ALKANES

• Alkanes are saturated hydrocarbons containing only carbon-carbon single bonds

and have the general formula CnH2n+2
• Alkanes form the homologous series in which each representative differs from the
subsequent one in –CH2– group.

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Nomenclature of alkanes
All alkanes are divided into two groups:
• alkanes with a normal (unbranched) carbon chain;
• alkanes with a branched carbon chain.
Alkanes have the suffix –ane.
Names of alkanes with a normal carbon chain
• first four members of the alkane’s homologous series – methane, ethane, propane and
butane – have common names;
• names of other hydrocarbons with a normal carbon chains are formed from the names
of Greek numerals;

Names of alkanes with a branched carbon chain:

1. Select the main carbon chain (the longest unbranched carbon chain) :

2. Number carbon atoms from that side of the chain to which the substituent is
closer:

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 3. Indicate the position of the substituents (alkyl groups) by digits (locants).

If substituents are on equal If identical substituents are on

distances from both ends of a equal distances from both ends of
molecule, the numbering a molecule, numbering is begun
beginning is defined by the with that end where the amount of
alphabetic order: substituents is higher:

Same alkyl radicals are designated by multiplying preffixies di-, tri-, tetra- etc.;

An alkyl – is the rest of a hydrocarbon, formed as a result of the hydrogen atom elimination:
The most important alkyl groups are listed below:

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Methods of preparation
Natural sources are oil, gas, coal etc.
Synthetic methods:
1. Oxosynthesis (the Fisher-Tropsh method):
• the catalytic hydrogenation of carbon (ІІ) oxide:

2. Catalytic hydrogenation of alkenes and alkynes:

3. Interaction of alkyl halides with metallic sodium (the Wurtz reaction):

4. Fusion of carboxylic acid salts with alkalis:

5. Hydrolysis of organometallic compounds

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Chemical properties

Alkanes are inert, low-active compounds.

What is the main reason of their inertness?

• alkane molecules consist of only single C–C and C–H bonds.
• each carbon atom is sp3-hybridized; four sp3-hybridized AO’s form four -bonds:
- C–C bond length in alkanes is 0.154 nm;
- bond angle is about 109o 28’.

Free-radical substitution (SR) reactions are characteristic to alkanes.

Besides, an oxidation and a cracking are also characteristic to them.
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Free-radical substitution reactions SR.
1.Halogenation.
• alkanes react with halogens with the formation of alkyl mono- and polyhalides;
• the reaction proceeds through the free-radical mechanism (SR) and has chain character:

The reaction involves three steps:

- initiation
- propagation
- termination

Initiation. The molecule of a halogen undergoes homolytic cleavage:

Propagation. Chlorine free radical attacks the С–Н bond in molecule of СН4, with the
formation of free methyl radical ∙CH3:

Free methyl radical attacks chlorine molecule and forms chloromethane CH3Cl and
chlorine free radical :

Termination. Occurs as a result of recombination (dimerization) of free radicals:

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2. Nitration
• is carried out by diluted (d.) nitric acid under heating and pressure:

• the reaction proceeds through the free-radical mechanism (SR):

3. Sulphochlorination
• under the action of sulphur (IV) oxide and chlorine under UV-irradiation alkanes form
alkanesulphonyl chlorides (R-SO2Cl):

• the reaction proceeds through the free-radical mechanism (SR):

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Oxidation.
Alkanes burn in the presence of oxygen:

Cracking of alkanes.
• is a process of their decomposition;
• it can be:
- thermal – t>8000C;
- catalytic – t=450-5500C in the presence of Al2O3, SiO2
Higher alkanes form a mixture of alkanes and alkenes under conditions of thermal
cracking:

Methane forms acetylene under the temperature of 1400-1500oC.

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 CYCLOALKANES
• are alicyclic hydrocarbons in which carbon atoms that form a cycle, are in sp3-
hybridization.
Classification.
Depending on the number of cycles in a molecule there are:
• monocyclic – 1 cycle;
• di(bi)cyclic – 2 cycles;
• polycyclic – more than 2 cycles.
Monocyclic cycloalkanes are subdivided into four groups:
- cycloalkanes with small cycles (three- and four-membered);
- cycloalkanes with normal cycles (five-, six- and seven-membered);
- cycloalkanes with middle cycles (from eight- to eleven-membered);
- macrocycles (twelve-membered and more).

Nomenclature
Names of monocyclic cycloalkanes are formed according to IUPAC rules by adding the
prefix cyclo- to the name of the alkane with the corresponding quantity of carbon atoms.

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Methods of preparation.
Natural sources
• cyclopropane, cyclohexane and their homologues can be isolated from oil.

Synthetic methods of preparation.

1.Interaction of a,-alkyl dihalides with sodium metallic or zinc
• intramolecular variant of the Wurtz reaction; allows to obtain three-, four- and five-
membered cycloalkanes:

2. Pyrolysis of calcium, barium or thorium salts of dicarboxylic acids.

• the pyrolysis (pyrogenic distillation) of dicarboxylic acid salts gives cyclic ketones
which are reduced to corresponding cycloalkanes then:

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Chemical properties of cycloalkenes.
• as for alkanes, free-radical substitution reactions (SR) are characteristic.

Cycloalkanes with small rings have specific chemical properties. Cyclopropane and
cyclobutane are unstable and undergo ring-opening addition reactions:
1. Hydrogenation:

2. Halogenation

3. Hydrohalogenation
• addition obeys Markovnikov’s rule:

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