Alkanes

Alkanes are fully saturated hydrocarbons - hydrocarbons have only Cs and Hs - saturated = all single bonds (max. # of Hs) Alkanes have the general formula CnH2n+2 - example: C4H10 They can be straight-chained or branched - example: CH3CH2CH2CH3 vs. (CH3)2CHCH3 Alkanes, and all other organic compounds, are named according the the IUPAC system (International Union of Pure and Applied Chemistry)

Alkanes
line-angle formula:
a line represents a carbon-carbon bond and an angle represents a carbon atom a line ending in space represents a -CH3 group hydrogen atoms are not shown in line-angle formulas
Ball-andstick model Line-an gle formula Conden sed structu ral formula CH3 CH2 CH3 Propan e CH3 CH2 CH2 CH3 Butane CH3 CH2 CH2 CH2 CH3 Pen tane

Naming Straight-Chain Alkanes and Alkyl Groups

The names of all alkanes end in -ane The number of carbons in a straight-chain alkane is indicated by putting a prefix before the -ane Examples: CH4 = methane CH3-CH3 = ethane CH3-CH2-CH3 = propane In branched alkanes the substituents (groups attached to the carbon chain) are called alkyl groups An alkyl group = an alkane with one H removed Alkyl groups are named by changing the ending of the alkane name to -yl Example: CH3-CH2- = ethyl

Classification of Carbons in Alkanes

Carbons can be classified by how many other Cs are attached to them: - No Cs = methyl CH4 -1C = primary (1) CH3-CH3 - 2 Cs = secondary (2) CH3-CH2-CH3 - 3 Cs = tertiary (3) CH3-CH(CH3)2 - 4 Cs = quaternary (4) C(CH3)4

Naming Branched Alkanes

First find the longest chain of Cs (parent) Number the Cs in parent chain (begin at end nearest 1rst branch point) Identify substituents and number by point of attachment to parent chain Write full name Example: CH3-CH(CH3)-CH2-CH3 = 2-methylbutane If there is more than one of a substituent a prefix is used and a number is given for each substituent Example: CH3-CH2-C(CH3)3 = 2,2-dimethylbutane

IUPAC Names
1. The name for an alkane with an unbranched chain of carbon atoms consists of a prefix showing the number of carbon atoms and the ending -ane 2. For branched-chain alkanes, longest chain of carbon atoms is the parent chain and its name is the root name 3. Name and number each substituent on the parent chain; use a hyphen to connect the number to the name
CH3 CH3 CHCH3
1 2 3

2-Methylprop ane

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

2-Methylpentane (n ot 4-methylpentane)

IUPAC Names
5. If the same substituent occurs more than once,
number the parent chain from the end that gives the lower number to the substituent encountered first indicate the number of times the substituent occurs by a prefix di-, tri-, tetra-, penta-, hexa-, and so on use a comma to separate position numbers
CH3 CH3 CH3 CH2 CHCH2 CHCH3
6 5 4 3 2 1

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

IUPAC Names
6. If there are two or more different substituents
list them in alphabetical order number the chain from the end that gives the lower number to the substituent encountered first if there are different substituents in equivalent positions on opposite ends of the parent chain, give the substituent of lower alphabetical order the lower number
CH3 CH3 CH2 CHCH2 CHCH2 CH3 CH2 CH3 3-Ethyl-5-methylhep tane (not 3-methyl-5-ethylheptan e)
2 1 3 4 5 6 7

IUPAC Names
7. Do not include the prefixes di-, tri-, tetra-, and so on, or the hyphenated prefixes secand tert- in alphabetizing;
alphabetize the names of substituents first, and then insert these prefixes
CH3 CH2 CH3 CH3 CCH2 CHCH2 CH3 CH3 4-Eth yl-2,2-d imethylhexan e (n ot 2,2-d imethyl-4-ethylhexane)
6 5

4 3

Conformations of Alkanes
Because alkanes have only single bonds they have free rotation about those bonds This allows for different spatial arrangements of the atoms called conformations Conformations are not the same as isomers Some conformations are more stable than others, so the compound spends more time in those For ethane(CH3-CH3): - when all Hs are lined up as you sight down the C-C bond, called eclipsed, this is highest energy - when none of the Hs are lined up, called staggered, this is lowest energy

Constitutional Isomerism
Constitutional isomers: compounds that have the same molecular formula but different structural formulas
for the molecular formulas CH4, C2H6, and C3H8, only one structural formula is possible; there are no constitutional isomers for these molecular formulas for the molecular formula C4H10, two constitutional isomers are possible

CH3 CH2 CH2 CH3 Bu tane (bp -0.5C)

CH3 CH3 CHCH3 2-Methylp ropan e (bp -11.6C)

Haloalkanes
Haloalkanes have one or more halogens replacing hydrogen on an alkane The halogens are numbered and named as substituents -F = fluoro - Cl = chloro - Br = bromo -I = iodo If more than one halogen is present, they are named in alphabetical order Example: CH3-CH(Br)-CH(Cl)-CH3 = 2-bromo-3-chlorobutane

Cycloalkanes
Carbons can also bond together to form rings Rings with only Cs, Hs and single bonds are called cycloalkanes Cycloalkanes have the general formula CnH2n The smallest is cyclopropane (C3H6) - cyclopropane is an unstable molecule - its forced to have bond angles of 120between the Cs, while they would normally be 109 (the carbons each have 4 electrons groups and should be tetrahedral) The only cycloalkanes with little or no strain are cyclopentane (C5H10) and cyclohexane (C6H12) Most cycloalkanes are not flat because they prefer tetrahedral geometry

Naming Cycloalkanes
Cycloalkanes are named by adding cyclo- to the parent alkane name Substituents are numbered when there is more than one of them They are numbered starting at the one that gives the others the lowest numbers Or, they are numbered alphabetically when there are only two, or both directions are equal
Cl

2-chloro-1,4-d imethylcyclohexane

Cis and Trans Isomers

Because cycloalkanes do not have free rotation around the carbons, it matters on which side of the ring a substituent is relative to other substituents Two substituents on the same side (top or bottom) of the ring are called Cis Two substituents on opposite sides of the ring are called Trans Cis and Trans isomers are stereoisomers; they have the same molecular formula, and the atoms are connected in the same order but are arranged in a different spacial orientation

Cyclohexane
axis th rough the cen ter of th e rin g

H H H H (a) Ball-and-s tick mod el sh ow ing all 12 hydrogen s (b) The s ix eq uatorial C-H bond s H H

H H H H

(c) The s ix axial C-H b on ds

Cyclohexane
the more stable conformation of a substituted cyclohexane ring has substituent group(s) equatorial rather than axial

CH3
CH3 Equatorial methylcyclohexane

Axial methylcyclohexane

Physical Properties of Alkanes and Cycloalkanes

Alkanes are nonpolar and are not soluble in water They have low melting and boiling points due to their weak intermolecular forces (dispersion) They are also less dense than water Alkanes are mostly obtained from crude oil - the crude oil is fractionated based on boiling pt. - heavier fractions are often cracked, put under high heat and pressure, to obtain more gasoline Alkanes are used extensively as fuels of various types (for heating, cooking, driving, etc.)

Reactions of Alkanes and Cycloalkanes

Because they are nonpolar, and their covalent bonds are strong, alkanes and cycloalkanes are relatively unreactive The two types of reactions that they do undergo are combustion and halogenation In combustion reactions, alkanes react with oxygen to form carbon dioxide, water and heat CH4 + 2O2 CO2 + 2H2O + Heat In halogenation reactions, halogens replace one or more Hs on an alkane (a substitution reaction) CH4 + Cl2 (+ light or heat) CH3Cl + HCl

Mechanism of Alkane Halogenation

These halogenations are radical reactions Radicals are molecules (or atoms) that have one or more unpaired electrons (the half-headed arrows represent movement of single electrons
1. Initiation:
Cl Cl

Light

Cl

Cl

H H

2. Propagation:

C H

Cl

C H

H-Cl

H H C H H

Cl

Cl

C H

Cl

Cl

3. Termination:

C H

Cl

C H

Cl