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Department of Chemistry & Biochemistry

Chemistry 221 – Introductory Organic Chemistry I

Thursday 18:00 – 21:15; CC-111.


Textbook: Organic Chemistry, 4th Ed.; Jones & Fleming
Instructor: Louis Cuccia
Office: L-SP 275-17
Email: cuccial@alcor.concordia.ca
Course web site: https://www.myconcordia.ca/
Online homework: SmartWork – wwnorton.com/smartwork
Classroom tools: iClickers will be used
Strategic learning leader: William Chu Kwan !
1
Chapter 2
Organic Chemistry – Chemistry of Life and Beyond…..
Synthesis

Functional Groups Reactions Mechanisms


electron
movement

Molecules
formula
shape
name

bonding

Atoms

3
Alkanes – Chapter 2
The electronic configuration of carbon (atomic number 6) is:

1s2 2s2 2p2

2p

2s
1s

4
C: 1s2 2s2 2px1 2py1

2p

2s
1s

5
Hybrid Orbitals
•  The Problem:!
–  We would expect two single bonds to carbon and bonding
by the 2p atomic orbitals would give a bond angle of
approximately 90°.!
–  instead we observe bond angles of approximately 109.5°,
120°, and 180°.!

•  The Solution:!
–  hybridization of atomic orbitals.!
–  2nd row elements use sp3, sp2, and sp hybrid orbitals for
bonding.!

6
Hybrid Orbitals
•  Hybridization of orbitals (L. Pauling).
–  the combination of two or more atomic orbitals
forms a new set of atomic orbitals, called hybrid
orbitals.
•  We deal with three types of hybrid orbitals.
sp3 (one s orbital + three p orbitals).
sp2 (one s orbital + two p orbitals).
sp (one s orbital + one p orbital).
•  Overlap of hybrid orbitals can form two types of bonds.
depending on the geometry of overlap.
σ bonds are formed by “direct” overlap.
π bonds are formed by “parallel” overlap. 7
sp3 hybridization → example: CH4!

The electronic configuration of carbon (atomic number 6) is:

1s2 2s2 2p2

2p

2s
1s
8
Carbon bonding to hydrogen
According to this configuration, carbon has two unpaired
electrons, and should form two bonds with two hydrogen
atoms.

But in methane, carbon is bonded to 4 hydrogens.

4 unpaired electrons are required!

2p

2s
1s

Lowest energy or ground state of C


9
Therefore, the 2s and three 2p orbitals are mixed, or hybridized
together, to yield four equivalent hybrid orbitals.
One s + three p = four sp3 hybrid orbitals.

 The number of hybrid AOs = the number of starting AOs

2p
Hybridize sp3
2s
1s 1s

Lowest energy or ground state of C sp3 hybridized carbon


10
One pure s orbital + Three pure p orbitals

Four hybrid sp3 atomic orbitals

11
4 hybrid sp3 orbitals

sp3 orbitals have their electron density concentrated in one


direction.

Hybrid orbitals are more directional, and thus capable of


stronger bonding (better overlap) than s or p orbitals.

12
hybrid sp3 orbitals

–  each sp3 hybrid orbital has two lobes of unequal size.

–  the sign of the wave function is positive in one lobe,


negative in the other, and zero at the nucleus.

–  the four sp3 hybrid orbitals are directed toward the corners
of a regular tetrahedron at angles of 109.5°
13
4 hybrid sp 3 orbitals

The four sp3 orbitals


each contain 1 electron
and orient themselves
as far apart from each
other as possible - along
the corners of a
tetrahedron.

14
Methane (CH4): the C sp3 hybrid orbitals and the H 1s
orbitals overlap to form σ bonds - tetrahedron shape

The C-H bond energy is 104 kcal/mol - each σC-H lowers the
energy by 104 kcal/mol 15
Consider the molecule ammonia, NH3: 1s2 2s2 2p3

There are four hybrid orbitals and one of the orbitals is filled
with a pair of electrons.!

2p
Hybridize sp3
2s
1s 1s

Lowest energy or ground state of N sp3 hybridized N

Basic geometry is tetrahedral, however lone pairs exercise more repulsion


than bond pairs so the bond angles are 107º (less than 109.5º). 16
When ammonia reacts with an acid such as HCl, the nonbonding
electrons of nitrogen form a σ bond with a proton (H+) which has
an empty 1s orbital.

HCl
+

The resulting ammonium ion (NH4+) has tetrahedral geometry


(109.5) and has an ionic bond to the chloride ion.

17
Water H2O: 1s2 2s2 2p4
There are four hybrid orbitals and two of the orbitals are filled
with a pair of electrons.
2p
hybridize sp3
2s
1s 1s

Lowest energy or ground state of O sp3 hybridized O

Basic geometry is tetrahedral, however lone pairs exercise


more repulsion than bond pairs so the bond angles are 104
(less than 109.5). 18
Bonding in CH4, NH3, and H2O (CN = 4)

19
sp2 Hybrid Orbitals!
One pure s orbital Two pure p orbitals

Three hybrid sp2 atomic


orbitals

20
sp2 Hybrid Orbitals!
One pure s orbital Two pure p orbitals

Three hybrid sp2 atomic


orbitals

21
3 hybrid sp 2 orbitals

The three sp2 orbitals


each contain 1 electron
and orient themselves as
far apart from each other
as possible - along the
corners of a triangle
(trigonal planar).
22
BH3

2p 2p
Hybridize (sp2) sp2
2s
1s 1s

Lowest energy or ground state of B sp2 hybridized boron

H H
B

23
Consider the methyl carbocation, CH3+:

Carbon has three electrons (instead of 4) in its valence shell.

There are a total of 5 electrons.

Three unpaired electrons are required for bonding.

Experimentally, the three C-H bonds are equivalent, therefore


there are three hybrid orbitals.

2p

2s
1s

ground state of C+
24
The methyl carbocation, CH3+
To be as far apart from each other as possible, the three
sp2 orbitals are oriented at the corners of an equilateral
triangle.

Trigonal planar geometry with 120° between the orbitals.

Each orbital contains an unpaired electron that forms a σ


bond to a hydrogen 1s orbital.

The empty pz orbital is perpendicular to the sp2 orbitals.

2p 2pz

2s hybridize sp2

1s 1s
s + px + py
ground state of C+ sp2 hybridized carbocation
25
•  Hydrocarbon: a compound composed only of
carbon and hydrogen.

•  Saturated hydrocarbon: a hydrocarbon


containing only single bonds.

•  n-alkane: a saturated hydrocarbon whose


carbons are arranged in an extended chain.

•  Aliphatic hydrocarbon: another name for an


alkane.

26
Connectivity
The connectivity in a molecule describes which atoms are
attached to others.
One compound has one and only one connectivity (or structure).

One molecular formula can give rise to many possible structures,


BUT one structure has one and only one molecular formula.

Compounds with the same molecular formula but different


structural formulas are called ISOMERS.

CONSTITUTIONAL ISOMERS differ in the the order and


the way in which the atoms are bonded together.

STEREOISOMERS have the same connectivities - they


differ only in the arrangement of their atoms in space.
27
Name Formula Structural Formula Structure

methanol CH4O CH3OH

pentane C5H12 CH3(CH2)3CH3

2-methylbutane C5H12 CH3CH2CH(CH3)CH3

Pentane and 2-methylbutane have the


same formula, but different structures.

pentane and 2-methylbutane are constitutional isomers


28
Alkanes
CH4 METHANE
CH3CH3 ETHANE
CH3CH2CH3 PROPANE
CH3CH2CH2CH3 BUTANE

Greek prefixes
After the first four members, the name is derived from
the Greek prefixes for the number of carbon atoms.

29
molecular condensed structural name
formula formula
CH4 CH4 METHANE
C 2H 6 CH3CH3 ETHANE
C 3H 8 CH3CH2CH3 PROPANE
C4H10 CH3CH2CH2CH3 BUTANE
C5H12 CH3(CH2)3CH3 PENTANE
C6H14 CH3(CH2)4CH3 HEXANE
C7H16 CH3(CH2)5CH3 HEPTANE
C8H18 CH3(CH2)6CH3 OCTANE
C9H20 CH3(CH2)7CH3 NONANE
C10H22 CH3(CH2)8CH3 DECANE
C11H24 CH3(CH2)9CH3 UNDECANE
30
Structure!
Carbon is tetravalent - it has four covalent bonds to other atoms.
Hydrogen is monovalent - it has one bond to another atom.
A hydrocarbon with n carbon atoms can hold a maximum of 2n+2
hydrogen atoms.

These are known as saturated hydrocarbons: CnH2n+2

Pentane has a molecular formula: C5H12

If a hydrocarbon has less than 2n+2 hydrogen atoms then there are
cyclic and/or atoms bonded to each other by more than one bond
(multiple bonds).
31
Alkanes

Alkanes are saturated hydrocarbons (all single bonds) with the


general formula CnH2n+2

removal of a hydrogen atom from an alkane gives rise to an alkyl group

32
Representations of n-hexane
Condensed formula: C6H14

Lewis structure

Line structures or skeletal


structural formula

Each junction of two straight 3D structures


Wedges and dashed
lines (or the end of a straight lines are used to
line) represents a carbon atom indicate orientation of
and the number of hydrogen groups in space.
atoms necessary to give the
wedges: coming out
carbon four bonds. dashes: going back

Ball-and-stick representation

33
What is the correct condensed formula of the following
molecule?

A) CH3CH2CHBrCHO
B) CH3CH2BrCHCOOH
C) CH3CH2CHBrCO2H
D) CH3CH2CBrCO2H
35
Arrow pushing
H

H H

H H

Neither formula is an accurate picture of benzene.

The double bonds in benzene are not fixed in position and the
electrons of the double bonds are delocalized over the entire
ring → ʻresonanceʼ.! 36
Conformation

•  Conformation: any three-dimensional


arrangement of atoms in a molecule that
results from rotation about a single bond.

•  Newman projection: a way to view a


molecule by looking along a carbon-
carbon bond.

37
conformations of ethane

eclipsed conformation

The conformations of a molecule are different arrangements in space


of the atoms within the molecule due to rotation around single bonds.

The eclipsed conformation has all the carbon-hydrogen bonds lined


up. This is the maximum energy conformation. 38
conformations of ethane

39
conformations of ethane

40
conformations of ethane

41
conformations of ethane

42
conformations of ethane

staggered conformation

The staggered conformation has the bonding electrons of the carbon-


hydrogen bonds as far apart as possible.

This is the lowest energy conformation.


43
conformations of ethane

44
conformations of ethane

45
conformations of ethane

46
conformations of ethane

47
conformations of ethane

48
The relative positions of the hydrogen atoms on
the two carbon atoms are best represented with
a Newman Projection.

49
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a dot,
and the carbon in the back is represented by a circle.
50
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a
dot, and the carbon in the back is represented by a circle.
51
A Newman projection

52
53
54
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a dot,
and the carbon in the back is represented by a circle.
55
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a
dot, and the carbon in the back is represented by a circle.
56
A Newman projection

57
58
59
Staggered conformation

60
60° dihedral angle
0° dihedral angle

staggered conformation eclipsed conformation

A Newman projection allows the visualization of the spacial


relationship between atoms bonded on adjacent carbon atoms.

The dihedral angle (θ) is the angle between groups on adjacent


carbon atoms as viewed in the Newman projection formula.

61
60° dihedral angle
0° dihedral angle

62
•  Staggered conformation: a conformation of a
carbon-carbon single bond where the atoms
on one carbon are as far apart as possible
from the atoms on the adjacent carbon.

63
•  Eclipsed conformation: a conformation of a
carbon-carbon single bond where the atoms
on one carbon are as close as possible to the
atoms on the adjacent carbon.

64
Energetics for ethane

The difference in energy between the staggered and


eclipsed conformation of ethane is about 3 kcal/mol.

65
Energetics for ethane
•  Torsional strain: the force that opposes the rotation
of one part of a molecule about a bond while the
other part of the molecule is held fixed.

•  the torsional strain between eclipsed and staggered


ethane is approximately 3.4 kcal/mol.

3.4 kcal/mol

66
Energetics for ethane

67
eclipsed

68
eclipsed

Ball-and-stick Space-filling

A 60° rotation converts the eclipsed conformation into the


staggered conformation
69
staggered

70
staggered

Ball-and-stick Space-filling

71
•  At room temperature, molecules have
enough kinetic energy to get over barriers as
high as 20 kcal/mol.

•  Therefore at room temperature, rotation


around the C-C bond in ethane is constant.

•  But the molecules spend most of their time in


the more favorable staggered conformations.

72
consider butane
CH3CH2CH2CH3

The most stable conformation has a


dihedral angle of 180° between the
methyl groups.

This staggered conformation is


called the anti-conformation
73
consider butane
CH3CH2CH2CH3

74
Butane, CH3CH2CH2CH3

• There are two other staggered conformations possible


for butane where there is a dihedral angle of 60°
between the methyl groups.
• These are called gauche conformations.
• butane gauche conformation → nonbonded interaction
strain is approx. 0.8 kcal/mol.
75
There are two different eclipsed
conformations for butane

methyl eclipsed with methyl methyl eclipsed with hydrogen

76
Forces involved in conformational preferences
•  Weak attraction/repulsion that exists between nonpolar molecules
are known as van der Waals interactions.

•  These forces are the result of the motion of electrons within bonds
and molecules.

•  The motion of electrons creates small distortions in charge


distribution resulting in temporary induced dipoles.

•  The effective size of molecules are represented in terms of van der


Waals radii for each atom. (molecules are not balls and sticks, but
rather space-filling).

•  When molecules (or parts of the same molecule) are not too close,
attractive van der Waals interactions can occur.

•  However, if the distance is too short (less than the van der Waals
radii of the interacting atoms, repulsive (unfavourable) van der
Waals interactions occur. 77
Butane

Eclipsed Eclipsed

78
Ethane

Replace two protons in methane to get butane


79
Butane conformations

80
Butane conformations
energy diagram

81
Butane conformations
energy diagram

82
Butane conformations
energy diagram

83
Butane conformations
energy diagram

84
Butane conformations
energy diagram

85
Butane conformations
energy diagram

86
Butane conformations
energy diagram

87
Butane conformations
energy diagram

88
Butane conformations
energy diagram

eclipsed form 89
Butane conformations
energy diagram

90
Butane conformations
energy diagram

91
Butane conformations
energy diagram

92
Butane conformations
energy diagram

93
Butane conformations
energy diagram

94
Butane conformations
energy diagram

gauche form 95
Butane conformations
energy diagram

96
Butane conformations
energy diagram

97
Butane conformations
energy diagram

98
Butane conformations
energy diagram

99
Butane conformations
energy diagram

100
Butane conformations
energy diagram

101
Butane conformations
energy diagram

102
Butane conformations
energy diagram
5 kcal/mol

fully eclipsed form 103


Butane conformations

104
Butane conformations

105
Butane conformations

106
Butane conformations

107
Butane conformations

108
Butane conformations

gauche form 109


Butane conformations
At room temperature, molecules have enough kinetic
energy to get over barriers as high as 20 kcal/mol.

Therefore at room temperature, there is rapid


interconversion between conformations in butane.

At room temperature, about 25% of butane molecules


are in gauche conformations, and 75% in the anti
conformation.

110
Energetics for butane

[anti]/[gauche] = 4

111
Which Newman projection represents that of butane, viewed along the C2-C3
bond with a dihedral angle of 60º?

A)  B)

C) D)
Hydrocarbons
space-filling models
Alkanes have the general formula CnH2n+2!

1 10
Compounds that differ from each other in their molecular formulas
by the unit -CH2- are members of a homologous series. 113
All alkanes have similar chemical properties, but their
physical properties vary with molecular weight and and the
shape of the molecule
The boiling points of linear alkanes increase steadily with
molecular weight.

The weak forces of attraction that exist between non-polar


molecules are called van der Waals attractive interactions.

These forces are the result of the constant motion of


electrons within the bonds and molecules.

These motions can create small momentary dipoles that can


subsequently induce a momentary dipole of the opposite
direction in a neighboring molecule (induced dipole).

The favorable interaction of induced dipoles causes a slight


attraction between molecules.
114
As the alkane length increases, the amount of intermolecular interactions
between molecules can increase - more favorable van der Waals interactions.
115
Constitutional isomers differ in the the order and the
way in which the atoms are bonded together.
For example: C5H12

straight-chain branched-chain

n-pentane 2-methylbutane 2,2-dimethylpropane


bp 36.1 °C bp 27.9 °C bp 9.5 °C
mp -129.7 °C mp -159.9 °C mp -16.6 °C

n-alkanes - n stands for normal (i.e. linear)

Q. How can you account for the differences in boiling points?


A. Van der Waals interactions
116
Van der Waals interactions

117
Constitutional Isomerism!

118
Nomenclature - IUPAC!
  Suffix -ane specifies an alkane!
  Prefix tells the number of carbon atoms!

119
methane, CH4

condensed Lewis 3D representation space-filling


formula structure representation

All hydrogen atoms on the carbon are equivalent.


The clouds on the space filling representation is known as the van
der Waals radii.
If goups are too crowded in a molecule, unfavorable nonbonding
interactions known as van der Waals repulsions occur.
120
ethane, C2H6

condensed Lewis 3D representation space-filling


formula structure representation

All hydrogen atoms in ethane are equivalent

chloroethane chloroethane chloroethane chloroethane

Different representations of chloroethane - all four structural formulas


represent the SAME molecule. They all have the same connectivity. 121
There are two DIFFERENT ways to replace two hydrogen
atoms with two chlorine atoms:

1,1-dichloroethane 1,2-dichloroethane

These compounds are constitutional isomers - the same


molecular formula, but different connectivities.

They have different physical properties (m.p., b.p.,


dipole moment….)

122
Propane, C3H8

condensed Lewis 3D representation space-filling


formula structure representation

two primary carbons and one secondary carbon.


123
Classification of C and H!
•  Primary (1°) C: a carbon bonded to one other carbon.
–  1° H: a hydrogen bonded to a 1° carbon.

•  Secondary (2°) C: a carbon bonded to two other carbons.


–  2° H: a hydrogen bonded to a 2° carbon.

•  Tertiary (3°) C: a carbon bonded to three other carbons.


–  3° H: a hydrogen bonded to a 3° carbon.

•  Quaternary (4°) C: a carbon bonded to four other carbons.

124
Same classification for amines!
•  Primary (1°) amine: nitrogen bonded to one carbon.
–  R-NH2 e.g. CH3NH2 methylamine

•  Secondary (2°) amine: nitrogen bonded to two carbons.


–  R2NH e.g. (CH3)2NH dimethylamine

•  Tertiary (3°) amine: nitrogen bonded to three carbons.


–  R3N e.g. (CH3)3N trimethylamine

•  Quaternary (4°) ammonium ion: nitrogen bonded to four carbons.


–  R4N+ e.g. (CH3)4N+Cl- tetramethylammonium chloride

125
Butane, C4H10

condensed Lewis 3D representation space-filling


formula structure representation

two primary carbons and two secondary carbons.


126
C4H10

the central carbon is a tertiary carbon.

2-methyl-propane

127
CH3-H = methane
CH3- = methyl
CH3-CH3 = ethane
CH3-CH2- = ethyl

CH3-CH2-CH3 = propane
CH3-CH2-CH2- = propyl

CH3-CH2-CH2-CH3 = butane
CH3-CH2-CH2-CH2- = butyl
128
IUPAC

International Union of Pure


and Applied Chemistry

129
IUPAC SYSTEM OF NAMING COMPOUNDS
1. Select the longest continuous chain of carbon atoms for
the basic name.
2. Number the carbons in the chain from the end nearest the
first branch.
3. Identify substituents (e.g. methyl, ethyl, bromo, chloro). If
more than one substituent of the same kind is present, use
the prefixes “di,” “tri” or “tetra.”
4. Locate the substituents by the number of the carbon to
which they are attached.
5. Put substituents in alphabetical order (prefixes (di, tri,
tetra, n-, sec-, tert-, do not count).
6. Use commas to separate numbers and separate numbers
from letters by a dash and write the whole name as one word
with the basic name at the end. 130
6 4 2
5 3 1

3-methylhexane
131
1 2 3 4 5

pentane
2-methylpentane
132
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8

decide longest chain


number the carbon atoms
133
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8

5-ethyl-2,3-dimethyloctane

134
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8

5-ethyl-2,3-dimethyloctane

135
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8

5-ethyl-2,3-dimethyloctane

136
7 6

3 4 5
4 1
5 6

1 2
7 3 2

In finding the longest straight chain of carbons,


it is often necessary to count around corners.

The chain is numbered so as to produce the


smallest number for a substituent.
heptane
3,4-dimethylheptane 137
8
7

6
5
4 2
3
1

octane
3,5-dimethyloctane
4-ethyl-3,5-dimethyloctane 138
2
3 1

9 8 7 6 5 4

nonane

3-methyl nonane

3-methyl-4-propylnonane

139
line structure

6 5 4 3 2
1

hexane

tetramethylhexane

2,2,3,4-tetramethylhexane
140
•  Number chain to make substituent locator numbers
as low as possible

141
What is the IUPAC name of the following compound?

A) 2,3-dimethyloctane
B) 2,3,6-trimethylheptane
C) 2,3,6-methylheptane
D) 2,5,6-trimethylheptane
E) both B and D
Provide an IUPAC name for the following:

A) 4-ethyl-4-methylhexane
B) 2,2-diethylpentane
C) 3-ethyl-3-methylhexane
D) 3-methyl-3-propylpentane
Cycloalkanes!
Cycloalkanes are cyclic hydrocarbons with the general formula CnH2n

145
Representations of cyclohexane!

3D structure line structure

146
Cycloalkanes
•  General formula CnH2n.
–  five- and six-membered rings are the most common.

•  Structure and nomenclature.


–  to name, prefix the name of the corresponding open-chain
alkane with cyclo-, and name each substituent on the ring.

–  if only one substituent, no need to give it a number.

–  if two substituents, number from the substituent of lower


alphabetical order.

–  if three or more substituents, number to give them the lowest


set of numbers and then list substituents in alphabetical
order.
CH3

methylcyclohexane

148
1-bromo-3-tert-butylcyclohexane
1-bromo-3-t-butylcyclohexane
149

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