What is Organic Chemistry?

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 Organic Compounds

Proteins
Hormones
O R O R O
H H OH
H 2N N N
N N OH
H H H
R O R O R
Nucleic Acids H H
Peptide NH2 HO
Estradiol
N

N O
Carbohydrates
H OH
HO O Vitamins
HO H H HO
O H H
HO O
HO H HO O
H OH O P O-
H OH O-
HO OH
Glucose Cytosine
Ascorbic acid

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 VITAL FORCE?

Urea Synthesis in 1828 by Friedric Wohler (only 28 yrs old)

O
NH4+ NCO- H C H
N N
Ammonium cyanate
H H
Urea
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 Organic Synthesis

Pharmaceuticals and cosmetics

O O
Fertilizers
OH O O

N N H 2N N N NH2
H H
HN
Isobutylidene diurea
Ciprofloxacin

Materials Detergents
O O
S O
O O
n
n Sodium Laureth Sulfate
Polyphenylene vinylene (PPV)

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Ch1. Review

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Organic chemists’ P-table:

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Models of Covalent Bonding

1. Lewis structures
2. Valence Bond
3. Molecular Orbital Theory

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7
Lewis Structure and the Octet

H C N O F

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Draw the Lewis structures of ethanol (C2H6O) and
methylamine (CH5N).

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Constitutional Isomers

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10
Formal Charge
If an atom in an ion or molecule has a non-zero charge, you must
indicate its formal charge.

Group Number — number of bonds — lone-pair electrons

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Indicate any formal charge(s).

H C H O N O
H

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12
Shapes around Carbon

H H
C C H C C H
H H

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Valence Bond Model

a s bond

a p bond

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 15
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Hybridization

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Valence Bond model of Methane

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 C2H4
Ethene (Ethylene)

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Build a model
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 20
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Ethyne (Acetylene)
C2H2

Participation: Build a model of methane, ethane and ethyne. Bring to class.

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Molecular Orbital (MO) Theory

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Molecular Orbital (MO) Theory

A mathematical treatment 23
Molecular Orbital (MO) Theory

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Bond Length and Strength

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(1) Verify that p is weaker than s bond.
(2) The C–H bond is the strongest in acetylene,
followed by than ethylene and ethane. Explain.
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Polarity
UNEQUAL distribution of electron density.

d+ d-

H F

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Polarity and Induction

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Polarity, Intermolecular Forces & Physical Properties

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Polarity, Intermolecular Forces & Physical Properties

OH

H 3C CH3

Bp?

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Dispersion

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Dispersion

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Decane Bp: 174.1°

OH
Acetic acid Bp: 117.9°C

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Soap

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Molview:
https://molview.org/
Build stearic acid and oleic acid.
Try different representations under ‘Models’.
Draw one representation for yourself.

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 Ch2.
Molecular Representations

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Line Structures

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Line structure

What are shown and what not?

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 2 4 6
1 3 5
Backbone is written as a zigzag line

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1 3 3
4 2
2 straight triple bond
1

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Write the molecular formulae.

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Other Representations

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3D Representations

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Practice

Br
HO
*

(1) Formula:
(2) C*: which group is pointing into the paper?
(3) Number of Csp2 and number of p bonds:

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Functional Groups

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1. List FGs that contain a single oxygen
2. List FGs that contain a single nitrogen?
3. List FGs that contain at least one Csp2 carbon?

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Carbon Atoms with Formal Charges
Formal charges must be shown.

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Formal Charges of O and N atoms

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Resonance
Multiple Lewis structures to represent the actual structure.

H 3C O

Acetate Ion

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Resonance forms are not switching back and forth.

Use the correct arrow.

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We use curved arrows to relate the resonance
structures.

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tudy of organic chemistry therefore requires a thorough mastery of dra
nd the following sections are designed to foster the necessary skills.
Curved Arrows

rved Arrows
We will use curved arrows to show electrons movement.
on, we will focus on curved arrows, which are the tools necessary to
• The
operly. arrow
Every starts
curved arrowwhere theand
has a tail electrons
head: are currently
located
Tail Head

ws used for drawing resonance structures do not represent the motion of

• The arrow ends where the electrons will end up after
ools that allow us to draw resonance structures with ease. These tools treat
the electron movement
moving, even though the electrons are actually not moving at all. In Ch
urved arrows that actually do represent the flow of electrons. For now, ke
rows in this chapter are just tools and do not represent a flow of electron
ential that the tail and head of every arrow be drawn in precisely the p
The sooner you master this skill, the easier the course will be.
ws where the electrons are coming from, and the head shows where 54
th
How to Draw Resonance Structures

1. Draw the same nuclei positions.

2. Draw in the first bonds (always s).
3. Move only p or lone pair electrons, with curve
arrows.
Do not break the Octet Rule
Do not break a single bond
4. Check formal charges and overall charge.

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 Resonance Pattern Recognition

BOLO: p bonds and positions next to p bonds.

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Allylic lone pair and Allylic carbocation

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Benzylic lone pair and carbocation

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Lone pair adjacent to a carbocation

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A p bond (between atoms of different
electronegativity)

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Conjugated p bonds (in a ring)

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Resonance Practice

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 Assessing Resonance Structures

o Typically, not all the resonance structures will

contribute equally to the hybrid (actual) structure).
o The following rules, listed in order of importance, allow
us to determine the MAJOR resonance form.

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RULE 1: The most significant resonance forms
have the greatest number of filled octets.

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 atom bearing a +2 or −2 charge is highly unlikely. In the example belo
ce form is the best Lewis structure and the largest contributor to the hybr
lled octets and no formal charges. The second resonance form is still a m
since Rule 2: The
it has filled structure
octets, with
but it is less fewer than
significant formal
the first because it
charges
The third resonanceisform
more is asignificant.
minor contributor because it has a carbon
octet
⊕
NH2 NH2 ⊝
NH2 ⊝
H C NH H C NH H C NH
⊕

Largest contributor Major contributor Minor contributor

where there is an overall net charge, as seen in the example below, the creat
is not favorable. For such charged compounds, the goal in drawing resonance
e the charge – relocate it to as many different positions as possible.
⊝ ⊝
O O O
⊝ ⊝
CH3 C CH2 CH3 C CH2 CH3 C CH2
⊕
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 NH2 NH2 ⊝
NH2 ⊝
H C NH H C NH H C NH
⊕

If the compound
Largest contributor has an overall
Major formal charge,
contributor focus
Minor contributor

only on drawing resonance forms that show the

s where there is an overall net charge, as seen in the example below, the creation
delocalization of the charge.
s is not favorable. For such charged compounds, the goal in drawing resonance for
ze the charge – relocate it to as many different positions as possible.
⊝ ⊝
O O O
⊝ ⊝
CH3 C CH2 CH3 C CH2 CH3 C CH2
⊕

Insignificant
resonance
Delocalized negative charge

things being equal, a structure with a negative charge on the more electronegative
more significant. To illustrate this, let’s revisit the previous example, in which t
nificant resonance forms. The first resonance form has a negative charge on oxyge
ond resonance form has a negative charge on carbon. Since oxygen is more electro
arbon, the first resonance form is the major contributor:
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 Insignificant
. Other things being equal, a structure with a negative charge on the
Delocalized negative charge
more electronegative
resonance element
will be more significant. To illustrate this, let’s revisit the previous example, in which there are
two things
significant resonance
equal, aforms. The first
withresonance form has aon
negative charge on oxygen, while
Other
willthe
Rule 3: a structure with a negative charge on
besecond
being
resonance form
more significant.
structure
Tohas a negative
illustrate
a negative
this,charge
charge
on carbon.
let’s revisit
the more
Since oxygen
the previous
electronegative element
is moreinelectronegative
example, which there are
twothan the more electronegative atom will be more
carbon, resonance
significant the first resonance
forms. Theformfirst
is the major contributor:
resonance form has a negative charge on oxygen, while
significant, and vice versa O
the second resonance form has a negative charge on carbon. Since oxygen is more electronegative
⊝
than carbon, the first resonance formO is the major contributor: ⊝
CH3 C CH2 CH3 C CH2
⊝
Major contributor
O Minor contributor
O
⊝
CH3 C CH2 CH3 C CH2
Similarly, a positive charge will be more stable on the less electronegative element. In the follow-
ing example, both resonance forms
Major have filled octets,Minor
contributor so wecontributor
consider the location of the positive
charge. Nitrogen is less electronegative than oxygen, so the resonance form with N+ is the
Similarly, a positive charge will be more stable on the less electronegative element. In the follow-
major contributor:
ng example, both resonance forms have filled octets, so we consider the location of the positive
charge. Nitrogen is less electronegative
H
O
⊕ than oxygen, Hso Othe resonance form with N+ is the
major contributor: H ⊕ H
N N
H ⊕ H H H
O
Minor contributor
O
Major contributor
H ⊕ H
N N
H H
Minor contributor Major contributor 67
ectron-rich site
CH3 C NH2
δ+ δ+

Practice the Skill 2.26: Draw the Electron-deficient

significant resonance
sites
forms for
tes
each compound below, and indicate the major resonance form.
kill 2.26

⊝
NH
O
⊝
O
(a) (b) (c) O
(c) O
H
O H N
H CH3 C C N
(d ) N (e) ⊝ (f ) ⊕

(f ) ⊕
2.27

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 Resonance structures Resonanc

In the first resonance structure, the bond between the left carbon
Resonance
is a double 2.12Stabilization
bond.TheBut
Resonance Hybrid
in the second resonance structure, that 79 same
Likewise, the bond between the right carbon atom and the mid
Resonance in one resonance structure and a double bond in the other reso
Hybrid
• Spreading of electrons over a larger space is called
hybrid, each of these bonds is shown with one solid line and on
n 2.7 thatdelocalization.
chemists draw resonance
actual structure structures
of this cationtoisdeal with the inadequacy
a combination of bond-
of the individual
o matter•how many
that areresonance
Delocalization somewherestructures
is a betweenare drawn,
stabilizing they
singlefactorcollectively
bonds to
and represent
molecules
double only Over
and
bonds.
ntity, often called the resonance hybrid, is a combination of the individual resonance
ions.
nance hybrid
that the π bond is delocalized between all three carbon atoms in
can be drawn by using partial bonds and partial charges to illustrate
of electrons.is As
consistent with MO theory for the allylic cation. The car-π electro
• A ’resonance stabilized cation’ is typically more
an example, let’s consider the resonance hybrid for an allylic
orbital
hat this cation (Figure
has two 2.4),structures.
resonance which isThese
spread out over
resonance all three
structures arecarbon
shown atom
stable.
drawing that depicts the resonance hybrid.

⊕ ⊕
δ+ δ+
Resonance structures Resonance hybrid

nce structure, the bond between the left carbon atom and the middle carbon atom
Next, resonance
But in the second let’s consider the formal
structure, charge
that same bond isindepicted
the hybrid. Thebond.
as a single central
69 ca
Resonance Stabilization: Delocalized p system

“Delocalized p bond and charge”

More stable

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If a lone pair participates in resonance, then it is
occupies a ________ (orbital).

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