Alkanes and Cycloalkanes

Chapter 3
3-1

Structure
Hydrocarbon:

a compound composed only of carbon and hydrogen Saturated hydrocarbon: a hydrocarbon containing only single bonds Alkane: a saturated hydrocarbon whose carbons are arranged in an open chain Aliphatic hydrocarbon: another name for an alkane

3-2

Hydrocarbons
Hydrocarb on s Saturated Un saturated

Class

Alkan es (Ch apter 2)

Alk enes (Chap ters 5-6) One or more carb on -carbon double b on ds H H C C H H Eth ene

A lkynes (Ch apter 7) One or more carbon-carb on trip le bonds H-C C-H Acetylen e

Arenes (Ch apter 21-22) On e or more ben zenelike rin gs

Carbon- Only carboncarbon carbon sin gle bondin g bond s HH Example H-C-C-H HH N ame Ethan e

Ben zene

3-3

Structure
Shape

tetrahedral about carbon all bond angles are approximately 109.5

3-4

Drawing Alkanes
Line-angle

formulas

an abbreviated way to draw structural formulas each vertex and line ending represents a carbon
Ball-and stick mod el Line-an gle formula Structu ral formu la CH3 CH2 CH3 Propane CH3 CH2 CH2 CH3 Butan e CH3 CH2 CH2 CH2 CH3 Pentan e

Homologues differ by the number of methylene units Methylene = CH2

3-5

Constitutional Isomerism
Constitutional

isomers: compounds with the same molecular formula but a different connectivity of their atoms
example: C4H10

CH3 CH2 CH 2 CH3 Butane (bp -0.5C)

CH3 CH3 CHCH3 2-Methylpropane (bp -11.6C)

3-6

Constitutional Isomerism
do these formulas represent constitutional isomers?
CH3 CH3 CH3 CH3 CHCH2 CH and CH3 CH2 CHCHCH3 CH3 CH3 (each is C7 H 16)

find the longest carbon chain number each chain from the end nearest the first branch compare chain lengths as well the identity and location of branches
CH3 5 CH3 4 CH3 CHCH2 CH 1 2 3 CH3
2 4

and
5

CH3 CH3 CH2 CHCHCH3 2 1 CH3

5 4 3

3-7

Constitutional Isomerism
Mole cular Formula CH 4 C5 H1 2 C1 0 H2 2 C1 5 H3 2 C2 5 H5 2 C3 0 H6 2 Constitutional Is ome rs 1 3 75 4,347 36,797,588 4,111,846,763

World population is about 7,000,000,000

Note molecular formulas follow a pattern: CnH2n+2 (applies to all isomers (by definition))
3-8

Nomenclature - IUPAC
Suffix

-ane specifies an alkane Prefix tells the number of carbon atoms

Pre fix Carbons meth1 eth2 prop3 but4 pent5 hex6 7 heptoct8 non9 dec10 Carbons Pre fix unde c11 dodec12 tride c13 te tradec14 pentadec- 15 hexadec16 heptadec- 17 octade c18 nonadec19 eicos 20
3-9

Nomenclature - IUPAC
Parent

name: the longest carbon chain Substituent: a group bonded to the parent chain
alkyl group: a substituent derived by removal of a hydrogen from an alkane; given the symbol RAlk ane CH4 CH3 CH3 Name Methane Eth ane Alk yl group Name CH3 CH3 CH2 Methyl group Eth yl group

3-10

Nomenclature - IUPAC
1.The name of a saturated hydrocarbon with an unbranched chain consists of a prefix and suffix 2. The parent chain is the longest chain of carbon atoms 3. Each substituent is given a name and a number
CH3 CH3 CHCH3
1 2 3

2-Methylprop ane

4. If there is one substituent, number the chain from the end that gives it the lower number
CH3 CH3 CH2 CH2 CHCH3
4 5 3 2 2 1 1 3 4

2-Methylpen tane

(not 4-meth ylp entane)

3-11

Nomenclature - IUPAC
5. If there are two or more identical substituents, number the chain from the end that gives the lower number to the substituent encountered first indicate the number of times the substituent appears by a prefix di-, tri-, tetra-, etc. use commas to separate position numbers
6 4 2 1 3 5

2,4-Dimethylhexan e (n ot 3,5-d imethylhexan e)

3-12

Nomenclature - IUPAC
6. If there are two or more different substituents, list them in alphabetical order number from the end of the chain that gives the substituent encountered first the lower number
1 2 3 4 5 6 7 7 6 5 4 3 2 1

3-Ethyl-5-methylh eptane

(n ot 3-methyl-5-ethylheptane)

3-13

Nomenclature - IUPAC
7. The prefixes di-, tri-, tetra-, etc. are not included in alphabetization alphabetize the names of substituents first and then insert these prefixes
1 3 4 5 6

4-Ethyl-2,2-dimethylhexane (not 2,2-dimethyl-4-ethylhexane)

3-14

Nomenclature - IUPAC
Alkyl
Name butyl 2-methylpropyl (isobutyl) 1-methylpropyl (sec- butyl)

groups
Conde nsed Structural Formula - CH 2 CH2 CH2 CH 3 - CH 2 CHCH3 CH3 - CH CH 2 CH3 CH3 CH3 Name methyl ethyl propyl Conde nsed Structural Formula - CH 3 - CH 2 CH3 - CH 2 CH2 CH3

1-methylethyl - CH CH 3 (isopropyl) CH3

1,1-dimethylethyl - CCH3 (tert- butyl) CH3

3-15

Nomenclature - Common
The

number of carbons in the alkane determines the name

all alkanes with four carbons are butanes, those with five carbons are pentanes, etc. iso- indicates the chain terminates in -CH(CH3)2; neothat it terminates in -C(CH3)3
CH3 CH3 CH2 CH2 CH3 Butane CH3 CHCH3 Is ob utane CH3 CH3 CH2 CH2 CH2 CH3 CH3 CH2 CHCH3 Pentan e Is op entane CH3 CH3 CCH3 CH3 N eopentan e
3-16

Classification of C & H
Primary

(1) C: a carbon bonded to one other

carbon
1 H: a hydrogen bonded to a 1 carbon
Secondary

(2) C: a carbon bonded to two other

carbons
2 H: a hydrogen bonded to a 2 carbon
Tertiary

(3) C: a carbon bonded to three other

carbons
3 H: a hydrogen bonded to a 3 carbon
Quaternary

(4) C: a carbon bonded to four other

3-17

carbons

Physical Properties
Intermolecular

forces of attraction (example)

Alkanes are non-polar, and interact mainly by dispersion forces (very weak electrostatic attraction between temporary dipoles) Not soluble in water (no H bonding or polarity) Oil and water dont mix this is why

3-18

Sources of Alkanes
Natural

gas

90-95% methane
Petroleum

gases (bp below 20C) naphthas, including gasoline (bp 20 - 200C) kerosene (bp 175 - 275C) fuel oil (bp 250 - 400C) lubricating oils (bp above 350C) asphalt (residue after distillation)

Coal

3-19

Physical Properties
Low-molecular-weight

alkanes (methane....butane) are gases at room temperature Higher molecular-weight alkanes (pentane, decane, gasoline, kerosene) are liquids at room temperature High-molecular-weight alkanes (paraffin wax) are semisolids or solids at room temperature

3-20

Melting points by size

Note that melting points depend on a) size of molecule, and b) ability to pack in solid. Odd number alkanes apparently do not pack well

3-21

Boiling points dont go that way

For homologous series, boiling points mirror size Branching lowers the bp
3-22

Physical Properties
Constitutional

isomers have different physical

properties
mp ( C) -95 -154 -118 -129 -98 bp ( C) 68.7 60.3 63.3 58.0 49.7 Density (g/mL) 0.659 0.653 0.664 0.661 0.649

Name hexane 2-methylpentane 3-methylpentane 2,3-dimethylbutane 2,2-dimethylbutane

3-23

Conformations
Conformation:

any three-dimensional arrangement of atoms in a molecule that results from rotation about a single bond Newman projection: a way to view a molecule by looking along a carbon-carbon single bond
H H H H H H

3-24

Conformations
Staggered

conformation: a conformation about a carbon-carbon single bond in which the atoms or groups on one carbon are as far apart as possible from the atoms or groups on an adjacent carbon
H H H H H H

3-25

Conformations
Eclipsed

conformation: a conformation about a carbon-carbon single bond in which the atoms or groups of atoms on one carbon are as close as possible to the atoms or groups of atoms on an adjacent carbon
H
H

H H

HH

3-26

Conformations
Torsional

strain

also called eclipsed interaction strain strain that arises when nonbonded atoms separated by three bonds are forced from a staggered conformation to an eclipsed conformation the torsional strain between eclipsed and staggered ethane is approximately 12.6 kJ (3.0 kcal)/mol

+12.6 kJ/mol

3-27

Conformations
Dihedral

angle (Q): the angle created by two intersecting planes

3-28

Conformations
Ethane

as a function of dihedral angle

3-29

Conformations
The

origin of torsional strain in ethane

originally thought to be caused by repulsion between eclipsed hydrogen nuclei alternatively, caused by repulsion between electron clouds of eclipsed C-H bonds theoretical molecular orbital calculations suggest that the energy difference is not caused by destabilization of the eclipsed conformation but rather by stabilization of the staggered conformation this stabilization arises from the small donor-acceptor interaction between a C-H bonding MO of one carbon and the C-H antibonding MO on an adjacent carbon; this stabilization is lost when a staggered conformation is converted to an eclipsed conformation
3-30

Conformations
anti

conformation

a conformation about a single bond in which the groups lie at a dihedral angle of 180
CH3 H H CH3 H H

3-31

Conformations
Steric

strain (nonbonded interaction strain):

the strain that arises when atoms separated by four or more bonds are forced closer to each other than their atomic (contact) radii will allow
Angle

strain:

strain that arises when a bond angle is either compressed or expanded compared to its optimal value
The

total of all types of strain can be calculated by molecular mechanics programs

such calculations can determine the lowest energy arrangement of atoms in a given conformation, a process called energy minimization
3-32

Conformations
conformations of butane as a function of dihedral angle

3-33

Anti Butane
Energy-minimized

anti conformation

the C-C-C bond angle is 111.9 and all H-C-H bond angles are between 107.4 and 107.9 the calculated strain is 9.2 kJ (2.2 kcal)/mol

3-34

Eclipsed Butane
calculated energy difference between (a) the nonenergy-minimized and (b) the energy-minimized eclipsed conformations is 5.6 kJ (0.86 kcal)/mol

3-35

Oxidation of Alkanes
Oxidation

is the basis for their use as energy sources for heat and power
heat of combustion: heat released when one mole of a substance in its standard state is oxidized to carbon 0 dioxide and water H
kJ(k cal)/mol CH4 + 2 O2 Methan e CH3 CH2 CH3 + 5 O2 Propane CO2 + 2 H2 O 3 CO2 + 4 H2 O -890.4 (-212.8) -2220 (-530.6)

3-36

Heat of Combustion
Heat

of combustion for constitutional isomers

S tru ctural formu la H 0 [k J (k cal)/mol] -5470.6 (-1307.5) -5465.6 (-1306.3) -5458.4 (1304.6)

Hydrocarbon Octane 2-Methylhep tane 2,2-D imeth ylhexan e 2,2,3,3-Tetramethylbu tane

-5451.8 (1303.0)

3-37

Heats of Combustion
For

constitutional isomers [kJ (kcal)/mol]

-5470.6 (-1307.5) -5465.6 (-1306.3) -5458.4 (1304.6)-5451.8 (1303.0)

8 CO2 + 9 H2 O

3-38

Sources of Alkanes
Natural

gas

90-95% methane
Petroleum

gases (bp below 20C) naphthas, including gasoline (bp 20 - 200C) kerosene (bp 175 - 275C) fuel oil (bp 250 - 400C) lubricating oils (bp above 350C) asphalt (residue after distillation)

Coal

3-39

Gasoline
Octane

rating: the percent 2,2,4-trimethylpentane

(isooctane) in a mixture of isooctane and heptane that has equivalent antiknock properties

Heptane (octane rating 0)

2,2,4-Trimethylpentane (octane rating 100)

3-40

Cycloalkanes
General

formula CnH2n and nomenclature

five- and six-membered rings are the most common

Structure

to name, prefix the name of the corresponding openchain alkane with cyclo-, and name each substituent on the ring if only one substituent, no need to give it a number if two substituents, number from the substituent of lower alphabetical order if three or more substituents, number to give them the lowest set of numbers and then list substituents in alphabetical order
3-41

Cycloalkanes
Line-angle

drawings

each line represents a C-C bond each vertex and line ending represents a C
C C C C C C C C H2 C H2 C CH2 CH2 C8 H1 6 CH3 CH3 CH CH

3-42

Cycloalkanes

Example: name these cycloalkanes

(a) (b)

(c)

(d)

3-43

Bicycloalkanes
Bicycloalkane:

an alkane that contains two rings that share two carbons

Bicyclo[4.4.0]decane (Decalin)

Bicyclo[4.3.0]nonane (Hydrindane)

Bicyclo[2.2.1]heptane (Norbornane)

3-44

Bicycloalkanes
Nomenclature

parent is the alkane of the same number of carbons as are in the rings number from a bridgehead, along longest bridge back to the bridgehead, then along the next longest bridge, etc. show the lengths of bridges in brackets, from longest to shortest
1 6 7 5 4 3 2

Bicyclo[2.2.1]h eptane
3-45

IUPAC - General
prefix-infix-suffix

prefix tells the number of carbon atoms in the parent infix tells the nature of the carbon-carbon bonds suffix tells the class of compound
Nature of Carbon-Carbon Bonds in the Parent Chain all single bonds one or more double bonds one or more triple bonds Suffix -e -ol Class hydrocarbon

Infix
-an-en-yn-

alcohol -al aldehyde -amine amine -one ketone -oic acid carboxylic acid
3-46

IUPAC - General
prop-en-e = propene CH3 CH=CH 2 eth-an-ol = ethanol OH but-an-one = butanone HC CH but-an-al = butanal pent-an-oic acid = pentanoic acid CH3 CH2 NH 2 cyclohex-an-ol = cyclohexanol O eth-yn-e = ethyne CH3 CH2 CH2 CH eth-an-amine = ethanamine
O
O CH3 CCH2 CH 3

CH3 CH2 OH

CH 3 CH 2 CH 2 CH 2 COH

3-47

Cyclopropane
angle strain: the C-C-C bond angles are compressed from 109.5 to 60 torsional strain: there are 6 sets of eclipsed hydrogen interactions strain energy is about 116 kJ (27.7 kcal)/mol
H H H

H H

3-48

Cyclobutane
puckering from planar cyclobutane reduces torsional strain but increases angle strain the conformation of minimum energy is a puckered butterfly conformation strain energy is about 110 kJ (26.3 kcal)/mol

3-49

Cyclopentane
puckering from planar cyclopentane reduces torsional strain, but increases angle stain the conformation of minimum energy is a puckered envelope conformation strain energy is about 42 kJ (6.5 kcal)/mol

3-50

Cyclohexane
Chair

conformation: the most stable puckered conformation of a cyclohexane ring

all bond C-C-C bond angles are 110.9 all bonds on adjacent carbons are staggered

3-51

Cyclohexane
In

a chair conformation, six H are equatorial and six are axial

3-52

Cyclohexane
For

cyclohexane, there are two equivalent chair conformations

all C-H bonds equatorial in one chair are axial in the alternative chair, and vice versa

3-53

Cyclohexane
Boat

conformation: a puckered conformation of a cyclohexane ring in which carbons 1 and 4 are bent toward each other
there are four sets of eclipsed C-H interactions and one flagpole interaction a boat conformation is less stable than a chair conformation by 27 kJ (6.5 kcal)/mol

3-54

Cyclohexane
Twist-boat

conformation

approximately 41.8 kJ (5.5 kcal)/mol less stable than a chair conformation approximately 6.3 kJ (1.5 kcal)/mol more stable than a boat conformation

3-55

Methylcyclohexane
Equatorial

and axial methyl conformations

CH3 +7.28 k J/mol CH3

3-56

Cis,Trans Isomerism
Stereoisomers:

compounds that have

the same molecular formula the same connectivity a different orientation of their atoms in space
Cis,trans

isomers

stereoisomers that are the result of the presence of either a ring (this chapter) or a carbon-carbon double bond (Chapter 8)

3-57

G0 axial ---> equatorial

given the difference in strain energy between axial and equatorial conformations, it is possible to calculate the ratio of conformations using the following relationship
G = -R T ln Ke q
0

axial --> equatorial Group C N F C CH I Cl Br OH G (k J/mol) 0.8 1.0 1.7 1.9 2.2 2.4 3.9 Group N H2 COOH CH= CH2 CH3 CH2 CH3 G (k J/mol) 5.9 5.9 7.1 7.28 7.3

CH( CH 3 ) 2 9.0 C( CH3 ) 3 21.0

3-58

Isomers
relationships

among isomers

3-59

Cis,Trans Isomers
1,2-Dimethylcyclopentane H H H H H H H

H H H HH3 C H CH3 H

H CH3 CH3

H3 C

CH3

H3 C

CH3

cis-1,2-D imeth ylcyclop entane

trans-1,2-D imethylcyclop entane

3-60

Cis,Trans Isomerism
1,4-Dimethylcyclohexane

H H3 C

CH3 H CH3

H H3 C

H CH3 CH3

H3 C t rans-1,4-D imethylcyclohexane

H3 C cis-1,4-D imethylcycloh exane

3-61

Cis,Trans Isomerism
trans-1,4-Dimethylcyclohexane

the diequatorial-methyl chair conformation is more stable by approximately 2 x (7.28) = 14.56 kJ/mol
CH3 H H CH3 (less s table) H (more s table) H H3 C CH3

3-62

Cis,Trans Isomerism
cis-1,4-Dimethylcyclohexane

H CH3 H CH3 H3 C

H conformation s are of equal s tability CH3

3-63

Steroids
The

steroid nucleus
C A B D

Cholestanol
CH3

H H HO H Choles tanol H HO H

CH3 H

H H

3-64