CHEMISTRY 226

SPIN-SPIN SPLITTING

1. Splitting in saturated acyclic molecules or groups: the (n + 1) rule

a. The number of lines in a multiplet = [number of hydrogens on adjacent carbons + 1]
b. Mnemonic for the relative intensities of lines within a multiplet (Pascal's triangle)
# of Hydrogens
on adjacent carbons Multiplicity Rel. intensities
0 singlet (s) 1
1 doublet (d) 1:1
2 triplet (t) 1:2:1
3 quartet (q) 1:3:3:1
4 quintet 1:4:6:4:1
5 sextet 1 : 5 : 10 : 10 : 5 : 1

2. The (n + 1) rule exemplified:

2-Bromopropane shows a six
hydrogen doublet for the two
equivalent methyl groups with GRAPHIC N/A
a single adjacent hydrogen
and a one hydrogen septet for
the hydrogen on the central
carbon with six nearest
neighbors.

3. Splitting patterns for some common alkyl groups

CH2CH3 CH(CH3)2 CH2CH2CH3

2H 3H 1H 6H 2H 2H 3H

• Pattern is most recognizable when ∆δ is large relative to J (the coupling constant).

• The separation between any two lines in a multiplet (the coupling constant) is identical.
• The relative intensities within a multiplet are given by the table above.
4. General rules of spin-spin splitting.
a. There is coupling between nonequivalent hydrogens on the same or adjacent carbons .
b. Each hydrogen splits the signal of a hydrogen to which it is coupled into two lines.
c. Specific cases
• Saturated acyclic molecule or group: the (n + 1) rule holds.
• Unsaturated acyclic unit: hydrogens on the same carbon may be nonequivalent. In
such cases coupling between structurally unique hydrogens must be considered and can
be reproduced by a tree diagram. See the example of vinyl acetate below.

GRAPHIC N/A

• Cyclic molecules or groups: hydrogens on the same carbon are often in nonequivalent
environments and are, therefore, coupled.
• Methylene hydrogens which are adjacent to a stereogenic carbon are not equivalent
(they are diastereotopic) and are coupled.
e. Hydrogens separated by a carbon atom are generally not coupled.

5. The tree diagram for Ha of vinyl acetate:

The signal for Ha is split successively by Hc and Hb with different coupling constants. The total
signal intensity for the four lines corresponds to one hydrogen. The result is a doublet of doublets.

O signal for Ha
CH3 C O Ha

C C Jab = 2 Hz Jac
split by Hc
Hc Hb
split by Hb
Jac = 16 Hz Jab