Lecture 1

INTRODUCTION TO
ORGANIC CHEMISTRY

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INTRODUCTION TO ORGANIC CHEMISTRY
• Valence bond theory
• Hybridization (sp3, sp2, sp), hybridization of N, O, P, S
• Drawing organic structures (condensed and skeletal
structures)
• EN, Polarity
• Formal charge, Resonances
• Intermolecular forces

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 Organic Chemistry
• Study of carbon compounds
• > 50 million known chemical compounds contain C
• C: group 4A
• 4 valence electrons forms 4 covalent bonds
• Able to bond with one another to form long chains and
rings (C-C)
• The only element that has the ability to form immense
diversity of compounds

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Valence Bond Theory

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 Valence Bond Theory
# bonds = 8 - #Valence Electron
• C: 4e (2s2 2p2) 4 bonds
• N: 5e (2s2 2p3) 3 bonds
• O: 6e (2s2 2p6) 2 bonds
• F, Cl, Br, I: 7e (ns2 np5) 1 bonds

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 Non-Bonding Electrons
• Lone pair - Valence electrons not used in bonding
• Example
• Nitrogen atom in ammonia (NH3)
• Shares six valence electrons in three covalent bonds
• Two valence electrons are nonbonding lone pair

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 Hybridizations of Carbon in organic compounds

• sp3 (alkanes)
• sp2 (C=C of alkenes)
• sp (C=C of alkynes)

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sp3 hybridization of C atom in Methane

• Carbon has 4 valence electrons (2s2 2p2)

• In CH4, all C–H bonds are identical (tetrahedral)
• sp3 hybrid orbitals: s orbital and three p orbitals
combine to form four equivalent, tetrahedrally
oriented orbitals

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 Methane structure
• sp3 orbitals in a C atom overlap with 1s orbitals of
an H atom to form four identical C–H bonds
• Each C–H bond has a strength of 439 kJ/mol and a
length of 109 pm
• Bond angle: Formed between two adjacent bonds

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 Ethane structure
• Two C’s bond to each other by σ overlap of an sp3
orbital from each
• Three sp3 orbitals on each C overlap with H 1s
orbitals to form six C–H bonds
• C–H bond strength in ethane is 421 kJ/mol
• C–C bond is 154 pm long and strength is 377 kJ/mol
• Bond angles of ethane are tetrahedral

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Ethane structure

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 Practice
• Draw a line-bond structure for propane, CH3CH2CH3
• Predict the value of each bond angle, and indicate the
overall shape of the molecule

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 Practice
• Draw a line-bond structure for propane, CH3CH2CH3
• Predict the value of each bond angle, and indicate the
overall shape of the molecule
• Solution:

• Geometry - Tetrahedral
• Bond angles - 109°(approximately)
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 sp2 hybridization of C in Ethylene

• sp2 hybrid orbitals: Derived by combination of an s

atomic orbital with two p atomic orbitals
• sp2 orbitals are in a plane with an angle of
120°from each other
• Remaining p orbital is perpendicular to the plane

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 Structure of Ethylene
• C=C bond: 2 sp2 σ bond; 2 p orbitals pi bond
• 4 H atoms form s bonds with 4 sp2 orbitals

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 Practice
• Draw electron-dot and line-bond structures of
formaldehyde
• Indicate the hybridization of the carbon orbitals

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 Practice
• Draw electron-dot and line-bond structures of
formaldehyde
• Indicate the hybridization of the carbon orbitals
• Solution:
• Two hydrogens, one carbon, and one oxygen can
combine in one way

• The orbitals are sp2-hybridized

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sp Hybridization

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 Orbitals of Acetylene
• 2 sp σ bond
• pz–pz pi bond; py–py pi bond

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 Bonding in Acetylene
• Sharing of six electrons forms triple bond CC
• Two sp orbitals form  bonds with
hydrogens
• Shortest and strongest carbon–carbon bond

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 Practice
• Draw a line-bond structure for propyne, C3H4
• Indicate the hybridization of the orbitals on each carbon
• Predict a value for each bond angle

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 Practice
• Draw a line-bond structure for propyne, C3H4
• Indicate the hybridization of the orbitals on each carbon
• Predict a value for each bond angle
• Solution:

• Bond angle
Between three carbon atoms is 180°
H–C1≡C2 is 180°
Between hydrogen and the sp3-hybridized carbon is 109°
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Hybridization of N, O, P, and S

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 Practice
• Identify all nonbonding lone pairs of electrons in the
oxygen atom in dimethyl ether, CH3–O–CH3
• What is its expected geometry

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 Practice
• Identify all nonbonding lone pairs of electrons in the
oxygen atom in dimethyl ether, CH3–O–CH3
• What is its expected geometry
• Solution:

• The sp3-hybridized oxygen atom has tetrahedral

geometry
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 Drawing Organic Structures
• Several shorthand methods have been developed
to write structures
• Condensed structures: C-H or C-C single bonds are
not shown, they are understood
• Example

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Kekulé vs Skeletal Structures

Atoms other than carbon

and hydrogen are shown

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 Practice
• How many hydrogens are bonded to each carbon in
the following compound
• Give the molecular formula of each substance

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 Practice
• How many hydrogens are bonded to each carbon in
the following compound
• Give the molecular formula of each substance

• Solution:

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 Electronegativity (EN)
• Intrinsic ability of an atom to attract the shared electrons in a covalent bond
• Differences in EN produce bond polarity

• F (EN = 4.0), Cs (EN = 0.7) C (EN = 2.5)

• Metals on left side of periodic table attract electrons weakly
• Halogens and other reactive nonmetals on right side attract electrons strongly
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 Electronegativity and polarity

C–H bonds are relatively nonpolar

C–O, C–X bonds are polar
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 Electrostatic Potential Maps

• Show calculated charge

distributions
• Colors indicate
electron-rich (red) and
electron-poor (blue)
regions
• Arrows indicate
direction of bond
polarity

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 Example
• Which element in each of the following pairs is
more electronegative?
• (a) Li or H
• (b) Cl or I

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 Example
• Which element in each of the following pairs is
more electronegative?
• (a) Li or H
• (b) Cl or I
• Solution:
• (a) Li (1.0) is less electronegative when compared to H
(2.1)
• (b) Cl (3.0) is more electronegative when compared to I
(2.5)

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 Polarity and Dipole Moments
• Polarity is represented by Dipole moment: measured in debyes, D
• 1 D = 3.336 x 10-30 coulomb meter

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 Absence of Dipole Moments

• In symmetrical molecules, the dipole moments of

each bond have one in the opposite direction
• The effects of the local dipoles cancel each other

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 Example
• Draw three-dimensional drawing of H2C=CH2
molecules
• Predict whether it has dipole moment

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 Example
• Draw three-dimensional drawing of H2C=CH2
molecules
• Predict whether it has dipole moment
• Solution:
• Drawing an arrow that points from the least
electronegative element to the most electronegative
element
•

Has zero dipole moment

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 Formal Charges
• Formal charge is the charge an atom would have if all bonding
electrons were shared equally between the bonding atoms
(ignore EN)
• Calculate formal charge
Formal charge = # (valence e) - # (unshared e) – # (bonds)
Formal Charge of some common organic spieces

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 Example
• Calculate formal charges on the four O atoms in the
methyl phosphate dianion

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 Example
• Calculate formal charges on the four O atoms in the
methyl phosphate dianion

• Solution:
For oxygen 1,2: 0

For oxygen 3,4: -1

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 Curved Arrows (see additional reading)*
• Bond formation or breakage can be symmetrical or unsymmetrical
• Symmetrical cleavage – Homolytic; 1 e movement
• Unsymmetrical cleavage – Heterolytic; 2 e movement

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 Rules for Using Curved Arrows
• Electrons move from a nucleophilic source to an
electrophilic sink

• The nucleophilic site can be neutral or negatively charged

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 Rules for Using Curved Arrows
• The electrophilic site can be neutral or positively charged

• The octet rule should be followed

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 Resonance (see additional reading)*
• Some molecules have structures that cannot be
shown with a single representation
• Such structures have delocalized pi bond and are
represented by resonance forms
• Resonance leads to stability

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 Example
• Benzene (C6H6) has two resonance forms with
alternating double and single bonds
• The “real” structure is a hybrid of the two individual forms
• All six carbon–carbon bonds are equivalent

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 Rules for Resonance Forms
• Only differ in the placement of their pi or nonbonding electrons
• Curved arrow indicates movement of electrons, not of the atoms

• Different resonance forms of a substance do not have to be equivalent

• When two resonance forms are nonequivalent, the actual structure
of the resonance hybrid resembles the more stable form
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 Allyl type resonances
• Any three-atom grouping with a p orbital on each
atom has two resonance forms

• Resonance forms differ by an exchange in position of the

multiple bonds and the asterisk
• From one end of the three-atom grouping to the other
• Recognizing three-atom groupings within larger structures
help generate resonance forms, symmetrically
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 Example
• Draw the indicated number of resonance forms for:
• The allyl cation, [H2CCHCH2]+ (2)

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 Example
• Draw the indicated number of resonance forms for:
• The allyl cation, [H2CCHCH2]+ (2)
• Solution:
• Locating three-atom groupings that contain a multiple
bond next to an atom with a p orbital
• Exchanging the positions of the bond and the electrons
in the p orbital, we have:

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 2,4-Pentanedione Anion
• Has a lone pair of electrons
• Has a formal negative charge on the central carbon
atom, next to a C═O bond on the left and on the
right
• Has three resonance structures

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 Intermolecular forces

• Noncovalent interactions: One of a variety of

nonbonding interactions between molecules
• Dipole–dipole forces
• Dispersion forces
• Hydrogen bonds

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 Dipole–Dipole Forces
▪ Occur between polar molecules as a result of
electrostatic interactions among dipoles
▪ Depending on orientation of the molecules, the
forces can be either attractive or repulsive

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 Dispersion Forces
• Occur between all neighboring molecules
• Arise due to constant change in electron distribution
within molecules

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 Hydrogen Bond Forces
• Forces are the result of attractive interaction
between a hydrogen bonded to an electronegative
O or N atom and an unshared electron pair on
another O or N atom

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H bond example

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 Example
• Of the two vitamins A and C, one is hydrophilic and
water-soluble while the other is hydrophobic and
fat-soluble
• Which is which?

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 Example
• Solution:

• Vitamin C has several polar ─OH groups that can form

hydrogen bonds with water
• It is water soluble(hydrophilic)
• Most of Vitamin A’s atoms can’t form hydrogen bonds
with water
• It is fat-soluble(hydrophobic)

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 References
• Organic chemistry, John McMurry

• Chapter 1 Reading: (Chapter number in this course

is different from the textbook)
• Hybridization: 1.6-1.10
• Draw organic structure: 1.12
• Polarity: 2.1-2.6
• Intermolecular forces: 2.13

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