Chapter 2: Alkanes

QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.
 Alkanes from Carbon and Hydrogen
•Alkanes are carbon compounds that contain only single bonds.
•The simplest alkanes are hydrocarbons – compounds that contain only carbon and hydrogen.
•Hydrocarbons are used mainly as fuels, solvents and lubricants:
H H
H H H H H H H H H H H
C
H C C C C H H C C C C C H C C
H H
H H H H H H CH2 H CH3 C C
H
H
CH3 H H

# of carbons boiling point range Use

1-4 <20 °C fuel (gasses such as methane, propane, butane)

5-6 30-60 solvents (petroleum ether)

6-7 60-90 solvents (ligroin)

6-12 85-200 fuel (gasoline)

12-15 200-300 fuel (kerosene)

15-18 300-400 fuel (heating oil)

16-24 >400 lubricating oil, asphalt

 Hydrocarbons

Formula Prefix Suffix Name Structure

H

CH4 meth- -ane methane H C H

C2H6 eth- -ane ethane H3C CH3

C3H8 prop- -ane propane

C4H10 but- -ane butane

C5H12 pent- -ane pentane

C6H14 hex- -ane hexane

C7H16 hept- -ane heptane

C8H18 oct- -ane octane

C9H20 non- -ane nonane

C10H22 dec- -ane decane

 Hydrocarbons

Formula Prefix Suffix Name Structure

H
CH4 meth- -ane methane H C H

H H
C2H6 eth- -ane ethane H C C H

H H

H
C3H8 prop- -ane propane H3C C CH3 or

H H
C4H10 but- -ane butane H3C C C CH3 or
H H

H
C4H10 but- -ane butane? H3C C CH3 or
CH3
 Hydrocarbons
Hydrocarbons

Formula Prefix Suffix Name Structure

H
CH4 meth- -ane methane H C H

H H
C2H6 eth- -ane ethane H C C H

H H

H
C3H8 prop- -ane propane H3 C C CH3 or

H H
C4H10 but- -ane butane H3C C C CH3 or
H H

H
C4H10 but- -ane iso-butane H3C C CH3 or
CH3
 Hydrocarbons
Hydrocarbons

Formula Prefix Suffix Name Structure

H H
C4H10 but- -ane butane H3C C C CH3 or
H H

H
C4H10 but- -ane iso-butane H3C C CH3 or
CH3

H H H
C5H12 pent- -ane pentane H3C C C C CH3 or
H H H

H H H
C5H12 pent- -ane iso-pentane H3C C C C H or

H CH3 H

H CH3 H

C5H12 pent- -ane iso-pentane???H C C C H

or

H CH3 H
 Hydrocarbons
Hydrocarbons

Formula Prefix Suffix Name Structure

H H
C4H10 but- -ane butane H3C C C CH3 or
H H

H
C4H10 but- -ane iso-butane H3C C CH3 or
CH3

H H H
C5H12 pent- -ane pentane H3C C C C CH3 or
H H H

H H H
C5H12 pent- -ane iso-pentane H3C C C C H or

H CH3 H

H CH3 H

C5H12 pent- -ane neo-pentane H C C C H

or

H CH3 H
IUPAC System of Naming Organic Compounds

1. Find the longest carbon chain

2. Name all the atoms (other than H) not in the longest chain as groups

3. Number groups from the end of the chain closest to the first group

4. List multiple groups in alphabetical order,

H H H I UPAC Name
2 4
H3C C C C CH3 Longest chain: pentane
pentane
1 3 5 Groups: none
H H H

H H H 3 1
4 2 Longest chain: butane 2-methylbutane
H3C C C C H Groups: one methyl not: 3-methylbutane
H CH3 H not:
2 4
1 3

3
H CH3 H Longest chain: propane
2 2,2-dimethylpropane
H C C C H 1 Groups: two methyls

H CH3 H
IUPAC System of Naming
HydrocarbonsOrganic Compounds

Formula Prefix Suffix I UPAC Name Structure

H H
C4H10 but- -ane butane H3 C C C CH3or

H H

H
C4H10 but- -ane iso-butane H3 C C CH3

CH3

H H H
C5H12 pent- -ane pentane H3C C C C CH3

H H H

H H H
C5H12 pent- -ane 2-methyl butane H3 C C C C H

H CH3 H

H CH3 H
C5H12 pent- -ane 2,2-dimethylpropane H C C C H

H CH3 H
 Naming Branches as “Groups”
Naming Branches as Groups

Group Formula Prefix Suffix Name Abbreviation Structure

H
–CH3 meth- -yl methyl –Me C H

H
H H

–C2H5 eth- -yl ethyl C C H

–Et
H H

H H

C C CH3 or
–C3H7 prop- -yl propyl –Pr
H H

H3C C CH3 or
–C3H7 iso-prop- -yl iso-propyl –i Pr

H H H
–C4H9 but- -yl butyl –Bu C C C CH3 or
H H H
 Naming Branches as “Groups”
Other Groups We May Encounter

Group Formula Name Structure Group Formula Name Structure

–C4H9 iso-butyl –F fluoro –F

–C4H9 sec-butyl –Cl chloro –Cl

–C4H9 tert-butyl –Br bromo –Br

–C5H11 neo-pentyl –I iodo –I

 Structural Isomers
How many structural isomers – compounds with the same chemical formula but different
connectivity – are there with the formula C7H16?
 Structural Isomers
How many structural isomers – compounds with the same chemical formula but different
connectivity – are there with the formula C7H16?

IUPAC Name CH3 IUPAC Name

2 4 6 4
2
heptane 2,2-dimethylpentane
1 3 5 7 1 CH3 3 5

CH3 CH3
4 6 3
2 2-methylhexane 2 4 2,3-dimethylpentane
1 3 5 1 5
CH3

2 4 6 CH3 CH3
3
3-methylhexane
1 5 2 4 2,4-dimethylpentane
CH3 1 3 5

CH3 2 CH3 4
2 6 3,3-dimethylpentane
4 4-methylhexane 1 3 5
1 3 5 CH3

2 4
CH3 3
–2 3 –6 3-ethylpentane
1 5
6 5 4 –4 2 3-methylhexane
1
–1 –3 5– 1 CH3
2
3-methylhexane
3 –4
2 4 4 6 2-ethylpentane
H3 C –2 5
2,2,3-Trimethyl-butane –3 5–
1 3 1–
 MethylM ethyl
and& Ethyl Compounds
Ethyl Compounds

Group Formula Name Abbreviation Structure

H
H3C– methyl –Me C H

H
H H
H5C2– ethyl –Et C C H

H H

H3C–H methane H5C2–H ethane

H3C–OH methyl alcohol (methanol) H5C2–OH ethyl alcohol (ethanol)

H3C–NH 2 methylamine (aminomethane) H5C2–NH 2 ethylamine (aminoethane)

H3C–F methyl fluoride (fluoromethane) H5C2–F ethyl fluoride (fluoroethane)

H3C–Cl methyl chloride (chloromethane) H5C2–Cl ethyl chloride (chloroethane)

H3C–Br methyl bromide (bromomethane) H5C2–Br ethyl bromide (bromoethane)

H3C–I methyl iodide (iodomethane) H5C2–I ethyl iodide (iodoethane)

H3C–CN methyl cyanide (cyanomethane, acetonitile) H5C2–CN ethyl cyanide (cyanoethane, proprionitile)

H3C–SH methanethiol (methyl mercaptan) H5C2–SH ethanethiol (ethyl mercaptan)

 Methyl and Ethyl Compounds
M ethyl & Ethyl Compounds

Group Formula Name Abbreviation Structure

H
H3C– methyl –Me C H

H
H H
H5C2– ethyl –Et C C H

H H

H
H C H
C H H3C–H methane H3C H5C2–H ethane
H

H3C methyl cation H3C–CH2 ethyl cation

C
C H
H H H3C–CH2 ethyl radical
H H3C methyl radical H3C
H

H3C methyl anion H3C–CH2 ethyl anion

C
C H
H H
H H3C
H
 Propyl Compounds
Propyl Compounds

Group Formula Name Abbreviation Structure

H H
H7C3– prop- –Pr C C CH3 or

H H
H
H7C3–
iso-prop- –iPr H3C C CH3 or

3 1 HO
2 3
OH propyl alcohol (1-propanol) 2 isopropyl alcohol (isopropanol; 2-propanol)
H2N 1
NH2 propyl amine (1-aminopropane) isopropyl amine (2-aminopropane)
F
F
propyl fluoride (1-fluoropropane) isopropyl fluoride (2-fluoropropane)
Cl
Cl
propyl chloride (1-chloropropane) isopropyl chloride (2-chloropropane)
Br
Br propyl bromide (1-bromopropane) isopropyl bromide (2-bromopropane)
I
I propyl iodide (1-iodopropane) isopropyl iodide (2-iodopropane)
 Structural Isomers of C7H16

2 4 6
1 7 heptane
What if we attatch the two ends together?
3 5

1 H2
7 2 C
H2C CH2
6 3
H2C CH2

5 4 H2C CH2

cycloheptane C7H 14

Cycloheptane contains two fewer hydrogens than heptane. They are not structural isomers.
 Cycloalkanes
Cycloalkanes

Compound Name Structure Group Name Structure

cyclopropane cyclopropyl

cyclobutane cyclobutyl

cyclopentane cyclopentyl

cyclohexane cyclohexyl

cycloheptane cycloheptyl

cyclooctane cyclooctyl
 Naming Cycloalkanes
Unlike "floppy" chains, rings have an additional consideration for multiple substitutions:

Me Me Me Me H
H H

H H H Me
Me H H

"flat" 1,2-dimethylcyclopropane "3-D" 1,2-dimethylcyclopropane "3-D" 1,2-dimethylcyclopropane

These are different compounds! They cannot be interconvertied by bond rotation.

Me Me Me H
H H

H H H Me
H H

cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane

cis – substituents on same side (of the ring)

trans – substituents on opposite sides (of the ring)

The above compounds are not structural isomers. Their connectivity is identical. They are stereoisomers – compounds that
differ in how substituents are arranged in space
 Naming Cycloalkanes
IUPAC Naming of Rings

How can we represent cis/trans isomers in a flat drawing?

Me Me

Me Me Me H
H H

H H H Me
H H
Me Me
cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane

A solid wedge means the bond is A dashed wedge means that the bond
pointing "up" and out of the page is pointing "down" and into the page
 Naming Cycloalkanes
IUPAC Naming of Rings

Don't let the wedges and dashes confuse you:

Me Me

Me Me

cis-1,2-dimethylcyclopropane cis-1,2-dimethylcyclopropane

These are the same compound!

Me

Me Me
H

H H
Me H
Flip over 180°

Me H
H
H

Me Me
H

Me
 3-Dimensional Structure/VSEPR Theory

A dashed wedge means: the substituent

X is behind the plane of the paper

109°
X
Atoms place substituents as far appart as possible: A
X
X
X A
X
A solid wedge means: the substituent is X
in front of the plane of the paper A = any atom X

X = any substituent (atom or lone pair)

H H F

C N O B
H H F
H H H F
H H F

tetrahedral electron-domain geometries

 3-Dimensional Structure

H H H H
H
H C C H C C
H H
H H H
each carbon is tetrahedral
"flat" ethane wedge/dash depiction of ethane

H
H
H

C C

H
H
H

"3-D" ethane
 3-Dimensional Structure
The Conformation of Ethane

If we look down the C–C bond axis, we get a different perspective:

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

W e can use a Newm an Projection to depict thisview:

The large circle is a stylized representation ofthe back atom

H H

Front atom appearsat vertex here

H H
H

Newm an Projection

But there is free rotation around single (σ) bonds:

these hydrogensare in
H the sam e plane H
H H
H H H
H
H H
C C
H C C
H H H H H
H H H H H HH
H
these hydrogensare in
The "staggered" conform ation the sam e plane
The "eclipsed" conform ation
 3-Dimensional Structure

these hydrogens are

H in the same plane H
H H
H H
H H
H H
C C
H C C
H H H H H
H H H H H HH
H
these hydrogens are
The "staggered" conformation in the same plane
The "eclipsed" conformation

The staggered conformation is the lowest energy conformation The elclpsed conformation is the highest energy confornation

H H
H
H H

H
H H H HH
H

The energy minimum The energy maximum

Molecules that differ by only rotations around single bonds are conformational Isomers.
 3-Dimensional Structure
Place substituents as far appart as possible:

180°

H3CCN H3C C N
Molecule is linear

120°

BF3 B

F F
Molecule is trigonal planar

2s 2px 2py 2pz

H

109° 2nd row valence orbitals

CH4 C
H
H
H
Molecule is tetrahedral

How can these molecular shapes arise from bonding between the available orbitals?
 Hybridization

180°

H3CCN H3C C N
Molecule is linear
2s 2px 2py 2pz

2nd row valence orbitals

this side gets bigger and

50% more spherical this side gets smaller and
50% more spherical

mixing
2px C C and C

2s

2 unhybridized orbitals 2 sp-hybridized orbitals

Only "X"-directionality; 50% s-like and 50% p-like

H3C C N H3C C N H3 C C N

sp-orbitals on the central carbon atom the σ-bond form ed bysp-orbitaloverlap

π-bonding in the triple bond

 Hybridization
F

120°
BF3
B

F F
Molecule is trigonal planar 2s 2px 2py 2pz

2nd row valence orbitals

this side gets bigger and

33% more spherical this side gets smaller and
33% more spherical

C
mixing and and
2px C C C
2s
2py

3 sp-hybridized orbitals
3 unhybridized orbitals
Only "X" and "Y"-directionality; 33% s-like and 67% p-like

F F

B F B F

F F

All 3 sp2-orbitals on the boron atom The σ-bonds between boron and fluorine
 Hybridization

109°

CH4 C
H
H
H
2s 2px 2py 2pz
Molecule is tetrahedral

2nd row valence orbitals

H H

mixing
C C
H H
H H
H H
2s 2px 2py 2pz
All 4 sp3-orbitals on the carbon atom The σ-bondsbetween carbon and hydrogen

All 4 unhybridized orbitals Each orbital has "X", "Y" and "Z"-directionality and are 25% s-like and 75% p-like