”
The functional group gets the lowest possible number.
© 2014 Pearson Education, Inc.

Molecular Formula and the
Degree of Unsaturation
molecular formula = CnH2n+2 – 2 hydrogens for

every π bond or ring
degree of unsaturation (or Hydrogen deficiency)
= the total numbers of π bonds and rings.
Don’t confuse with
the 2 x π bonds in
a triple bond!!!
Remember you can have molecules which have multiple double bonds (π
bonds) as long as the π-bonds are between different sets of carbons - i.e.
dienes

Week 1-3:
Video 6

Week 1-3:
Video 6a

2 Ways to lock the geometry
1. with a π-bond
2. with a ring

Remember:
A terminal alkene is neither cis nor trans

Week 1-3:
Video 6b

Remember:
A terminal alkene is not cis / trans
and
neither E / Z
Vinylic and Allylic Carbons
vinylic carbon: the sp2 carbon of an alkene

allylic carbon: a carbon adjacent to
a vinylic carbon
Substituents are stated in alphabetical order.


Nomenclature of Cyclic Alkenes
A number is not needed to denote the position

of the functional group;
it is always between C1 and C2.



Double Bonds Have
Restricted Rotation
Rotation about a double bond breaks the π bond.

Alkenes Have Cis–Trans Isomers
cis trans
Cis: The hydrogens are on the same side of the ring.
Trans: The hydrogens are on opposite sides of the ring.
They have different configurations;

they can be separated.
Which Is Cis and Which Is
Trans?
Problematic for alkenes that do not have a hydrogen

attached to each of the sp2 carbons.
The E,Z System of
Nomenclature
Z = Zusammen (together)
E = Entgegen (opposite)
Relative Priorities
The relative priorities of the two groups

depends on the atomic numbers of the
atoms attached to the sp2 carbon.
The greater the atomic number, the higher
the priority.
The E and Z Isomers
If there is a tie, then consider the atomic numbers

of the atoms that are attached to the “tied” atoms.

E and Z
If an atom is doubly bonded to another atom, the

priority system treats it as if it were singly bonded to
two of those atoms.
If an atom is triply bonded to another atom, the
priority system treats is as if it were singly bonded to
three of those atoms.
E and Z
If two isotopes are being compared, the mass number

is used to determine the relative priorities.

Alkynes: Structure &
Nomenclature

Nomenclature of Alkynes
An alkyne is a hydrocarbon that contains a
carbon–carbon triple bond.
General formula: CnH2n–2 (acyclic)
CnH2n–4 (cyclic)

Nomenclature of Alkynes
•The “yne” suffix is assigned the lowest

number.
•The substituents are assigned so the lowest
number is in the name.
Week 1-3:
Video 7

Please note:
The next slide from the video
contains mistakes in numbering the
parent chain.
The triple bond should receive the

lowest number, despite the
presence of alkyl substituents.

The triple bond
should receive the
lowest number,
despite the presence
Correct
numbering of alkyl substituents
Correct name:
6-methyl-2-heptyne
Week 1-3:
Video 8
Naming Alkenes & Alkynes on the Same Compound
ENYNE

Priority is given
to which
functional group
you hit first!!

In this case the alkene
gets the priority!!

The substituent must
have the lowest
number!! Error in Video !!
The alkene gets the lower number even though the
other substituents get higher numbers

A Double Bond and a Triple
Bond

Double and Triple are Tied
When the same number is obtained for both,

the double bond gets the lower number.

Benzene: Structure &
Nomenclature
150
Benzene is an Aromatic
Compound
Benzene is cyclic, planar, and has an

uninterrupted cloud of π electrons.
Benzene is an unusually stable compound.
Benzene Structure
• Molecular formula: C6H6  unsaturated system
• Kekule structure of benzene-conjugated system of double bonds
• Benzene = planar; each carbon is sp2-hybridized

= all carbon-carbon bond lenghts are identical (1.39 Å)
= regular hexagon; H-C-C & C-C-C bond angles  120°
152
Many Substituted Benzenes
are Found in Nature

Some Drugs Have
Substituted Benzene Rings

Substituted Benzene Rings Appear
in Many Commercial Compounds

Some Substituted Benzenes are
Toxic

The Nomenclature of
Substituted Benzenes
some monosubstituted benzenes are

named
just by adding the name of the
substituent to “benzene”
The Nomenclature of
Substituted Benzenes
some monosubstituted benzenes have

names
that incorporate the substituent
Alkyl-Substituted Benzenes
• Name as alkyl-substituted benzenes when the

alkyl group has a name.
• Name as phenyl-substituted alkanes otherwise.
• Toluene (methyl substituent on benzene) is an
exception.

Nomenclature of Disubstituted Benzenes
The relative positions of two substituents can be

indicated
by numbers or by prefixes.
ortho = adjacent
meta = separated by one carbon
para = opposite one another
Nomenclature of Disubstituted
Benzenes
• The substituents are listed in alphabetical order.

• The first substituent is given the 1-position.
• The ring is numbered to give the second substituent
the lowest possible number.
Benzenes
• Some substituents can be incorporated into a

name.
• An incorporated substituent is given the 1-position.
• With a second substituent, “methylbenzene” is
used rather than “toluene.”

Benzenes
Some disubstituted benzenes have both substituents

incorporated into the name.

Nomenclature of
Polysubstituted Benzenes
List substituents alphabetically and number

so that the lowest possible numbers result.
An incorporated substituent is given the 1-position.

Nomenclature of Benzene
derivatives
• Monosubstituted benzene
– Use two systems:
• (i) state name of substituent (as prefix to) parent name
(= benzene)
165
derivatives
• Monosubstituted benzene cont.
• (ii) name of monosubstituted benzene incorporates the
name of substituent:
For example: methylbenzene = toluene
hydroxybenzene = phenol Memorize!!!!!
aminobenzene = aniline
166
derivatives
• Monosubstituted benzene cont.
• Benzene rings with alkyl substituents are named as alkyl
substituted benzene (except toluene) or as phenyl-substituted
alkanes
• When benzene ring is a substituent  phenyl

• Benzene ring with methylene group  benzyl
Phenyl group Benzyl group 167

Week 1-3:
Video 9
Video 9a

Phenyl and Benzyl Substituents

Aryl Means Benzene
or Substituted Benzene
Each of the structures above could be

abbreviated as ArOH.

Exercise 3
• Draw the structure of each of the
following:
(i) 2-phenylhexane
(ii) benzyl alcohol
(iii) 3-benzylpentane
174
derivatives
• Disubstituted benzene
– Use prefixes ortho- (or o-), meta- (or m-), para- (or p-) to
indicate relative position of two substituents on benzene ring
o
o
1,3-dibromobenzene m m
meta-dibromobenzene
m-dibromobenzene p
1,2-dibromobenzene
1,4-dibromobenzene
ortho-dibromobenzene
para-dibromobenzene
o-dibromobenzene
p-dibromobenzene
Ignore the positions of the double bonds in the benzene ring when numbering the ring 175
derivatives
• Disubstituted benzene
• If one of the substituents can be incorporated into a
name, that name is used and the incorporated
substituent is given the 1-posistion
2-chlorotoluene 4-nitroaniline 2-ethylphenol

ortho-chlorotoluene para-nitroaniline ortho-ethylphenol
Ignore the positions of the double bonds in the benzene ring when numbering the ring 176
Benzenes
• Some substituents can be incorporated into a

name.
• An incorporated substituent is given the 1-position.
• With a second substituent, “methylbenzene” is
used rather than “toluene.”

Vinylic and Allylic Carbons
vinylic carbon: the sp2 carbon of an alkene

allylic carbon: a carbon adjacent to
a vinylic carbon
Exercise 4
• Name the following:
• Draw structures of the following:

(i) m-phenylstyrene
(ii) p-divinylbenzene 179
derivatives
• Polysubstituted Benzenes
– If one of the substituents can be
incorporated into a name, that name is
used as the parent name
– If no group imparts a special name then
substituents are numbered so that the
lowest possible numbers are used.
Substituents are listed in alphabetic order
181
Exercise 5
• Draw the structure of each of the
following:
(i) m-dichlorobenzene
(ii) o-nitroaniline
(iii)2,5-dinitrobenzaldehyde
(iv)4-bromo-2,6-difluorotoluene
(v) 2,4,6-trinitrotoluene (TNT)
182

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Week 1-3

Alkanes & Alkenes & Alkynes Aromatic

Saturated hydrocarbons Unsaturated hydrocarbons

An example involving An example involving

cyclopropane cyclobutane cyclopentane cyclohexane cycloheptane

Alkane Alkyl group Abbreviation

1 CH2 group 2 CH2 groups

Homologues differ by a CH2 group.

Remember: Substituents gets the lowest number !!

They have a substituent on a substituent

Primary hydrogens are attached to primary carbons.

When two or more chains have the same length,

• Common names never have numbers.

• Substituents are stated in alphabetical order.

If more than one name has the same low number,

Two-carbon bridge Two-carbon bridge

Bridgehead One-carbon bridge

• Bridge lengths are indicated by numbers placed in

CH2CH3 CH3 CH2CH2CH3

C6H14 can be arranged in five ways:

Alkyl groups are used to build common names:

Common names sometimes use “n” to

If a name does not have a prefix “n”, “iso”, “sec”, or

Replace “ane” of alkane with “ene.”

The functional group gets the lowest possible number.

© 2014 Pearson Education, Inc.

molecular formula = CnH2n+2 – 2 hydrogens for

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

vinylic carbon: the sp2 carbon of an alkene

Substituents are stated in alphabetical order.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

A number is not needed to denote the position

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

Rotation about a double bond breaks the π bond.

They have different configurations;

Problematic for alkenes that do not have a hydrogen

The relative priorities of the two groups

If there is a tie, then consider the atomic numbers

© 2014 Pearson Education, Inc.

If an atom is doubly bonded to another atom, the

If two isotopes are being compared, the mass number

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

•The “yne” suffix is assigned the lowest

© 2014 Pearson Education, Inc.

The triple bond should receive the

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.

When the same number is obtained for both,