Chemistry 122

Introductory Organic Chemistry

Winter Quarter 2018

Dr. Thomas H. Schultz
What is Organic chemistry?
What is Organic chemistry?
The study of carbon and its compounds.
What is Organic chemistry?
The study of carbon and its compounds.
First we will talk about compounds just containing carbon
and hydrogen, these compounds are called
hydrocarbons.
What is Organic chemistry?
The study of carbon and its compounds.
First we will concentrate on compounds just containing
carbon and hydrogen, these compounds are called
hydrocarbons.
Hydrocarbon Classification

Hydrocarbons

Alkanes Cycloalkanes Alkenes Cycloalkenes Alkynes

1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H?
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H?
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
H
C
H H
H
CH4
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
H H H
C H C C H
H H H H
H
CH4 C2H6
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
H H H H H H
C H C C H H C C C H
H H H H H H H
H
CH4 C2H6 C3H8
1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
H H H H H H
C H C C H H C C C H
H H H H H H H
H
CH4 C2H6 C3H8

D. Polarity? Polar or nonpolar?

1. Alkanes (saturated) hydrocarbons, or aliphatic hydrocarbons)
A. General formula of CnH2n+2
B. Examples
a. CH4 b. C2H6 c. C3H8 d. C4H10
C. Draw Lewis Structures
H H H H H H
C H C C H H C C C H
H H H H H H H
H
CH4 C2H6 C3H8

D. Polarity? Polar or nonpolar? Nonpolar

E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H H H H
H C C C C H
H H H H

Butane, C4H10
Primary carbon = ?
Secondary carbon =
Tertiary carbon =
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H H H H
H C C C C H
H H H H

Butane, C4H10
Primary carbon = 2
Secondary carbon = ?
Tertiary carbon =
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H H H H
H C C C C H
H H H H

Butane, C4H10
Primary carbon = 2
Secondary carbon = 2
Tertiary carbon =
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H H H H
H C C C C H
H H H H

Butane, C4H10
Primary carbon = 2
Secondary carbon = 2
Tertiary carbon = ?
G. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H H H H
H C C C C H
H H H H

Butane, C4H10
Primary carbon = 2
Secondary carbon = 2
Tertiary carbon = 0
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H
H C H
H H
H C C C H
H H H
Isobutane C4H10

Primary carbon = ?
Secondary carbon =
Tertiary carbon =
G. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H
H C H
H H
H C C C H
H H H
Isobutane C4H10

Primary carbon = 3
Secondary carbon = ?
Tertiary carbon =
E. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H
H C H
H H
H C C C H
H H H
Isobutane C4H10

Primary carbon = 3
Secondary carbon = 0
Tertiary carbon = ?
G. Types of carbon

1. Primary (1◦) Carbon connected to one carbon atoms.

2. Secondary (2◦) Carbon connected to two carbon atoms.
3. Tertiary (3◦) Carbon connected to three carbon atoms.
4. How many primary, secondary, and tertiary carbons in the
two different structures of C4H10

H
H C H
H H
H C C C H
H H H
Isobutane C4H10

Primary carbon = 3
Secondary carbon = 0
Tertiary carbon = 1
1. Alkanes (Continued)

F. There are two different structures for C4H 10 called

isomers, because they contain different types of
carbon.

Structure 1 H H H H
H C C C C H
H H H H

Butane, C4H10
H
Structure 2 H C H
H H
H C C C H
H H H
Isobutane, C 4H10
 Isomerism
Constitutional Isomers (Structural Isomers) are different
compounds of the same formula. The different structures
from the previous slide for the formula C4H10 is an example
of Constitutional isomers.
 Isomerism
Constitutional Isomers (Structural Isomers) are different
compounds of the same formula. The different structures
from the previous slide for the formula C4H10 is an example
of Constitutional isomers.

How many isomers are there of an alkane containing five

carbons (C5H12)?

Isomer Strategy – Draw Lewis possible different length

chains of carbons atoms connected with a covalent bond.
 Isomerism
Constitutional Isomers (Structural Isomers) are different
compounds of the same formula. The different structures
from the previous slide for the formula C4H10 is an example
of Constitutional isomers.

How many isomers are there of an alkane containing five

carbons (C5H12)?

Isomer Strategy – Draw Lewis possible different length

chains of carbons atoms connected with a covalent bond.
Chains of 5 carbon atoms
H H H H H

H C C C C C H

H H H H H
 Isomerism
Chains of 4 carbon atoms
H H H H

H C C C C H

H H H C HH

H
 Isomerism
Chains of 4 carbon atoms Chains of 3 carbon
atoms H
H H H H HH C H H

H C C C C H H C C C H
H H H C HH HH C HH
H
H
 Isomerism
Chains of 4 carbon atoms Chains of 3 carbon
atoms H
H H H H
HH C H H
H C C C C H
H C C C H
H H H C HH
HH C HH
H
H

There are three isomers of C5H12

 NOMENCLATURE
1. Common system
a. Works best for low molecular weight hydrocarbons
b. Steps to give a hydrocarbon a common name:
1. Count the total number of carbon atoms in the
molecule.
2. Use the Latin root from the following slide that
corresponds to the number of carbon atoms followed
by the suffix “ane”.
3. Unbranced hydrocarbons use the prefix normal, or n-,
4. Branched hydrocarbons use specific prefixes, as
shown on a subsequent slide
 NOMENCLATURE
Common system Examples

1. Give a name for the following compound

H H H
H C C C H
H H H

Step #1, count the number of carbons and write down the memorized Latin name
for that number (next slide)
Step #2, since this structure fits the alkane general formula, use the “ane” suffix

propane Alkane suffix

Three carbon Latin root

 Examples
Latin Latin H H H H
Hydrocarbon Hydrocarbon H C C C C H
Roots Roots H H H H

n-butane
Number of Latin Number of Latin
H
Carbons Root Carbons Root H
C H
1 meth 12 dodec H H
2 eth 13 tridec H C C C H
3 prop 14 tetradec H H H
4 but 15 pentadec isobutane
5 pent 16 hexadec H
H H C H H
6 hex 17 heptadec
7 hept 18 octadec
H C C C H
8 oct 19 nonadec
9 non 20 eicos H H C H H
10 dec 21 unicos H
11 undec 22 doicos neopentane
 2. Systematic System of Nomenclature (IUPAC)

•Find the longest continuous chain of carbon atoms.

•Use a Latin root corresponding to the number of carbons in the
longest chain of carbons.
•Follow the root with the suffix of “ane” for alkanes
•Carbon atoms not included in the chain are named as
substituents preceding the root name with Latin root followed
by “yl” suffix.
•Number the carbons, starting closest to the first branch.
•Name the substituent's attached to the chain, using the carbon
number as the locator in alphabetical order.
•Use di-, tri-, etc., for multiples of same substituent.
• If there are two possible chains with the same number of
carbons, use the chain with the most substituent's.
Substituent Names (Alkyl groups)
Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
H3C CH2 C CH CH2 CH2 CH3 Which one?
CH3

H3C
CH CH2 CH3
CH3
H3C CH2 C CH CH2 CH2 CH3
CH3
 Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
Which one?
H3C CH2 C CH CH2 CH2 CH3
CH3
The one with the most
H3C number of substituent's
CH CH2 CH3
CH3
H3C CH2 C CH CH2 CH2 CH3
CH3
 Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
Which one?
H3C CH2 C CH CH2 CH2 CH3
CH3
The one with the least
H3C number of substituent's
CH CH2 CH3
CH3 The top structure has
H3C CH2 C CH CH2 CH2 CH3 four substituent's and
the bottom has three
CH3 substituent's.
 Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
Which one?
H3C CH2 C CH CH2 CH2 CH3
CH3
The one with the least
H3C number of substituent's
CH CH2 CH3
CH3 The top structure has
H3C CH2 C CH CH2 CH2 CH3 four substituent's and
the bottom has three
CH3 substituent's.

Name = ?
 Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
Which one?
H3C CH2 C CH CH2 CH2 CH3
CH3
The one with the most
H3C number of substituent's
CH CH2 CH3
CH3 The top structure has
H3C CH2 C CH CH2 CH2 CH3 four substituent's and
the bottom has three
CH3 substituent's.

Name = ? heptane
 Systematic Nomenclature continued.

H3C
CH CH2 CH3
CH3
Which one?
H3C CH2 C CH CH2 CH2 CH3
CH3
The one with the least
H3C number of substituent's
CH CH2 CH3
CH3 The top structure has
H3C CH2 C CH CH2 CH2 CH3 four substituent's and
the bottom has three
CH3 substituent's.

Name = 3,3,5-trimethyl-4-propylheptane
Another Example:

CH3 CH3
H3C CH CH CH2 CH2 CH CH3
CH2CH3

Name = 3-ethyl-2,6-dimethylheptane
Another Example:

CH3 CH3
H3C CH CH CH2 CH2 CH CH3
CH2CH3

Name = 3-ethyl-2,6-dimethylheptane

Notice substituent's are in alphabetical order; di, tri, etc. do

not participate in the alphabetical order
 Line Structures
A quicker way to write structures'
CH3 CH3
H3C CH CH CH2 CH2 CH CH3 (Condensed Structure)

CH2CH3
ethyl methyl

(A line structure of the above

condensed structure)

methyl
 Complex Substituent's
•If the branch has a branch, number the carbons from the point of
attachment.
•Name the branch off the branch using a locator number.
•Parentheses are used around the complex branch name.

3
1 1
2

1-methyl-3-(1,2-dimethylpropyl)cyclohexane
 Alkane Physical Properties
Solubility: hydrophobic (not water soluble)
Density: less than 1 g/mL (floats on water)

Boiling points increase with increasing carbons (little

less for branched chains) due to dispersion forces
being larger.

Melting points increase with increasing carbons (less for

odd-number of carbons).
 Boiling Points of Alkanes
Branched alkanes have less surface area contact,
so weaker intermolecular forces.
 Melting Points of Alkanes
Branched alkanes pack more efficiently into a crystalline
structure, so have higher m.p.
 Reactions of Alkanes
I. Combustion reaction
H
heat
+ O2 CO2 + H2O
H C H

H
heat
+ O2 CO2 + H2O

II. Cracking reaction

heat +
catalyst

III. Halogenation reaction (substitution reaction)

sun + HCl
+
+ Cl2
Cl Cl

Butane 2-chlorobutane 1-chlorobutane

Sample problem:
Which isomer of C5H12 has the most monochloro isomers?
Problem solving process:
Step 1 draw the isomers of C5H12
Step 2 react each isomer with chlorine
Step 3 count the products
Sample problem:
Which isomer of C5H12 has the most monochloro isomers?

Problem solving process:

Step 1 draw the isomers of C5H10
Step 2 react each isomer with chlorine
Step 3 count the products

+ Cl2

+ Cl2

+ Cl2
Sample problem:
Which isomer of C5H12 has the most monochloro isomers?

Problem solving process:

Step 1 draw the isomers of C5H10
Step 2 react each isomer with chlorine
Step 3 count the products
Cl Cl

+ Cl2 + +

2-chloropentane Cl 1-chloropentane 3-chloropentane

+ Cl2

+ Cl2
Sample problem:
Which isomer of C5H12 has the most monochloro isomers?

Problem solving process:

Step 1 draw the isomers of C5H10
Step 2 react each isomer with chlorine
Step 3 count the products
Cl Cl

+ Cl2 + +

2-chloropentane Cl 1-chloropentane 3-chloropentane

Cl
Cl
+ Cl2 Cl

Cl
1-chloro-3-methylbutane 2-chloro-3-methylbutane 2-chloro-2-methylbutane 1-chloro-2-methylbutae

+ Cl2
Sample problem:
Which isomer of C5H12 has the most monochloro isomers?

Problem solving process:

Step 1 draw the isomers of C5H10
Step 2 react each isomer with chlorine
Step 3 count the products
Cl Cl

+ Cl2 + +

2-chloropentane Cl 1-chloropentane 3-chloropentane

Cl
Cl
+ Cl2 Cl

Cl
1-chloro-3-methylbutane 2-chloro-3-methylbutane 2-chloro-2-methylbutane 1-chloro-2-methylbutae
Cl
+ Cl2

1-chloro-2,2-dimethylpropane
Sample problem:
Which isomer of C5H12 has the most monochloro isomers?

Problem solving process:

Step 1 draw the isomers of C5H10
Step 2 react each isomer with chlorine
Step 3 count the products
Cl Cl

+ Cl2 + +

2-chloropentane Cl 1-chloropentane 3-chloropentane

Cl
Cl
+ Cl2 Cl

Cl
1-chloro-3-methylbutane 2-chloro-3-methylbutane 2-chloro-2-methylbutane 1-chloro-2-methylbutae
Cl
+ Cl2

1-chloro-2,2-dimethylpropane
Winner!
 Conformers of Alkanes
•Structures resulting from the free rotation of
a C-C single bond
•May differ in energy. The lowest-energy
conformer is most prevalent.
•Molecules constantly rotate through all the
possible conformations.
 Ethane Conformers
Staggered conformer has lowest energy.
Dihedral angle = 60 degrees
H Dihedral angle
H H

H H
H

Newman
projection sawhorse
model
 Ethane Conformers (2)
Eclipsed conformer has highest energy
Dihedral angle = 0 degrees

=>
 Conformational Analysis
•Torsional strain: resistance to rotation.
•For ethane, only 12.6 kJ/mol

=>
Propane Conformers
Note slight increase in torsional strain
due to the more bulky methyl group.
 Butane Conformers C2-C3
Highest energy has methyl groups eclipsed.
Steric hindrance
Dihedral angle = 0 degrees

totally eclipsed (methyl groups)

=>
 Butane Conformers (2)
Lowest energy has methyl groups anti.
Dihedral angle = 180 degrees

Staggered-anti
=>
 Butane Conformers (3)
•Methyl groups eclipsed with hydrogens
•Higher energy than staggered conformer
•Dihedral angle = 120 degrees

=>
Eclipsed (hydrogen and methyl)
 Butane Conformers (4)
•Gauche, staggered conformer
•Methyls closer than in anti conformer
•Dihedral angle = 60 degrees

Staggered-gauche =>
Conformational Analysis
 Cycloalkanes
•Rings of carbon atoms (-CH2- groups)
•Formula: CnH2n
•Nonpolar, insoluble in water
•Compact shape
•Melting and boiling points similar to branched
alkanes with same number of carbons
•Slightly unsaturated compared to alkanes
 Naming Cycloalkanes
•Count the number of carbons in the cycle
•If the bonds are single then use the suffix “ane”
•First substituent in alphabet gets lowest number.
•May be cycloalkyl attachment to chain.

cyclopropane cyclobutane cyclopentane cyclohexane cycloheptane

CH 3 H3CH 2C CH 3

mehtylcyclopropane 1-ethyl-2-methylcyclobutane 2-cyclopropylheptane

 Cis-Trans Isomerism
(a type of stereoisomerism)

Cis: like groups on same side of ring

Trans: like groups on opposite sides of ring
 Cycloalkane Stability
• 6-membered rings most stable
• Bond angle closest to 109.5
• Angle (Baeyer) strain
• Measured by heats of combustion per -CH2 -
Heats of Combustion/CH2
Alkane + O2  CO2 + H2O
697.1 686.1
658.6 kJ 664.0 662.4 663.6 kJ/mol
658.6

Long-chain
 Cyclopropane
• Large ring strain due to angle compression
• Very reactive, weak bonds

=>
 Cyclopropane (2)
Torsional strain because of eclipsed hydrogens
 Cyclobutane
• Angle strain due to compression
• Torsional strain partially relieved by ring puckering

=>
 Cyclopentane
• If planar, angles would be 108, but all
hydrogens would be eclipsed.
• Puckered conformer reduces torsional strain.
 Cyclohexane
• Combustion data shows it’s unstrained.
• Angles would be 120, if planar.

• The chair conformer has 109.5 bond angles

and all hydrogen's are staggered.

• No angle strain and no torsional strain.

Chair Conformer
Boat Conformer
Conformational Energy
Axial and Equatorial Positions
Monosubstituted Cyclohexanes
1,3-Diaxial Interactions
Disubstituted Cyclohexanes
 Cis-Trans Isomers
Bonds that are cis, alternate axial-equatorial
around the ring.

CH3

CH3
One axial, one equatorial

=>
 Bulky Groups
• Groups like t-butyl cause a large energy
difference between the axial and equatoria
l conformer.

• Most stable conformer puts t-butyl equatorial

regardless of other substituents.

=>
End of Chapter 2