Organic Chemistry

Lecture 4:
Alkane and Cycloalkane

1
 Functional Groups
Group of atoms in a molecule that have a characteristic
behavior (reacts in a typical way), generally
independent on the rest of the molecule

Double bonds in simple and complex alkenes

react with bromine in the same way
2
Some Common Functional Groups

3
Some Common Functional Groups

4
Some Common Functional Groups

5
Some Common Functional Groups

6
Hydrocarbon Economy

Why did Imperial Japan

lose in WWII?
Coal : electricity

Fossil fuels

Oil: transportation
oking

Natural gas: heating + co

7
 Hydrocarbons

Compound comprised of only C and H.

Alkane Alkene Alkyne Aromatics

8
 Hydrocarbons

Compound comprised of only C and H.

Alkane Alkene Alkyne Aromatics

Name with “-ane” at the end

9
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 1: Identify the parent chain

• Choose the longest chain

1
0
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 1: Identify the parent chain

• Choose the longest chain

• If same length, choose chain with greater number of substituents

1
1
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 1: Identify the parent chain

• Choose the longest chain

• If same length, choose chain with greater number of substituents

Ex: Identify the parent chain and name it

C10 - decane
1
2
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 1: Identify the parent chain

• Choose the longest chain

• If same length, choose chain with greater number of substituents

• If there is a ring, use “cyclo” to indicate

1
3
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 2: Naming the substituents ethyl

n-butyl

methyl methyl

Ex: Identify and name all substituents

1
4
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 2: Naming the substituents

• Regarding complex substituents

Number the C on the substituent,

going away from the parent chain
10
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 2: Naming the substituents

• When alkyl is attached to the ring, the

ring is generally treated as parent

• But if the ring has less atom than the

rest, name the ring as substituent
(cycloalkyl)

16
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 3: Number the parent chain

• Begin with the end that is nearest to a substituent

7 9
6 8 10

5 4 2
3 1

17
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 3: Number the parent chain

• Begin with the end that is nearest to a substituent

• If there is a tie, then the second locant should be as low as possible:

• If still not break the tie, then the lowest number should be assigned alphabetically

• Same rule
applied for
cycloalkanes
18
 Alkane - Nomenclature

IUPAC Nomenclature (International Union of Pure and Applied Chemistry)

Step 4: Organizing multiple groups

• With more than 2 substituents, list them in alphabetical order.

• With 2 or more of the same alkyl group, use prefixs to avoid naming them
several times

5-butyl-6-ethyl-2,4-dimethyldecane

19
 Practice

Give the IUPAC name for the following

Note:
When substituents are
alphabetized, iso- is used as part
of the alkyl group name, but the
hyphenated prefixes are not. Thus,
isobutyl is alphabetized with i, but
n-butyl, tert-butyl, and sec-butyl
are alphabetized with b. The
number prefixes di-, tri-, tetra-…
are ignored in alphabetizing.

4-isopropyl-2,2,3,6-tetramethyloctane

20
 Alkane - Nomenclature

IUPAC vs. common name

Paracetamol
(Acetaminophen)

N-(4-Hydroxyphenyl)ethanamide 16
 Physical Properties

1.Solubility and density

• Blowout in
• Alkane is hydrophobic
Gulf of Mexico
• Density ~ 0.7 g/ml
• Oil floats on
water

2. Boiling and melting point

17
 Chemical Reactions

1. Combustion

CO2: Source of global warming

2. Cracking (thermal and catalytic cracking)

3. Reforming: (to increase octane number)

4. Halogenation:

23
 Newman Projection

C-C single bond can rotate to make different conformations

Back carbon

Front carbon

24
 Newman Projection

Can we determine chirality from Newman Projection?

Why is it important? The conformations have different energy levels
20
 Practice

In each case below, draw a Newman projection as viewed from the angle indicated

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 Solutions

(a) (b)

(c) (d)

(e)
(f)

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Conformation of Ethane

Torsional strain = 12 kJ/mol

(energy barrier to rotate)

Instability caused by 3
eclipsing interactions
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Conformation of Ethane
24
Conformation of Ethane

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 Conformation of Propane

Torsional strain = 14 kJ/mol

6??
kJ/mol

Energy barrier 12-14 kJ/mol : significant or not?

At room temperature, a sample of ethane or propane gas has ~99% of its

molecules in staggered conformations.
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 Practice
1. For each of the following compounds, predict the energy barrier to rotation
(looking down any one of the C−C bonds). Draw a Newman projection and
then compare the staggered and eclipsed conformations.
(Remember that we assigned 4 kJ/mol to each pair of eclipsing H’s and
6 kJ/mol to an H eclipsing a methyl group)

(a) 2,2-Dimethylpropane (b) 2-Methylpropane

2. Label the molecule as chiral (C), achiral (A), or achiral/meso (M).

If chiral, designate each chiral center as R or S

32
 Why HIV/AIDS is the Disease of the Century?

Acquired immunodeficiency syndrome (AIDS) is caused by the human

immunodeficiency virus (HIV). Why is it so hard to cure?
HIV can undergo genetic mutations
→ virus changes geometry of the cavity where the drugs are supposed to bind
→ The new strain of the virus becomes drug resistant
→ Anti-HIV drugs are not 100% effective

New hope! Using flexible drug compound

33
 Alkyl Halide

Halogenation of alkane:

Alkyl halide

• Alkyl halides are synthetic precursors for many reactions

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 Alkyl Halide

2 types of reactions:

• Substitution (when treated with nucleophile)

• Elimination (when treated with base)

Why alkyl halides are active for these reactions?

• X: electron withdrawing
-> C becomes electrophilic
-> C can be attacked by nucleophiles

• Cl-, Br-, I- are good leaving groups

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 Nomenclature and Uses of Alkyl Halide

• Halogens are simply treated as substituents

• Name: flouro-, chloro-, bromo- and iodo-

Rank halogen = alkyl group

Practice: Assign a systematic name for each of the following compounds

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 Nomenclature and Uses of Alkyl Halide
Alkyl halide: generally called organohalide

Many are toxic

Kill mosquitos Shampoo Coolant fluid

But not all: Kill head lice
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Cycloalkane

38
 Cycloalkane

Naming bicyclic compounds

Bicyclics: two joined rings

Bicycloheptane

Identify the bridgeheads (the 2 C atoms where the ring joins together)

Bicyclo[2.2.1]heptane

2 [Order numbers from largest to smallest]

2

Bicyclo[3.1.1]heptane

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 Cycloalkane

Naming bicyclic compounds

Bicyclics with substituents: number the parent to assign locants to the substituents

Start at one of the bridgeheads : begin numbering along the longest path

→ Then go to the second longest path

→ Finally go along the shortest path

8-methylbicyclo[3.2.1]octane

If there is a tie, choose the one giving substituent lowest number

6-methylbicyclo[3.2.1]octane

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 Cycloalkane

Naming bicyclic compounds

Parent: bicyclo[3.2.0]heptane

2-Isopropyl-7,7-dimethylbicyclo[3.2.0]heptane

4-ethyl-1-methylbicyclo[3.2.1]octane 36
2,2,5,7-tetramethylbicyclo[4.2.0]octane
 Cycloalkane

Why there is ring strain ?

Adolph von Baeyer (Nobel Prize 1905) → cyclopentane is most stable True or not ??
→ very large cycloalkane does not exist
Angles in planar geometric shape

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 Cycloalkane

Cyclopropane
Bent bond
Non-linear overlap

• Severe ring strain

• Together with significant torsional strain

Locked eclipsed conformation

→ Cyclopropane is highly unstable, very reactive

(used to be used as anesthetic) 38
 Cycloalkane

Cyclobutane

Less ring strain but more torsional strain

→ lightly folded to relieve from eclipsing of the bonds

Cyclopentane

The molecule is lightly folded to reduce torsional strain

→ but there is still some strain
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 Cyclohexane

Cyclohexane: very common in nature (due to their stability and selectivity)

Zero ring strain -> bond angles are 109.5°

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 Cyclohexane

Adopt twist
conformation

Flagpole interaction

46
 Cyclohexane

How to draw chair conformation

Chair conformation always contains 3 sets of parallel lines

47
 Cyclohexane

• Draw axial positions

• Draw equatorial positions

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 Cyclohexane

Ring-flip

CH3 axial CH3 equatorial

49
 Cyclohexane
Draw both chair conformations of bromocyclohexane:
• Draw the first chair :

• Draw the second chair :

50
 Practice
Draw both chair conformations for each of the following compounds:

51
Cyclohexane

52
 Practice

(a) As depicted above, is the adenine group (highlighted) occupying an axial or an

equatorial position? Is the CH2OH group occupying an axial or an equatorial
position?

(b) Convert the Newman projection into a bond-line chair form.

cis or trans? Can cis become trans through changing conformations?

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 Stability of Both Chair Conformations

Reduce steric hindrance

-> more stable

The most stable conformation of 5-hydroxy-1,3-dioxane

has the OH group in an axial position, rather than an
equatorial position. Provide an explanation for this
observation.

54
 Disubstituted Cyclohexane

UP or DOWN does not

change during ring flip

Draw both conformations for each of the following compounds:

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