Organic Chemistry for Engineers

CHE 153

Michael Konney Laryea

 Course outline
Lecture 1 (Introduction)

• Atomic Structure
• Isotopes
• The Structural Theory of Organic Chemistry
• Chemical Bonds: The Octet Rule
• Empirical and Molecular Formulae
• The Structure of Methane and Ethane: sp3 Hybridization
• The Structure of Ethene (Ethylene): sp2 Hybridization
• The Structure of Ethyne (Acetylene): sp Hybridization
• How to Interpret and Write Structural Formulas
 Course outline
Lecture 2 (families of carbon compounds)

•Hydrocarbons
•Functional Groups
 Course outline
Lecture 3 (Hydrocarbons: Nomenclature & Preparation )

•Introduction to Alkanes & Cycloalkanes

•Shapes of Alkanes
•IUPAC Nomenclature of Alkanes & Alkyl Halides
•Nomenclature of Alkenes & Cycloalkenes
•Nomenclature of Alkynes
•Physical Properties of Alkanes & Cycloalkanes
•Synthesis of Alkanes and Cycloalkanes
 Course outline
Lecture 4 (Alkenes and Alkynes I)

•Introduction to Alkenes and Alkynes

•Relative Stabilities of Alkenes
•Cycloalkenes
•Synthesis of Alkenes via Elimination Reactions
•Zaitsev ’s Rule and Hofmann’s Rule
•Acid-Catalyzed Dehydration of Alcohols
•Synthesis of Alkynes by Elimination Reactions
•Hydrogenation: The Function of the Catalyst
 Course outline
Lecture 5 (Addition Reactions)

•Addition Reactions of Alkenes

•Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and
Markovnikov’s Rule
•Alcohols from Alkenes through Hydroboration–Oxidation: Anti-
Markovnikov Syn Hydration
•Oxidation and Hydrolysis of Alkylboranes
•Summary of Alkene Hydration Methods
•Protonolysis of Alkylboranes
•Electrophilic Addition of Bromine and Chlorine to Alkenes
•Oxidation of Alkenes: Syn 1,2-Dihydroxylation
•Electrophilic Addition of Bromine & Chlorine to Alkynes
•Addition of Hydrogen Halides to Alkynes
•How to Plan a Synthesis: Some Approaches & Examples
 Course outline
Lecture 6 (Reactions of Aromatic Compounds)

•Electrophilic Aromatic Substitution Reactions

•A General Mechanism for Electrophilic Aromatic
Substitution
•Halogenation of Benzene
•Nitration of Benzene
•Sulfonation of Benzene
•Friedel–Crafts Acylation
•Limitations of Friedel–Crafts Reactions
•Substituents Can A ect Both the Reactivity of the Ring
and the Orientation of the Incoming Group
•How Substituents A ect Electrophilic Aromatic
Substitution: A Closer Look
•Synthetic Applications
ff
ff
 Recommendation
Books
Organic Chemistry - Francis A. Carey
Organic Chemistry - T. W. Graham Solomons
Organic Chemistry - John E. McMurry

Online resource
https://molview.org
 FUNDAMENTALS:

General Introduction

Ch. 1-1
1. Introduction
❖ The name Organic Chemistry came from
the word organism
❖ Organic Chemistry is the study of carbon
compounds. Carbon, atomic number 6,
is a second-row element. Although
carbon is the principal element in
organic compounds, most also contain
hydrogen, and many contain nitrogen,
oxygen, phosphorus, sulfur, chlorine, or
other elements Ch. 1-2
❖ Most of the compounds found in nature -
those we rely on for food, medicine, clothing
(cotton, wool, silk), and energy (natural gas,
petroleum) - are organic as well
❖ Important organic compounds are not,
however, limited to the ones we find in
nature
❖ Chemists have learned to synthesize millions
of organic compounds never found in
nature, including synthetic fabrics, plastics,
synthetic rubber, medicines, and even things
like photographic film & Super glue
Ch. 1-3
2. Atomic Structure
❖ Compounds
● made up of elements combined in
different proportions
❖ Elements
● made up of atoms
❖ Atoms
● positively charged nucleus containing
protons and neutrons
● with a surrounding cloud of negatively
charged electrons
Ch. 1-4
❖ Each element is distinguished by its atomic
number (Z)

❖ Atomic number = number of protons in

nucleus

Ch. 1-5
Ch. 1-6
2A. Isotopes
❖ Although all the nuclei of all atoms
of the same element will have the
same number of protons, some
atoms of the same element may
have different masses because they
have different numbers of
neutrons. Such atoms are called
isotopes
Ch. 1-7
❖ Examples

(1) 12C 13C 14C

(6 protons (6 protons (6 protons

6 neutrons) 7 neutrons) 8 neutrons)

(2) 1H 2H 3H

Hydrogen Deuterium Tritium

(1 proton (1 proton (1 proton
0 neutrons) 1 neutron) 2 neutrons)
Ch. 1-8
2B. Valence Electrons
❖ Electrons that surround the nucleus exist in
shells of increasing energy and at increasing
distances from the nucleus. The most
important shell, called the valence shell,
is the outermost shell because the electrons
of this shell are the ones that an atom uses
in making chemical bonds with other atoms
to form compounds
❖ The number of electrons in the valence shell
(called valence electrons) is equal to the
group number of the atom
Ch. 1-9
❖e.g.Carbon is in group IVA
●Carbon has 4 valence electrons

❖e.g.Nitrogen is in group VA
●Nitrogen has 5 valence electrons

❖e.g. Halogens are in group VIIA

●F, Cl, Br, I all have 7 valence
electrons
Ch. 1-10
3. The Structural Theory of
Organic Chemistry

❖ Number of covalent bonds usually formed by

some elements typically encountered in
organic compounds
Element # of covalent bonds Element # of covalent bonds

H 1 F 1
C 4 Cl 1
N 3 (or 4) Br 1
O 2 I 1
Ch. 1-11
❖ Thus
●C is tetravalent
●O is divalent
●H and halogens are monovalent

C O H Br

(tetravalent) (divalent) (monovalent)

Ch. 1-12
❖ Important:
● Do not draw any structure with more
than 4 bonds on a carbon

C C C

4 bonds

Ch. 1-13
❖3 bonds on carbon ⇒ need a charge
on carbon
Br
C C

C
B
H
C C

C Never draw 5 (or more) bonds on carbon

Ch. 1-14
❖ Oxygen
● Usually divalent

O H3C O H H3C CH3

(diethyl ether) (methanol) (acetone)

Ch. 1-14
❖ Lone pair electrons on oxygen can donate electrons to a
Lewis acid
● 3 bonds on oxygen (with a positive charge on oxygen)

e.g.

H3C H3C H3C

+ O H O H
O H
H H
H
dative
covalent bond

Ch. 1-15
 BF3
O F O
B
H3C CH3 H3C CH3
F F

empty p-orbitals
❖ One bond on oxygen
● Usually need a negative charge on oxygen

e.g.

O O
H OH
R O R O
3A.Isomers: The Importance of
Structural Formulas
❖ Differentcompounds that have the same
molecular formula. Such compounds are
called isomers

e.g.
OH O
1-Butanol Diethyl ether
●Both have the molecular formula
C4H10O

●They are constitutional isomers

●Constitutional isomers usually have

different physical properties (e.g.,
melting point, boiling point, and
density) and different chemical
properties (reactivity)
4. Chemical Bonds:
The Octet Rule

❖ Ionic (or electrovalent) bonds are

formed by the transfer of one or more
electrons from one atom to another to
create ions

❖ Covalent bonds result when atoms

share electrons
❖ OctetRule
●In forming compounds, they gain,
lose, or share electrons to give a
stable electron configuration
characterized by 8 valence electrons
●When the octet rule is satisfied for
C, N, O and F, they have an electron
configuration analogous to the noble
gas Ne
❖ Recall:electron configuration of noble
(inert) gas

# of e-s in outer shell

H [1s2] 2
Ne 1s2[2s22p6] 8
Ar 1s22s22p6[3s23p6] 8
4A.Ionic Bonds

❖ Atomsmay gain or lose electrons and form

charged particles called ions

● An ionic bond is an attractive force

between oppositely charged ions
❖ Electronegativity (EN)

● The intrinsic ability of an atom to

attract the shared electrons in a
covalent bond

● Electronegativities are based on an

arbitrary scale, with F the most
electronegative (EN = 4.0) and Cs the
least (EN = 0.7)
 element H
(EN) (2.1)
Li Be B C N O F
……..………
(1.0) (1.6) (2.0) (2.5) (3.0) (3.5) (4.0)
Na Mg Si P S Cl
………………...……
(0.9) (1.2) (1.8) (2.1) (2.5) (3.0)
K Br
………………………..…………………………………
(0.8) (2.8)
Rb I
………………………………………………..…………
(0.8) (2.5)
Cs
……………………………………………………………………
(0.7)
 give 1 e- to
Na Cl
1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p5

(1 e- in outermost shell) (7 e- in outermost shell)

ionic bonding

+ –
Na Cl
1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6

8 8
4B.Covalent Bonds & Lewis Structures

❖ Covalent bonds form by sharing of

electrons between atoms of similar
electronegativities to achieve the
configuration of a noble gas

❖ Molecules are composed of atoms

joined exclusively or predominantly by
covalent bonds
❖ Example

:Cl. . Cl:
: :

: :
[Ne] 3s2 3p5 [Ne] 3s2 3p5
covalent bonding

:Cl—Cl:
: :
: :
❖ Ions, themselves, may contain covalent
bonds. Consider, as an example, the
ammonium ion

H
+
H N
N H H
H H
H H
(ammonia) (ammonium cation)
(3 bonds on N) (4 bonds on N with
a positive charge on N)

40
Empirical and molecular formula
12. The Structure of Methane and
Ethane: sp3 Hybridization

Ground state of a carbon atom

C
1s 2s 2px 2py 2pz

42
❖ Hybridization
● sp3
sp3
covalent hybridized
bond H carbon
H C H
H
(line bond structure)

43
❖ Hybridization
● sp3 H
H C H
H
(Lewis structure)

109o H Tetrahedral
structure
C H
H H
Carbon with
(3-D stucture) 4 σ bonds
44
12A. The Structure of Methane

45
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47
48
12B. The Structure of Ethane

49
50
13. The Structure of Ethene
(Ethylene): sp2 Hybridization
❖ sp2
1 σ bond + 1 π bond
o
~120
H H
o 2
~120 C C sp hybridized carbon
H H
o
~120

51
❖ sp2
3-Dimensional View

π-bond
(π-orbitals overlap)
H H
C C
H H

Planar structure
Carbon with (3σ + 1π) bonds
52
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56
57
58
13A. Restricted Rotation and the
Double Bond
❖ There is a large energy barrier to
rotation associated with groups joined
by a double bond
● ~264 kJmol-1 (strength of the π bond)
● To compare: rotation of groups joined
by C-C single bonds ~13-26 kJmol-1

59
60
13B. Cis–Trans Isomerism
❖ Stereochemistry of double bonds
H R
H identical to H
R H
H H

H H
i
H3C identical to Pr
H H
i
Pr CH3

61
H3C different from
CH3 CH3

(trans) CH3 (cis)

● Restricted rotation of C=C

62
 ● Cis-Trans System
⧫ Useful for 1,2 disubstituted alkenes

e.g.
(1) H Br
Cl Cl
Br vs. H
H H
trans -1-Bromo- cis-1-Bromo-
2-chloroethane 2-chloroethane

63
(2) H

vs. H
H H
trans -3-Hexene cis -3-Hexene

(3)
Br

Br Br vs. Br
trans -1,3- cis -1,3-
Dibromopropene Dibromopropene

64
14. The Structure of Ethyne
(Acetylene): sp Hybridization
❖ sp
1 σ bond + 2 π bond
H C C H
o
180 2
sp hybridized carbon

Linear structure
Carbon with (2 σ + 2 π) bonds

65
66
67
68
❖ sp orbital
● 50% s character, 50% p character

❖ sp2 orbital
● 33% s character, 66% p character

❖ sp3 orbital
● 25% s character, 75% p character

69
70
17. How to Interpret and Write
Structural Formulas

71
17A. Dash Structural Formulas
❖ Atoms joined by single bonds can
rotate relatively freely 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

72
17B. Condensed Structural Formulas

73
17C. Bond-Line Formulas

74
75
17D. 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
76
 Br
H

H OH Cl
H
Examples of bond-line formulas that include
three-dimensional representations

H NH2 Br H
HO

An example involving An example involving

trigonal planar geometry linear geometry
77