Nomenclature of Alkanes, Alkyl, and Alkyl halides

Monday, July 28, 2014

3:41 PM

IUPAC Substitutive Nomenclature of Alkanes and Alkyl Halides

The names for several of the unbranched alkanes are listed in Table 4.3.

A. Nomenclature of Unbranched Alkyl Groups

Alkyl groups
 one H atom is removed from an alkane
 Names end in -yl

Ex. 1. CH3CH2CH2CH2CH2CH2CH2
2. CH3CH2CH2CH2CH2CH2

A. Nomenclature of Branched-chain Alkyl Groups

A name may have as many as four features: locants, prefixes, parent compound, and suffixes

Locant - tells the location of attachment of a substituent to the parent compound

Prefix - words added at the beginning, usually name of substituents
Parent - the longest carbon chain
Suffix - group of letters that is added to the end of the parent name to change its meaning

 In general, numbering of the chain always begins at the end nearer the group named a suffix.

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1. Determine the parent name of the alkane -- the longest continuous carbon chain & with the greater number of substituent

Example:

2. Number the longest chain beginning with the end of the chain nearer the substituent

Example:

2.1 When branching occurs at an equal distance from either end of the longest chain, choose the numbering that gives the lower number at
the first point of difference or the sum of set of locants must be the lowest possible number

1 3 5
and NOT 2 4 6

Example:

2.2. When two different numbering schemes give equivalent sets of locants, choose the direction that gives the lower locant t o the group that appears first
in the name

Example:

3. Designate the location of the substituent using the rule 2 (locant-substituentparent)

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 Example:

4. When two or more substituent are present, give each substituent a number corresponding to its location on the longest chain

4.1. Substituents should be listed alphabetically.

4.2. In deciding on alphabetical order, disregard the multiplying prefixes such as "di" and "tri"

Example:

5. When two substituent are present on the same carbon atom, use the number twice:

6. Indicate the two or more identical substituent by prefixes di-, tri-, tetra-, and so on. Commas are used to separate numbers from each other.

B. Nomenclature of Branched alkyl Groups

Carbon atoms are classified according to their degree of substitution by other carbon atoms:

 A primary (1 ) carbon is directly attached to one other carbon. H

C C Atom other than carbon

H
A secondary (2 )carbon is directly attached to two other carbon atoms.

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  A secondary (2 )carbon is directly attached to two other carbon atoms. C

C C Atom other than carbon

H
 A tertiary (3 )carbon is directly attached to three other carbon atoms. C

C C Atom other than carbon

C
 A quaternary (4 )carbon is directly attached to four other carbon atoms C

C C C

 Systemic nomenclature for alkyl groups is similar to that for branched-chain alkanes, with the provision that numbering always begins at the point
where the group is attached to the main chain

Three-Carbon Groups : Isopropyl (common name); 1-methylethyl (systematic name)

Four-Carbon Groups:

isobutyl = 2-methylpropyl
sec-Butyl = 1-Methylpropyl
tert-butyl = 1,1-dimethylethyl

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 Five-Carbon Group:

NOTE: Though structure-defining prefixes (i.e., iso, sec-, & tert-) are approved by IUPAC for the unsubstituted groups, however the one written in italics
and separated from the name by a hyphen (i.e., sec- & tert-) should be disregarded in deciding on alphabetical order except when they are compared
with each other

Examples:

C. Classification of Hydrogen Atoms

 The hydrogen atoms of an alkane are classified on the basis of the carbon atom to which they are attached
 A hydrogen atom attached to a primary carbon is a primary hydrogen atom

D. Nomenclature of Alkyl Halides

Haloalkanes - IUPAC substitutive system

 When the parent chain has both halo and an alkyl substituent attached to it, number the chain from the end nearer the first substituent,
regardless of whether it is halo or alkyl.

Example:

Cl

 If two substituent are at equal distance from the end of the chain, then number the chain from the end nearer the substituent that has
alphabetical precedence:
Example:

Cl

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 Alkyl Halides - IUPAC functional class nomenclature (common nomenclature system)

The chemistry of Petroleum Refining

The primary source of alkanes is petroleum. A petroleum refinery.

The tall towers are
 Petroleum is a complex mixture of organic compounds, most of which are fractioning columns
alkanes and aromatic hydrocarbons. It also contains small amounts of used to separate
oxygen-, nitrogen-, and sulfur-containing compounds. components of crude
oil according to their
The first step in refining petroleum is distillation; the object here is to separate boiling points.
the petroleum into fractions based on the volatility of its components.

Cracking - is a process of converting a mixture of alkanes from the gas oil fraction
(C12 and higher) to smaller, more highly branched hydrocarbons containing 5-10
carbon atoms.

1. Catalytic cracking - employs vey high temperature (~500 ) in the presence

of variety of catalysts
2. Thermal cracking - employs vey high temperature (~500 ) but without
catalyst

Octane Rating

 The highly branched compound 2,2,4-trimethylpentane (called isooctane in the petroleum industry) burns very smoothly (without knocking) in internal
combustion engines and is used as one of the standards by which the octane rating of gasolines is established

 According to this scale, 2,2,4-trimethylpentane has an octane rating of 100.

 Heptane, CH3(CH2)5CH3, a compound that produces much knocking when it is burned in an internal combustion engine, is given an octane rating of 0.

Mixtures of 2,2,4-trimethylpentane and heptane are used as standards for octane ratings between 0 and 100:

Example: Gasoline that has the same characteristics in an engine is a mixture of 87% 2,2,4 -trimethylpentane and 13% heptane
would be rated as 87-octane gasoline.

Reference:
1. Solomons T. W.G. and Fryhle C. B. (2011). Organic Chemistry (10th ed.) USA: John Wiley & Sons, pp 137-146, and 154-156.
2. Carey, F. A (2006). Organic Chemistry (6th ed.) NY, USA: McGraw Hill, pp 76-82, 85-88, and 100.

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