John McMurry, Professor Emeritus

3.3 • Alkyl Groups

If you imagine removing a hydrogen atom from an alkane, the partial structure that remains is called an alkyl group. Alkyl groups are not stable compounds themselves, they are simply parts of larger compounds and are named by replacing the -ane ending of the parent alkane with an -yl ending. For example, removal of a hydrogen from methane, CH₄, generates a methyl group, –CH₃, and removal of a hydrogen from ethane, CH₃CH₃, generates an ethyl group, –CH₂CH₃. Similarly, removal of a hydrogen atom from the end carbon of any straight-chain alkane gives the series of straight-chain alkyl groups shown in Table 3.4. Combining an alkyl group with any of the functional groups listed earlier makes it possible to generate and name many thousands of compounds. For example:

The molecular structures and ball and stick models of methane, a methyl group, methyl alcohol, and methylamine. Grey, black, blue, and red spheres represent hydrogen, carbon, nitrogen, and oxygen, respectively.

Table 3.4 Some Straight-Chain Alkyl Groups

Alkane	Name	Alkyl group	Name (abbreviation)
CH₄	Methane	–CH₃	Methyl (Me)
CH₃CH₃	Ethane	–CH₂CH₃	Ethyl (Et)
CH₃CH₂CH₃	Propane	–CH₂CH₂CH₃	Propyl (Pr)
CH₃CH₂CH₂CH₃	Butane	–CH₂CH₂CH₂CH₃	Butyl (Bu)
CH₃CH₂CH₂CH₂CH₃	Pentane	–CH₂CH₂CH₂CH₂CH₃	Pentyl, or amyl

Just as straight-chain alkyl groups are generated by removing a hydrogen from an end carbon, branched alkyl groups are generated by removing a hydrogen atom from an internal carbon. Two 3-carbon alkyl groups and four 4-carbon alkyl groups are possible (Figure 3.4).

The molecular structures and ball and stick models of propane, propyl, isopropyl, butane, butyl, sec-butyl, isobutane, isobutyl, and tert-butyl. Black and grey spheres represent carbon and hydrogen, respectively.

Figure 3.4 Alkyl groups generated from straight-chain alkanes.

One further comment about naming alkyl groups: the prefixes sec- (for secondary) and tert- (for tertiary) used for the C₄ alkyl groups in Figure 3.4 refer to the number of other carbon atoms attached to the branching carbon atom. There are four possibilities: primary (1°), secondary (2°), tertiary (3°), and quaternary (4°).

The general structure of primary, secondary, tertiary, and quaternary carbons which are bonded to one, two, three, and four other carbons, respectively.

The symbol R is used here and throughout organic chemistry to represent a generalized organic group. The R group can be methyl, ethyl, propyl, or any of a multitude of others. You might think of R as representing the Rest of the molecule, which isn’t specified.

The terms primary, secondary, tertiary, and quaternary are routinely used in organic chemistry, and their meanings need to become second nature. For example, if we were to say, “Citric acid is a tertiary alcohol,” we would mean that it has an alcohol functional group (–OH) bonded to a carbon atom that is itself bonded to three other carbons.

The molecular structures of the general class of tertiary alcohols and citric acid (specific tertiary alcohol) are shown.

In addition to speaking of carbon atoms as being primary, secondary, or tertiary, we speak of hydrogens in the same way. Primary hydrogen atoms are attached to primary carbons (RCH₃), secondary hydrogens are attached to secondary carbons (R₂CH₂), and tertiary hydrogens are attached to tertiary carbons (R₃CH). There is, however, no such thing as a quaternary hydrogen. (Why not?)