ORGANIC CHEMISTRY I

Alkanes & Cycloalkanes

Dr. Sri Sutji Susilowati, M.Si., Apt
M. Salman Fareza, M.Si.

Pharmacy Departement
Jenderal Soedirman University

I. Classes of Organic Compounds

Hydrocarbons (C & H only)
aliphatic
alkanes
C

aromatic

Heteroatomic compounds
alcohols R OH
ethers

alkenes

aldehydes
ketones

C C

alkynes
C C

cyclic compounds

R O R'
O
R C H
O

R'

carboxylic acids
esters
amines
amides

O
C OH

R C OR'
R NH2

O
R C NH2

II. Alkanes
A. General formula: CnH2n + 2

CH4

methane (natural gas, swamp gas)

CH3CH3

(C2H6)

ethane

CH3CH2CH3

(C3H8)

propane (LPG)

CH3CH2CH2CH3 (C4H10)

75-85% CH4
5-10% C2H6
1-5% C3H8

butane

II. Alkanes
B. Isomers: normal and branched alkanes
C4H10

CH3 CH2 CH2 CH3

butane lighters:
5% n-butane
95% isobutane

n-butane
H H H H
H
C
C
C
C
H
H H H H
straight chain

Chem3D
CH3

constitutional
isomers

CH CH3
CH3

isobutane
branched chain
4

II. Alkanes
B. Isomers: normal and branched alkanes
C5H12

CH3

CH2

CH3

CH2

CH2

CH2

CH3

CH CH3

n-pentane
isopentane

CH3
CH3
CH3

CH3

neopentane

CH3

C6H14
C10H22
C20H42

5 isomers
75 isomers
366,319 isomers

obviously need system of nomenclature

II. Alkanes
B. Isomers: normal and branched alkanes
Question 2-1. Draw the constitutional isomers of the following. Click on
the arrow to check your answers.
C6H14 (5)

C7H16 (9)

Check Answer

II. Alkanes
B. Isomers: normal and branched alkanes
Answer 2-1. Draw the constitutional isomers of the following. Click on
the arrow to check your answers.
C6H14 (5)

C7H16 (9)

II. Alkanes
B. Isomers: normal and branched alkanes
Types of carbons:

methyl carbons

CH3
CH3

CH CH2

CH3
methylene carbon
methine carbon

II. Alkanes
C. Structure-property relationships
Intermolecular attractions: London (or van der Waals) forces (weak)
b.p.
CH4
-160C
C2H6
-89
vs
C3H8
-42
n-C4H10 -0.4
n-C5H10 36
Branching: lowers b.p.

-0.4C

greater surface area

for attraction

-10.2C

Chem3D
36C

28C

9C

IV. Chemical Properties of Alkanes

A. Combustion
C8H18 +

Heats (enthalpies) of combustion: Hcomb

~
1307.5 kcal
~

~
1306.3 kcal
~

~
1304.6 kcal
~

~
1303.0 kcal
~

CO2 + H2O

More branched isomers have lower Hcomb, are more stable.

10

IV. Chemical Properties of Alkanes

B. Oxidation and reduction in organic molecules
CH4 + Br2 CH3Br + HBr

OH

H C H

H C H

OH

oxidation
more C-O bonds, fewer C-H bonds
reduction
fewer C-O bonds, more C-H bonds
11

IV. Chemical Properties of Alkanes

B. Oxidation and reduction in organic molecules

H3C

CH3

H2C

CH2

HC

CH

oxidation
fewer C-H bonds
reduction
more C-H bonds
H2C=CH2 + H2O2 HOCH2CH2OH
H2C=CH2 + H2O CH3CH2OH
H2C=CH2 + H2 CH3CH3
12

IV. Chemical Properties of Alkanes

B. Assigning oxidation numbers:
1. For each atom in a bond, assign a +1 to the more
electropositive atom and a -1 to the more electronegative
atom. (If the atoms are the same, each atom gets a 0.)
-1

Cl
+1

+1 +1
-1 C
+1

-1

O
-1

2. Total each atom.

-1

Cl
+1

+1 +1
-1 C
+1

-1

O
-1

Oxidation number of carbon is

+1 +1 +1 -1 = +2
13

IV. Chemical Properties of Alkanes

Question 2-5. Determine oxidation numbers for the carbons
in each of the following molecules. Click on the arrow to check
your answers.
H C N
H O

2
H C

1
C O H

Br

H
H C Cl
OH

Check Answer

14

IV. Chemical Properties of Alkanes

Answer 2-5. Determine oxidation numbers for the carbons
in each of the following molecules. Click on the arrow to check
your answers.
H C N

C = +2

H O

2
H C

1
C O H

C1 = +3; C2 = -1

Br

H
H C Cl

C=0

OH

15

IV. Chemical Properties of Alkanes

Question 2-6. Determine whether the following reactions will
be oxidation, reduction, or neither. Check your answers by clicking
on the arrow.
Br Br
H2C

CH2

Br2

H2C

CH2

H H
H2C

CH2

+ H2O

H C C H
H OH

Check Answer

16

IV. Chemical Properties of Alkanes

Answer 2-6. Determine whether the following reactions will
be oxidation, reduction, or neither. Check your answers by clicking
on the arrow.
Br Br
H2C

CH2

Br2

H2C

CH2

Oxidation: Each carbon

changes from a -2 to a -1.

H H
H2C

CH2

+ H2O

H C C H
H OH

Neither. One carbon changes from a -2 to a -3 (gets

reduced), but the other carbon goes from a -2 to a -1
(gets oxidized.) No net change.

Check Answer

17

V. Conformations of Alkanes
A. Ethane: torsional strain

H
H C
H

C H
H

staggered
conformation

rotate 60

in between:
skewed

H C
H

C H
H

eclipsed
conformation

Newman projections: sight along C-C bond

H
H

H
H

H
H

H
H

Chem3D

H
H

H
H

Stereoisomers:
Isomers with the
same connectivity,
but different 3-D
orientation of their
atoms in space.
18

V. Conformations of Alkanes
A. Ethane: torsional strain

H
H

H
H

H
H

H
H

H
H

H
H

lower energy

higher energy

G ~ 3 kcal/mol
K ~ 0.01
torsional strain

Ea ~ 3 kcal/mol

= barrier to free rotation

(but at room temp most

molecules have KE > Ea so
rotation is essentially free)

0
H
H

H
H

H
H

H
H

H
H

H
H
H

H
H

H
H

krot ~ 106 s-1

19

V. Conformations of Alkanes
B. Butane: steric repulsions

CH3CH2CH2CH3

CH3

CH33

CH3
I
anti
(180)

CH3

H3C

CH3

CH3
CH3

CH3

H3C

CH3
II

III
gauche
(60)

IV

gauche ~ 0.8 kcal higher energy than anti

- van der Waals repulsions
= steric strain
eclipsed:3 kcal torsional strain
+ 0.3 kcal each CH3-H eclipse
+ ~ 3 kcal each CH3-CH3 eclipse

V
gauche
(60)

VI

Chem3D

20

V. Conformations of Alkanes
B. Butane: steric repulsions
CH3

CH3

H3C

CH3

CH33

CH3
CH3

CH3

H3C

CH3
I

CH3
II

III

IV

VI

4
G

~6

2
3.6

0.8

0.8

3.6

0
I

II

III

IV

VI

21

VI. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

Ring strain = bond angle strain

+ torsional strain (eclipsing)
+ steric strain (van der Waals)

22

VI. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes
Hcomb

per CH2

small

normal

medium
large > C12

166.6 kcal

Total
ring strain
31.5 kcal

162.7

26.4

157.3

7.0

156.1

157.0

6.3

157.3

9.6

156.2

1.2

angle strain and

torsional strain

minimal strain

transannular
steric strain
23

VI. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

H H

poor overlap = bond angle strain

(i.e., 109.5 sp3 in 60 triangle)

H
H

H
H

plus ,

H
H

H
H

all Hs eclipsed =
torsional strain

H
Chem3D
24

VI. Conformations of Cycloalkanes

A. Stabilities of cycloalkanes

H
H

H
H

H
H

Chem3D

H
H

H
H

planar, 90
but all eclipsed

H
H
H

H
H

puckered, 88
slightly more angle strain,
but less eclipsing strain

envelope
relieves eclipsing
planar, 108
but all eclipsed
25

VI. Conformations of Cycloalkanes

B. Conformations in cyclohexane
1. chair and boat conformations

H
H

H
H

H
H

H
H

flagpole interaction

chair conformation
- all staggered
- no eclipsing
- no steric strain
no ring strain
(99.99% at room temp.)

H
H
H

H
H

H
H

G ~ 7 kcal

Chem3D

boat conformation
- eclipsing ~ 4 kcal
- steric strain ~ 3 kcal
ring strain ~ 7 kcal
skewed boat ~ 1.5 kcal
more stable than boat
(0.01% at room temp.)

26

VI. Conformations of Cycloalkanes

B. Conformations in cyclohexane
2. equatorial and axial positions

H
H

H
H

H
H

H
H

axial positions

equatorial positions

3. chair-chair interconversion

H
H

H
H

H
H

H
H

H
H

H
H

H
H
H

Ea ~ 10 kcal

27

VI. Conformations of Cycloalkanes

B. Conformations in cyclohexane
4. drawing cyclohexane chairs

28

VI. Conformations of Cycloalkanes

Ray

C. Substituted cyclohexanes
CH3

1,3-diaxial
repulsions

CH3
H

CH3
H
equatorial
(95%)
no steric strain
(anti)

Chem3D

axial
(5%)
steric repulsions
(gauche)

G ~ 1.8 kcal
(or 0.9 kcal
per CH3-H
repulsion)

29

VI. Conformations of Cycloalkanes

C. Substituted cyclohexanes
More pronounced effect with larger groups:

(99.99%)

G ~ 5.5 kcal

(0.01%)

locked in equatorial conformation

30

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3

CH3

CH3

trans-

cis-1,4-dimethylcyclohexane
stereoisomers

*configurational
conformational
(cannot convert from
(can be converted from
one to another without
to another by rotation
breaking bonds)
about a bond)
*geometric isomers
31

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3
CH3
CH3
CH3

CH3
H

CH3

G ~ 3.6 kcal

CH3

H
CH3

diequatorial
no repulsions

diaxial
4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal
32

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3
CH3

H3C

CH3

CH3

H
CH3

equatorial-axial
2 x 0.9 = 1.8 kcal

CH3

CH3

G = 0 kcal

axial-equatorial
2 x 0.9 = 1.8 kcal
33

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3
CH3

CH3
H

CH3

CH3

1 gauche interaction
= 0.9 kcal

G ~ 2.7 kcal

H
H

CH3

4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal

34

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
CH3

CH3

CH3
CH3

H3C

no repulsions

CH3

G ~ 5.4 kcal

2 1,3-diaxial CH3-H = 1.8 kcal

1 1,3-diaxial CH3-CH3 = 3.6 kcal

35

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Larger groups predominate in determining conformation:
CH3

tBu

CH3

G ~ 3.7 kcal

CH3

1.8 kcal

5.5 kcal
36

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Question 3-1. Draw the most stable chair form of the following compounds.
Explain. Click on the arrow to check your answers.
CH(CH3)2

CH3

CH3

CH3

CH3

Check Answer

37

VI. Conformations of Cycloalkanes

D. Disubstituted cyclohexanes
Answer 3-1. Draw the most stable chair form of the following compounds.
Explain. Click on the arrow to check your answers.
CH(CH3)2

CH3

CH3

CH3

CH3
CH3

CH3
CH3

CH3

All groups can be equatorial. This

chair form is more stable than the
other, where all are axial.

CH(CH3)2

Isopropyl is bigger than a methyl

group, so more stable chair is where
38
larger group is equatorial.