Organic Chemistry

Alkanes & cycloalkanes

Alkanes Alk
general formula CnH2n+2 alkanes are saturated (each C is bound to 4 other atoms)

Alkanes
Hydrocarbon chains where all the bonds between carbons are SINGLE b d b t b bonds Name uses the ending ane Examples: Methane, Propane, Butane, Octane, Methane, Propane, Butane, Octane, 2-methylpentane methylpentane

Summary: IUPAC Rules for Alkane Nomenclature

1. Find and name the longest continuous carbon chain. This is called the parent c a . (Examples: methane, s s ca ed e pa e t chain ( a p es e a e, chain. propane, etc.) 2. Number the chain consecutively, starting at the end nearest an attached group (substituent). g p (substituent). ) 3. Identify and name groups attached to this chain. (Examples: methyl-, bromo-, etc.) methyl- bromo4. Designate the location of each substituent group with the number of the carbon parent chain on which the group is attached. Place a dash between numbers and letters. (Example: 3-chloropentane) 35. Assemble the name, listing groups in alphabetical order. The prefixes di, tri, tetra etc., used to designate several groups of the same kind, are not considered when alphabetizing. Pl l h b ti i Place a comma b t between multiple lti l numbers. (Example: 2,3-dichloropropane) 2,3-

Step 1 Find the parent chain 1. chain.

Where is the longest continuous chain of carbons?

Prefixes for # of Carbons

1 2 3 4 5 Meth Eth Prop But Pent 6 7 8 9 10 Hex Hept p Oct Non Dec

IUPAC Names for Alkanes

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Endings
Alkanes (all C-C single bonded parent chain) Cend in ane Methane CH4 Methane Ethane C2H6 Ethane Propane C3H8 Propane Attached carbon groups (substituents) end i yl Att h d b (substituents) d in l b tit t Methyl CH3 Methyl Ethyl CH3CH2Ethyl l Propyl CH3CH2CH2 Propyl
3-ethylpentane

Step 2. Number the parent chain.

Number the parent chain so that the attached groups are on the lowest numbers
Methyl is on carbon #2 of the parent chain Methyl is on carbon #4 of the parent chain 1 5 2 4 3 3 4 2 5 1 GREEN is the right way for this one!

1 8

27 3 6 4 5 5 4 7 2 6 3 8 1 1 7 2 6 3 5 4 4 5 3 6 72 1

Groups on 4, 6, and 7 Groups on 2, 3, and 5

Groups on 2 and 5

Groups on 3 and 6

Step 3. Name the attached groups 3 groups.

Carbon (alkyl) groups ( y (alkyl) g p Methyl CH3 Methyl Ethyl CH3CH2Ethyl y Propyl CH3CH2CH2 Propyl Halogens Fluoro (F-) (F Chloro (Cl-) Cl Bromo (Br-) (Br Iodo (I-) (I-

Step 4. Designate where the group is i attached to the parent chain. h d h h i

Use the numbers of the parent chain from step 2 to designate the location of the attached groups to the parent chain.
2-methyl

Step 5. Alphabetize the groups, combine lik groups, and assemble. bi like d bl
The prefixes di, tri, tetra di, etc., used to designate several groups of the same kind ki d Prefixes are not considered when alphabetizing (Example: dimethyl = m for alphabetizing) Parent chain goes LAST

1,1,1-trichloro-1fluoromethane

1,1-dichloro-1,1difluoromethane

Draw Some Simple Alkanes

2-methylpentane 3-ethylhexane th lh 2,2-dimethylbutane 2,2 2,3-dimethylbutane 2,3-

Order of Priority
IN A TIE halogens get the lower number TIE, before alkyl groups

4-chloro-2-methylpentane or chloro2-chloro-4-methylpentane? chloro-

Order of Priority
IN A TIE between SIMILAR GROUPS the GROUPS, group lower ALPHABETICALLY gets the lower number

4 bromo 2 chloropentane 4-bromo-2-chloropentane or 2-bromo-4-chloropentane ?

Isomers
St i ht chain alkanes: A alkane Straight h i alkanes: An lk lk that has all its carbons connected in a row. row. Branched chain alkanes: An alkane alkanes: that has a branching connection of carbons. carbons. Isomers: Compounds with same Isomers: molecular formula but different structures. structures.

 There is only one possible way that the carbons in methane (CH4), ethane (C2H6), arranged. and propane (C3H8) can be arranged.

However, However carbons in butane (C4H10) can be arranged in two ways; four carbons in a row ways; (linear alkane) or a branching (branched alkane) alkane) alkane). These two structures are two isomers for butane. butane.

Isomers

methane 1 isomer

ethane 1 isomer

propane 1 isomer

Isomers

normal butane (n-butane) (n butane)

isobutane

Different isomers are completely different compounds. compounds. They have different structures, different physical properties such as melting p y p p g point and boiling point, and may have different physiological properties. properties.

Learning Check
Draw all possible structural isomers of C5H12

Types of Carbon Atoms

Primary carbon y a carbon bonded to one other carbon Secondary carbon (2o) a carbon bonded to two other carbons Tertiary carbon a carbon bonded to three other carbons (3o) ( o) (1

H C C H H
H C C C H

H C C C C

Alkanes
Example: Name the following compounds:

CH3 CHCH3 CH3 C CH2 CH2Br CH2CH3

CH3 CH CH3 CH3 CH CH CH2 CH CH3 CH2CH3 CH3 C CH3 CH3

Structural Formulas
Alkanes are written with structural formulas that are Expanded to show each bond bond. Condensed to show each carbon atom and its attached hydrogen atoms atoms. Line to show bonds as lines and omit hydrogens
H H C H H C H H C H H H3C H2 C CH3

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Expanded and Condensed Structures St t

TABLE 11.3

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Line Bond Line-Bond Formulas

Because each C atom has a tetrahedral arrangement, the order of atoms is not a straight line, but a zigzag pattern. A line-bond formula abbreviates the carbon atoms and shows only the zigzag pattern of bonds from carbon atom t carbon atom. b d f b t to b t

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Alkanes
Example: Write the condensed structure for the following compounds: t t f th f ll i d 3,33,3-dimethylpentane 2-methyl-4-sec-butyloctane methyl- sec-bu y oc a e e y 1,2-dichloro1,2-dichloro-3-methylheptane

Cycloalkanes
Are cyclic alkanes alkanes. Have 2H fewer than the open chain. Are named by using the prefix cyclo before cyclothe name of the alkane chain with the same number of carbon atoms.

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Cycloalkanes
The structural formulas of cycloalkanes are usually y y represented by geometric figures, Cyclopropane CH2 Cyclobutane CH2 CH2 CH2 CH2 CH2 CH2
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Cycloalkanes

cyclopropane

Cycloalkanes
cyclobutane

cyclopentane

cyclohexane

Cycloalkanes

Naming Cycloalkanes with Substituents S b tit t

The name of a substituent is placed in front of the cycloalkane name. CH3 methylcyclobutane Number ring with two substituents 1-bromo-2-chlorocyclopentane 1 bromo 2 chlorocyclopentane Br B
Cl
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Nomenclature of Cycloalkanes

Name each of the following :

Name each of the following :

Name each of the following :

Name each of the following :

Some Properties of Alkanes

The properties of alkanes include being N Nonpolar. l Insoluble in water. L Less d dense th water than t Flammable in air. Relatively unreactive.

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Alkanes with 1-4 Carbon Atoms 14

Alkanes with 1-4 carbon atoms are 14 Methane, ethane, propane, and butane. Gases at room temperature. fuels. Used as heating fuels

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Alkanes with 5-17 Carbon Atoms

Alkanes with 5-8 carbon atoms are Liquids at room temperature. Pentane, hexane, heptane, and octane. Very volatile. Used to make gasoline. Alkanes with 9-17 carbon atoms Are liquids at room temperature g g points. Have higher boiling p Are found in kerosene, diesel, and jet fuels.

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Alkanes with 18 or more Carbon Atoms

Alkanes with 18 or more carbon atoms Have high molar masses. temperature. Are waxy solids at room temperature Used in waxy coatings of fruits and vegetables. vegetables

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Crude Oil
The hydrocarbons in crude oil are Separated by boiling points. Heated to higher temperatures to produce prod ce gases that can be removed and cooled.

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Alkane Reactions
1. Combustion
The Th combustion of carbon compounds, especially h d b ti f b d i ll hydrocarbons, h b b has been th the most important source of heat energy for human civilizations throughout recorded history.

CH3-CH2-CH3 + 5 O2 > 3 CO2 + 4 H2O + heat Two points concerning this reaction are important: 1. Since all the covalent bonds in the reactant molecules are broken, the quantity of heat evolved in this reaction is related to the strength of these bonds (and of course, the strength of the bonds formed in (and, course the products). 2. The stoichiometry of the reactants is important. If insufficient oxygen pp products will consist of carbon monoxide, a , is supplied some of the p highly toxic gas.

Combustion of Alkanes
Alkanes Undergo combustion by reacting with oxygen to p produce carbon dioxide, , water, and energy. Are typically not very reactive d t strong Cti due to t C C single bonds.
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alkane + O2

CO2 + H2O + energy gy

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Balancing A Combustion Equation

Write the equation C5H12 + O2 Balance C C5H12 + O2 Balance H C5H12 + O2 Balance O with O2 C5H12 + 8O2

CO2 + H2O 5CO2 + H2O 5CO2 + 6H2O 5CO2 + 6H2O balanced

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2. Halogenation
Halogenation is the replacement of one or more hydrogen atoms in an organic compound by a halogen ( g p y g (fluorine, chlorine, bromine or , , iodine).

CH4 + Cl2 + energy > CH3Cl + HCl When alkanes react with halogens: One or more hydrogens will be replaced with halogens y g p g Halogens prefer to go to the more substituted (location with more surrounding carbons) location Tertiary is more reactive than secondary which is more reactive than primary Light or heat is required to form the radicals Radicals have unpaired electrons and violate the octet rule (reactive)

Free Radical Halogenation Mechanism M h i

Light Li ht 1. 2. 2 3.
X R R X H X

+ X
R R

+ X
X

+ X
X

+ X

+ X

used to indicate an unpaired electron (free radical) X = shorthand for a halogen atom R = shorthand for an organic compound or group

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Free Radical Halogenation g Mechanism

1. inisiation 1 inisiation,

2. propagation

radical reaction with Cl2:

3. termination;

Predicting the Major Product of Free Radical H l R di l Halogenation ti

Halogens p g prefer more substituted location on molecule Tertiary is more reactive than secondary which is more reactive than primary Reactivity depends on ease of forming radical Below radicals listed from easiest to form to hardest
C C C C C H C C H H C C H H C H

tertiary

secondary

primary

methyl
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Predict the Major Product

H H C H H C H H C H CH3 H2C H2C CH Br + B2 CH2 H

+ Cl2

+ Br2

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Predict the Major Product

H H C H H C H H C H CH3 H2C H2C CH H2 C C CH2 H H Cl C H CH3 Br H C H H

+ Cl2

C H

+ HCl

+ Br2
CH2 H2 C

+ HBr

+ Br2

Br

+ HBr

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